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Talkbacks State plans survey on prostitution
his daughter in law, Tamar. When she conceived, she was going to be stoned to death until she produced the signet ring Judah gave her until he could pay her. She was allowed to live.
King David handled the harlotry of two of his concubines who had sex with one of his sons, differently. He locked the two women into a building and provided them with food and water. They lived there alone the rest of their lives in judgment of the defilement, so they must have been willing participants bracelet alhambra van cleef copy like harlots on the street who have sex for money.
Empress Theodora, wife of Roman Emperor Justinian, handled prostitution similarly. She established convents where prostitutes were forced to live and be locked in without sex. Since the malady was considered to be incurable, the detention was for life.
The Prophet Isaiah says Jerusalem will be attacked by enemies in the last years of the Gentile world rule era because of women with wanton eyes, the flaunting of sodomy, and cheating the poor. Prostitution in God's Holy City and Mountains of Jerusalem is an abomination and should not be legalized there.
If prostitution is legalized since the Patriarch Judah was himself a willing participant in sex with what he supposed was a harlot, it should be in an area where there are no families or residences or businesses, like a ranch in the desert, apart from the cities that would lose divine protection for legalizing the defilement of women's bodies that to the Lord should be sacred.
Moses executed harlots AND those who visited them. Adultery and fornication were remedied with the deaths of the participants unless the women cried out and was not saved by others.
There needs to be a re education of people in schools and adult education on the sanctity of the reproductive body parts. Tom Van Asperen has an excellent study program (notebook) on how the reproductive parts of the male and female correspond to objects in the Temple of the Lord. The cost used to be about $50. and includes an anatomy book and a workbook.
In fake van cleef gold bracelet dire, financial straits, a young lady decided to peddle herself on some street corner. When a prospective customer asked for prices, she informed him that it was $5 to look and touch, but $25 to go all the way. When customer indicated to have only $5 to his name, she invited him to her room where she intended to relieve him of his $5. When she got rather fidgety 5 minutes into the process and customer asked for the reason of her odd behavior, she informed him that "Honey, I do believe I'm gonna have to lend you $20."
In Germany the legalization was in the end even supported by the Greens (which are close to the women rights movement) because it obviously betters the situation of the women involved (they can get health care, can call the police for support etc. as their activities are no longer illegal).
Furthermore the women are (and shall be) encouraged by specialized social workers to leave prostitution by finding another job and appartment, solving the debt problems of prostitutes etc.
As prostitution exists in every country (even in Iran as "temporary marriage"), it can be "forbidden" but won't disappear.
During the "prohibition" in the US alcohol was banned but that didn't end the desire of hard working Americans for a glass of Whisky in the evening.
All what happened was that by smuggling some people became extremely rich.
Again, blind dedication to a principle is cancerous.
The goal of completely 100% eliminating all prostitution is not possible in the real world. Therefore this is an irrational objective.
Irrational objectives always lead to irrational methods. Most often supported by appeals for support on an emotional and/or idealistic basis.
There is nothing wrong with having visions of Utopia, as long as we acknowledge Utopia is not a constructive objective.
I say spend more time and effort just moving in a productive direction with realistic goals.
The question really boils down to whether or not humans are capable of moderation.
Arguments, for and against legalization, will always exist. And no society will ever reach a concensus on that basis. While expensive debate continues, those who exchange van cleef and arpels bracelet alhambra replica sex for money, continue to be victimized. That truth is really the only practical argument. Sex workers, practicing legally receive health care, protection, education and support services. Sex workers practicing illegally are frequently slaves, forced to indure unsafe activities, and have no recourse when victimized. Since the practice of prostitution is never completely eradicated, and when efforts made to cause it so force those invilved to hide further, the money is always wasted. It costs less to legalize prostitution, tax it, and remove as much of the criminal element as possible.
his daughter in law, Tamar. When she conceived, she was going to be stoned to death until she produced the signet ring Judah gave her until he could pay her. She was allowed to live.
King David handled the harlotry of two of his concubines who had sex with one of his sons, differently. He locked the two women into a building and provided them with food and water. They lived there alone the rest of their lives in judgment of the defilement, so they must have been willing participants bracelet alhambra van cleef copy like harlots on the street who have sex for money.
Empress Theodora, wife of Roman Emperor Justinian, handled prostitution similarly. She established convents where prostitutes were forced to live and be locked in without sex. Since the malady was considered to be incurable, the detention was for life.
The Prophet Isaiah says Jerusalem will be attacked by enemies in the last years of the Gentile world rule era because of women with wanton eyes, the flaunting of sodomy, and cheating the poor. Prostitution in God's Holy City and Mountains of Jerusalem is an abomination and should not be legalized there.
If prostitution is legalized since the Patriarch Judah was himself a willing participant in sex with what he supposed was a harlot, it should be in an area where there are no families or residences or businesses, like a ranch in the desert, apart from the cities that would lose divine protection for legalizing the defilement of women's bodies that to the Lord should be sacred.
Moses executed harlots AND those who visited them. Adultery and fornication were remedied with the deaths of the participants unless the women cried out and was not saved by others.
There needs to be a re education of people in schools and adult education on the sanctity of the reproductive body parts. Tom Van Asperen has an excellent study program (notebook) on how the reproductive parts of the male and female correspond to objects in the Temple of the Lord. The cost used to be about $50. and includes an anatomy book and a workbook.
In fake van cleef gold bracelet dire, financial straits, a young lady decided to peddle herself on some street corner. When a prospective customer asked for prices, she informed him that it was $5 to look and touch, but $25 to go all the way. When customer indicated to have only $5 to his name, she invited him to her room where she intended to relieve him of his $5. When she got rather fidgety 5 minutes into the process and customer asked for the reason of her odd behavior, she informed him that "Honey, I do believe I'm gonna have to lend you $20."
In Germany the legalization was in the end even supported by the Greens (which are close to the women rights movement) because it obviously betters the situation of the women involved (they can get health care, can call the police for support etc. as their activities are no longer illegal).
Furthermore the women are (and shall be) encouraged by specialized social workers to leave prostitution by finding another job and appartment, solving the debt problems of prostitutes etc.
As prostitution exists in every country (even in Iran as "temporary marriage"), it can be "forbidden" but won't disappear.
During the "prohibition" in the US alcohol was banned but that didn't end the desire of hard working Americans for a glass of Whisky in the evening.
All what happened was that by smuggling some people became extremely rich.
Again, blind dedication to a principle is cancerous.
The goal of completely 100% eliminating all prostitution is not possible in the real world. Therefore this is an irrational objective.
Irrational objectives always lead to irrational methods. Most often supported by appeals for support on an emotional and/or idealistic basis.
There is nothing wrong with having visions of Utopia, as long as we acknowledge Utopia is not a constructive objective.
I say spend more time and effort just moving in a productive direction with realistic goals.
The question really boils down to whether or not humans are capable of moderation.
Arguments, for and against legalization, will always exist. And no society will ever reach a concensus on that basis. While expensive debate continues, those who exchange van cleef and arpels bracelet alhambra replica sex for money, continue to be victimized. That truth is really the only practical argument. Sex workers, practicing legally receive health care, protection, education and support services. Sex workers practicing illegally are frequently slaves, forced to indure unsafe activities, and have no recourse when victimized. Since the practice of prostitution is never completely eradicated, and when efforts made to cause it so force those invilved to hide further, the money is always wasted. It costs less to legalize prostitution, tax it, and remove as much of the criminal element as possible.
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Scholen universiteiten universiteiten Nederlands
Universiteit van Auckland is de grootste universiteit op dit moment. Studeren ruim 38000 studenten hier heeft het een hoofdcampus in het hart van Auckland. Deze universiteit biedt verschillende soorten cursussen zoals onderwijs, kunst, wetenschap, techniek, bio ingenieur, bedrijfskunde, gezondheid en wetenschap. Volgens de populaire ratingbureau, heeft de Universiteit van Auckland verdiend de bovenpositie tussen's werelds beste universiteiten een bachelor degree van cleef and arpels bracelet alhambra replica duurt drie jaar en voor eer n meer jaar toegevoegd.
Nieuw Zeeland biedt de perfecte locatie voor studenten uit meer dan 90 verschillende landen te wonen deze superieure Universiteit. Gelegen in de hoofdstad van Nieuw Zeeland, studenten hier genieten van alhambra bracelet van cleef knock off het drukke stedelijke levensstijl, hoewel een mooie haven en parken in de buurt.
Victoria Universiteit van Wellington
Onderwijs is kritisch voor de algehele ontwikkeling van een kind; Het omvat de ontwikkeling van de geest, lichaam en geest. Er zijn verschillende openbare en particuliere scholen geschikt voor uw kind in hedendaagse educatieve ecosysteem. Openbare scholen, vanwege hun traditionele onderwijsmethoden, gebrek aan individuele aandacht en gespecialiseerde studieprogramma's niet toestaan dat uw kind de aandacht die ze nodig hebben te krijgen. Ouders zijn interesse in de particulier onderwijs voor hun kinderen als privscholen een groot werk doen bij de voorbereiding van studenten voor hun levenslange liefde voor het leren.
Vandaag, leven we in een geglobaliseerde bedrijfsscenario om het verplicht te stellen voor de juiste aanpak en natuurlijk getalenteerde professionals. Dit is waar instellingen zoals symbiose Institute of International Business komen in beeld. Aanbod gespecialiseerde management programma's op het gebied van International Business, Agribusiness en energie milieu, SIIB heeft alhambra bracelet van cleef replica geholpen duizenden studenten hun droom van de bouw van corporate loopbaan.
Universiteit van Auckland is de grootste universiteit op dit moment. Studeren ruim 38000 studenten hier heeft het een hoofdcampus in het hart van Auckland. Deze universiteit biedt verschillende soorten cursussen zoals onderwijs, kunst, wetenschap, techniek, bio ingenieur, bedrijfskunde, gezondheid en wetenschap. Volgens de populaire ratingbureau, heeft de Universiteit van Auckland verdiend de bovenpositie tussen's werelds beste universiteiten een bachelor degree van cleef and arpels bracelet alhambra replica duurt drie jaar en voor eer n meer jaar toegevoegd.
Nieuw Zeeland biedt de perfecte locatie voor studenten uit meer dan 90 verschillende landen te wonen deze superieure Universiteit. Gelegen in de hoofdstad van Nieuw Zeeland, studenten hier genieten van alhambra bracelet van cleef knock off het drukke stedelijke levensstijl, hoewel een mooie haven en parken in de buurt.
Victoria Universiteit van Wellington
Onderwijs is kritisch voor de algehele ontwikkeling van een kind; Het omvat de ontwikkeling van de geest, lichaam en geest. Er zijn verschillende openbare en particuliere scholen geschikt voor uw kind in hedendaagse educatieve ecosysteem. Openbare scholen, vanwege hun traditionele onderwijsmethoden, gebrek aan individuele aandacht en gespecialiseerde studieprogramma's niet toestaan dat uw kind de aandacht die ze nodig hebben te krijgen. Ouders zijn interesse in de particulier onderwijs voor hun kinderen als privscholen een groot werk doen bij de voorbereiding van studenten voor hun levenslange liefde voor het leren.
Vandaag, leven we in een geglobaliseerde bedrijfsscenario om het verplicht te stellen voor de juiste aanpak en natuurlijk getalenteerde professionals. Dit is waar instellingen zoals symbiose Institute of International Business komen in beeld. Aanbod gespecialiseerde management programma's op het gebied van International Business, Agribusiness en energie milieu, SIIB heeft alhambra bracelet van cleef replica geholpen duizenden studenten hun droom van de bouw van corporate loopbaan.
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Standard Height for Water Drain Lines in a Bathroom Vanity
During construction, plumbers install a home's basic plumbing system before fixtures are installed in a process called the plumbing rough in. During the rough in, plumbers install the home's drain and waste lines, the pipes that will deliver used water to the sewer or septic tank, and the supply lines, the pipes that will deliver fresh water to the home from the water supply. knock off van cleef arpel ring After the lines are roughed in, they're capped to await the installation of fixtures.
Because the rough in is usually completed well before fixtures are installed, or perhaps even selected, the roughed in lines are usually not installed with regard to the requirements of a particular fixture.
There are no universal standards for the height of drain lines and water supply lines in bathrooms, but most plumbers install the lines within a common range of knock off van cleef between the finger ring heights to make them compatible with most fixtures.
Sink drain lines are typically between 18 and 20 inches above the finished floor. Water supply lines are usually just a couple of inches higher, between 20 and 22 inches from the floor, and installed one to each side of the drain line. These heights are compatible with most common vanity sinks.
The precise height of the drain and supply lines is usually not a concern during the installation of a vanity sink because the installation process allows for some variation in the position of the lines.
The drain line connects to the sink via a P trap, a curved piece that prevents sewer gas from entering the bathroom, and a tailpiece, a straight piece that extends from the sink drain to the trap. In most cases, a standard tailpiece is the right length to reach from the sink to the trap, but in the case of a high drain line or an unusually low sink, the tailpiece can be cut to fit. In the case of a low drain line or high sink, an extra long tailpiece will usually make up the difference.
Roughed in water supply lines connect to the sink's faucet with flexible supply line connectors. These connectors are typically made from flexible plastic, vinyl or stainless steel, and they're available in a range of lengths. Because they're flexible, they can accommodate supply lines of varying heights.
A problem may arise if the drain line is extremely high or the sink is extremely low so that, after the sink is installed, the sink's drain is lower than the drain line. In this case, the sink will not drain properly because the wastewater from the sink would have to flow uphill.
In some cases, such as with pedestal sinks, the construction of the sink may limit the flexibility of drain or supply line connections. With most vanity sinks, however, the open space under the vanity allows plenty of room for adjustment.
In cases where the drain line emerges from the floor rather than the wall, it may be difficult to install the sink without using an S shaped trap, a solution that is prohibited by most building codes. In this van cleef and arpels engagement ring knock off case, you should consult a plumber to sort out your options.
In extreme cases, the drain line may need to be moved to make the installation work, and that requires the services of a plumber.
What Is the Standard Height of a Bathroom Vanity?
For decades, standard bathroom vanity height was 30 to 32 inches, but this range may be less common today. Vanity comfort heights.
Recommended Height of a Faucet for Vessel Sink
A vessel sink is a bowl that rests above the vanity surface. The type of vanity you have chosen will dictate the.
DIY Modifying the Height of a Vanity
If you have to hunch over so much when brush your teeth or look closely into the bathroom mirror that it uncomfortable.
How to Build a Vanity Cabinet
Many homeowners save money by learning how to build custom cabinetry. Understanding the steps to complete a project such as a bathroom.
How to Plumb a Bathroom Vanity Sink Drain
After the rough in plumbing stage is complete, you are ready to plumb the vanity fixture drain. Vanity drains, also known as pop up.
How to Rough in Shower Plumbing
Remodeling a bathroom brings it up to date, increases style and adds value to your home. A benefit to doing all the.
Standard Height for Countertops With Vessel Sinks
Vessel sinks combine the old fashioned charm of an independent washbasin with the convenience of modern running water and elimination of wastewater. The.
During construction, plumbers install a home's basic plumbing system before fixtures are installed in a process called the plumbing rough in. During the rough in, plumbers install the home's drain and waste lines, the pipes that will deliver used water to the sewer or septic tank, and the supply lines, the pipes that will deliver fresh water to the home from the water supply. knock off van cleef arpel ring After the lines are roughed in, they're capped to await the installation of fixtures.
Because the rough in is usually completed well before fixtures are installed, or perhaps even selected, the roughed in lines are usually not installed with regard to the requirements of a particular fixture.
There are no universal standards for the height of drain lines and water supply lines in bathrooms, but most plumbers install the lines within a common range of knock off van cleef between the finger ring heights to make them compatible with most fixtures.
Sink drain lines are typically between 18 and 20 inches above the finished floor. Water supply lines are usually just a couple of inches higher, between 20 and 22 inches from the floor, and installed one to each side of the drain line. These heights are compatible with most common vanity sinks.
The precise height of the drain and supply lines is usually not a concern during the installation of a vanity sink because the installation process allows for some variation in the position of the lines.
The drain line connects to the sink via a P trap, a curved piece that prevents sewer gas from entering the bathroom, and a tailpiece, a straight piece that extends from the sink drain to the trap. In most cases, a standard tailpiece is the right length to reach from the sink to the trap, but in the case of a high drain line or an unusually low sink, the tailpiece can be cut to fit. In the case of a low drain line or high sink, an extra long tailpiece will usually make up the difference.
Roughed in water supply lines connect to the sink's faucet with flexible supply line connectors. These connectors are typically made from flexible plastic, vinyl or stainless steel, and they're available in a range of lengths. Because they're flexible, they can accommodate supply lines of varying heights.
A problem may arise if the drain line is extremely high or the sink is extremely low so that, after the sink is installed, the sink's drain is lower than the drain line. In this case, the sink will not drain properly because the wastewater from the sink would have to flow uphill.
In some cases, such as with pedestal sinks, the construction of the sink may limit the flexibility of drain or supply line connections. With most vanity sinks, however, the open space under the vanity allows plenty of room for adjustment.
In cases where the drain line emerges from the floor rather than the wall, it may be difficult to install the sink without using an S shaped trap, a solution that is prohibited by most building codes. In this van cleef and arpels engagement ring knock off case, you should consult a plumber to sort out your options.
In extreme cases, the drain line may need to be moved to make the installation work, and that requires the services of a plumber.
What Is the Standard Height of a Bathroom Vanity?
For decades, standard bathroom vanity height was 30 to 32 inches, but this range may be less common today. Vanity comfort heights.
Recommended Height of a Faucet for Vessel Sink
A vessel sink is a bowl that rests above the vanity surface. The type of vanity you have chosen will dictate the.
DIY Modifying the Height of a Vanity
If you have to hunch over so much when brush your teeth or look closely into the bathroom mirror that it uncomfortable.
How to Build a Vanity Cabinet
Many homeowners save money by learning how to build custom cabinetry. Understanding the steps to complete a project such as a bathroom.
How to Plumb a Bathroom Vanity Sink Drain
After the rough in plumbing stage is complete, you are ready to plumb the vanity fixture drain. Vanity drains, also known as pop up.
How to Rough in Shower Plumbing
Remodeling a bathroom brings it up to date, increases style and adds value to your home. A benefit to doing all the.
Standard Height for Countertops With Vessel Sinks
Vessel sinks combine the old fashioned charm of an independent washbasin with the convenience of modern running water and elimination of wastewater. The.
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So His Class Bought Him A van cleef engagement ring knock off Pair For Christmas
On the first day of school, high school psychology teacher Taylor Kerby complimented a student on his shoes a pair of red Vans. Kerby mentioned he knock off van cleef flower ring wanted a pair, but when the holidays rolled around, his students noticed he still hadn't bought the shoes for himself.
So they pooled their money. And on Dec. 19, they did this:
One of Kerby's students, Dyani Heredia Urias, 17, posted a video of the sweet moment to Twitter, where it received over 145,000 likes and 52,000 knock off van cleef & arpels butterfly ring retweets.
"I was sincerely touched. I had no idea they were planning anything," Kerby, who teaches at Edgewood High School in West Covina, California, told The Huffington Post. "I found out later that they had planned it on a day when a they had a substitute. When I returned the day after the sub had written a scathing report about how talkative and disruptive they had been. In retrospect I'm glad I didn't give anyone a detention."
Heredia Urias told HuffPost that two of her peers, Faye and Olivia, organized everything. Class members pitched in $2 each for the pair of sneakers and presented them to Kerby in the beginning of class.
"This class is insane, in all of the best ways," Kerby told HuffPost. "It's interesting, when I tell someone I'm a teacher, without fail they say something like, 'How do you deal with the kids?'"
On the first day of school, high school psychology teacher Taylor Kerby complimented a student on his shoes a pair of red Vans. Kerby mentioned he knock off van cleef flower ring wanted a pair, but when the holidays rolled around, his students noticed he still hadn't bought the shoes for himself.
So they pooled their money. And on Dec. 19, they did this:
One of Kerby's students, Dyani Heredia Urias, 17, posted a video of the sweet moment to Twitter, where it received over 145,000 likes and 52,000 knock off van cleef & arpels butterfly ring retweets.
"I was sincerely touched. I had no idea they were planning anything," Kerby, who teaches at Edgewood High School in West Covina, California, told The Huffington Post. "I found out later that they had planned it on a day when a they had a substitute. When I returned the day after the sub had written a scathing report about how talkative and disruptive they had been. In retrospect I'm glad I didn't give anyone a detention."
Heredia Urias told HuffPost that two of her peers, Faye and Olivia, organized everything. Class members pitched in $2 each for the pair of sneakers and presented them to Kerby in the beginning of class.
"This class is insane, in all of the best ways," Kerby told HuffPost. "It's interesting, when I tell someone I'm a teacher, without fail they say something like, 'How do you deal with the kids?'"
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South Africa hooker Du Plessis back to face All Blacks
(Reuters) Bismarck du Plessis, the central character in last van cleef necklace clover copy month's controversial test between New Zealand and South Africa, was restored to the Springbok side for Saturday's re match in Johannesburg.
The hooker was one of two changes announced on Wednesday to the starting line up for the Rugby Championship decider at Ellis Park where South Africa must score four tries and win by more than seven points to snatch the title from the world champion All Blacks.
Two weeks before that Du Plessis was sent off against the All Blacks in Auckland after earning a second yellow card, although there was widespread condemnation of the first caution from French referee van cleef and arpels alhambra turquoise necklace replica Romain Ponte for a tackle on flyhalf Dan Carter for which the hooker was later exonerated.
South Africa lost 29 15 but felt they might have made a better contest of it had they not been reduced to 14 men early in the second half.
Englebrecht is struggling with a quad muscle injury but will be given time to prove his fitness, Meyer said in a statement.
"But if he can't make it, Jan (Serfontein) will start with Juan (de Jongh) on the bench."
Kruger's elevation back to the startling line up in the second row opens up a place on the bench for uncapped Franco van der Merwe, likely to get a debut run as a replacement on his home ground.
"Franco's attitude since day one has been fantastic, he's waited patiently and always stayed positive, which is what we as a team knock off mother of pearl van cleef necklace stand for," the coach added.
Team: 15 Zane Kirchner, 14 Willie le Roux, 13 JJ Engelbrecht or Jan Serfontein, 12 Jean de Villiers (captain), 11 Bryan Habana, 10 Morne Steyn, 9 Fourie du Preez; 8 Duane Vermeulen, 7 Willem Alberts, 6 Francois Louw, 5 Juandre Kruger, 4 Eben Etzebeth, 3 Jannie du Plessis, 2 Bismarck du Plessis, 1 Tendai Mtawarira
Replacements: 16 Adriaan Strauss, 17 Gurthro Steenkamp, 18 Coenie Oosthuizen, 19 Franco van der Merwe, 20 Siya Kolisi, 21 Ruan Pienaar, 22 Pat Lambie, 23 Jan Serfontein or Juan de Jongh.
(Reuters) Bismarck du Plessis, the central character in last van cleef necklace clover copy month's controversial test between New Zealand and South Africa, was restored to the Springbok side for Saturday's re match in Johannesburg.
The hooker was one of two changes announced on Wednesday to the starting line up for the Rugby Championship decider at Ellis Park where South Africa must score four tries and win by more than seven points to snatch the title from the world champion All Blacks.
Two weeks before that Du Plessis was sent off against the All Blacks in Auckland after earning a second yellow card, although there was widespread condemnation of the first caution from French referee van cleef and arpels alhambra turquoise necklace replica Romain Ponte for a tackle on flyhalf Dan Carter for which the hooker was later exonerated.
South Africa lost 29 15 but felt they might have made a better contest of it had they not been reduced to 14 men early in the second half.
Englebrecht is struggling with a quad muscle injury but will be given time to prove his fitness, Meyer said in a statement.
"But if he can't make it, Jan (Serfontein) will start with Juan (de Jongh) on the bench."
Kruger's elevation back to the startling line up in the second row opens up a place on the bench for uncapped Franco van der Merwe, likely to get a debut run as a replacement on his home ground.
"Franco's attitude since day one has been fantastic, he's waited patiently and always stayed positive, which is what we as a team knock off mother of pearl van cleef necklace stand for," the coach added.
Team: 15 Zane Kirchner, 14 Willie le Roux, 13 JJ Engelbrecht or Jan Serfontein, 12 Jean de Villiers (captain), 11 Bryan Habana, 10 Morne Steyn, 9 Fourie du Preez; 8 Duane Vermeulen, 7 Willem Alberts, 6 Francois Louw, 5 Juandre Kruger, 4 Eben Etzebeth, 3 Jannie du Plessis, 2 Bismarck du Plessis, 1 Tendai Mtawarira
Replacements: 16 Adriaan Strauss, 17 Gurthro Steenkamp, 18 Coenie Oosthuizen, 19 Franco van der Merwe, 20 Siya Kolisi, 21 Ruan Pienaar, 22 Pat Lambie, 23 Jan Serfontein or Juan de Jongh.
The 7 Most Terrifying Corporate Mascots of All
If this commercial was a horror movie, it would surely feature a friendly, 70 year old farmer who, on seeing this terror descending upon his farm, would let out a blood curdling scream and and take cover behind a bale of hay. But after noticing the Giant's calm, smiling face and gentle demeanor he would foolishly step from behind his makeshift shelter and attempt to make nice with a few stammering "H h hey buddy's" and an ice breaking "Are ya lost?"
All fears would be put to rest when Big Green magically produced a can of Niblets and bent down as if to make a peace offering to the gentle farmer. It's at that point our beloved farmer would be bludgeoned to death with the can of corn and promptly devoured.
We shudder to think where these neighborhood skip fests eventually ended. After earning the trust of neighborhood kids and parents through a series of fun filled group activities, the Candies Man would inevitably start popping up at "other" times.
Like when that one kid with the absentee father and the alcoholic mother happened to be walking home from school alone. Out of the blue, there stands the M Candies Man, smiling with that come hither grin with a half guzzled bottle of scotch in one hand, a bag of M in the other and a cigarette dangling from his lips.
Have we ever seen a more stark portrayal of the family devastated by drug addiction? While Victor Vicious and his tiny Cloverfield like offspring are busy wreaking havoc on defenseless grandma, Sugar Bear is nonchalantly sitting under a tree satiating his demons with a bowl of Crisp, terrifying in his apathy toward the situation, all like "evvvvvvvs maaaannnnn, I'll get to that bitch when I get to her. Quit harshing my mellow."
By the time he gets off his junkie ass and comes to grandma's rescue, the "vitamin stealer" has made a Hurricane Katrina like skeleton of her once proud abode.
Probably settling a drug debt of some sort. But honestly, this is the direction things were headed anyway. It's clear from this commercial that Sugar Bear was spiraling out of control. It wouldn't have been long before he was stealing grandma's shit, including the siding off her house, to support his habit. Once that well ran dry, it's just a matter of time before he's blowing some grizzly bear in the back of a van for an eighth of Crisp and half a grapefruit as part of his less than wholesome breakfast. As troubling as Bobby and his goth eye shadow is .he has nothing on Snap, Crackle Pop.
Notice how they just snapped and made that mushy cereal disappear? That's not a power that's generally limited to cereal. They could've done the same small van cleef necklace imitation to those three equally frightening mushy cereal henchmen. But they didn't. Because they wanted to fuck some shit up.
How do three mini guys who work in the breakfast cereal industry even develop such a propensity for random violence? There's really only one van cleef and arpels white gold alhambra necklace fake explanation. The whole cereal thing is just magic alhambra necklace copy a front; Snap, Crackle Pop are hired killers.
We're not sure why Bobby wanted those mushy dudes killed, but he knew where they would be and he knew who to call to get the job done.
Imagine if you will, that you're a kid who has just recently seen this commercial and you're young enough to actually believe it. You walk in the house one hot summer afternoon and request a snack. Next thing you know, without warning your dad says "Sure, champ!" The he tosses you an orange from across the kitchen. Suddenly, the seconds become hours as that little orange sphere of potential death comes hurling in your direction. Visions of your entire childhood flash before your eyes as you ponder why dear old dad would place you in such a precarious situation, your entire life depending on your ability to catch an orange.
Just as the orange reaches your trembling little hands, it caroms off your left middle finger and falls helplessly to the floor, at which point you turn and run screaming from the kitchen and out into the cold, cruel gaze of the other neighborhood kids who notice that you've just pissed your pants. Those kids then mock you relentlessly about the incident well into your high school years. Good luck coming out of that ordeal without a crippling drinking problem. While not altogether unpleasant tasting, they look like and (presumably) have the consistency of a heaping pile of bird shit wrapped in a corrugated cardboard sleeve. To help improve upon this unsavory image, the marketing forces at Fig Newtons came up with this:
We're not sure if that's what a fig looks like or if the damn things have garlic in them. Anyway, hate it all you want, but this just offers further evidence that the music industry is justified in valuing looks over talent. Sure, this guy may have nailed the oh so difficult choreography and hit every note with pinpoint accuracy, but if the second best auditioner looked even kind of normal, they should have gotten the job.
In this dude's disgusting hands, this looks less like a campy dance designed to get kids fired up about figs and more like a field sobriety test that's gotten completely out of hand.
This early version of Ronald McDonald isn't the most terrifying corporate mascot we've ever seen. It's the most terrifying anything we've ever seen.
If this commercial was a horror movie, it would surely feature a friendly, 70 year old farmer who, on seeing this terror descending upon his farm, would let out a blood curdling scream and and take cover behind a bale of hay. But after noticing the Giant's calm, smiling face and gentle demeanor he would foolishly step from behind his makeshift shelter and attempt to make nice with a few stammering "H h hey buddy's" and an ice breaking "Are ya lost?"
All fears would be put to rest when Big Green magically produced a can of Niblets and bent down as if to make a peace offering to the gentle farmer. It's at that point our beloved farmer would be bludgeoned to death with the can of corn and promptly devoured.
We shudder to think where these neighborhood skip fests eventually ended. After earning the trust of neighborhood kids and parents through a series of fun filled group activities, the Candies Man would inevitably start popping up at "other" times.
Like when that one kid with the absentee father and the alcoholic mother happened to be walking home from school alone. Out of the blue, there stands the M Candies Man, smiling with that come hither grin with a half guzzled bottle of scotch in one hand, a bag of M in the other and a cigarette dangling from his lips.
Have we ever seen a more stark portrayal of the family devastated by drug addiction? While Victor Vicious and his tiny Cloverfield like offspring are busy wreaking havoc on defenseless grandma, Sugar Bear is nonchalantly sitting under a tree satiating his demons with a bowl of Crisp, terrifying in his apathy toward the situation, all like "evvvvvvvs maaaannnnn, I'll get to that bitch when I get to her. Quit harshing my mellow."
By the time he gets off his junkie ass and comes to grandma's rescue, the "vitamin stealer" has made a Hurricane Katrina like skeleton of her once proud abode.
Probably settling a drug debt of some sort. But honestly, this is the direction things were headed anyway. It's clear from this commercial that Sugar Bear was spiraling out of control. It wouldn't have been long before he was stealing grandma's shit, including the siding off her house, to support his habit. Once that well ran dry, it's just a matter of time before he's blowing some grizzly bear in the back of a van for an eighth of Crisp and half a grapefruit as part of his less than wholesome breakfast. As troubling as Bobby and his goth eye shadow is .he has nothing on Snap, Crackle Pop.
Notice how they just snapped and made that mushy cereal disappear? That's not a power that's generally limited to cereal. They could've done the same small van cleef necklace imitation to those three equally frightening mushy cereal henchmen. But they didn't. Because they wanted to fuck some shit up.
How do three mini guys who work in the breakfast cereal industry even develop such a propensity for random violence? There's really only one van cleef and arpels white gold alhambra necklace fake explanation. The whole cereal thing is just magic alhambra necklace copy a front; Snap, Crackle Pop are hired killers.
We're not sure why Bobby wanted those mushy dudes killed, but he knew where they would be and he knew who to call to get the job done.
Imagine if you will, that you're a kid who has just recently seen this commercial and you're young enough to actually believe it. You walk in the house one hot summer afternoon and request a snack. Next thing you know, without warning your dad says "Sure, champ!" The he tosses you an orange from across the kitchen. Suddenly, the seconds become hours as that little orange sphere of potential death comes hurling in your direction. Visions of your entire childhood flash before your eyes as you ponder why dear old dad would place you in such a precarious situation, your entire life depending on your ability to catch an orange.
Just as the orange reaches your trembling little hands, it caroms off your left middle finger and falls helplessly to the floor, at which point you turn and run screaming from the kitchen and out into the cold, cruel gaze of the other neighborhood kids who notice that you've just pissed your pants. Those kids then mock you relentlessly about the incident well into your high school years. Good luck coming out of that ordeal without a crippling drinking problem. While not altogether unpleasant tasting, they look like and (presumably) have the consistency of a heaping pile of bird shit wrapped in a corrugated cardboard sleeve. To help improve upon this unsavory image, the marketing forces at Fig Newtons came up with this:
We're not sure if that's what a fig looks like or if the damn things have garlic in them. Anyway, hate it all you want, but this just offers further evidence that the music industry is justified in valuing looks over talent. Sure, this guy may have nailed the oh so difficult choreography and hit every note with pinpoint accuracy, but if the second best auditioner looked even kind of normal, they should have gotten the job.
In this dude's disgusting hands, this looks less like a campy dance designed to get kids fired up about figs and more like a field sobriety test that's gotten completely out of hand.
This early version of Ronald McDonald isn't the most terrifying corporate mascot we've ever seen. It's the most terrifying anything we've ever seen.
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Scooter Vans
Scooter vans can allow an unoccupied scooter to be loaded into many of the minivans and SUVs. The availability of power application makes it possible to load and unload. There are many individuals needing assistance for going long distances such as shopping or to a picnic. In this case, it is not necessary to be able to lift an occupied scooter into the van. All that is needed is the lift for transport.
In order to accommodate the scooter occupant as the driver, the lift will need to be installed on knock off van ring the driver side sliding door. This places it close enough to the occupant that it is easy transfer from the scooter to the seat or vice versa. If immediate occupancy is not required, scooter vans may have a trailer hitch mounted lift. This locates the scooter outside the van and leaves the interior of the van intact.
When considering the purchase of scooter vans, make sure the model you choose is a viable model for adapting to scooter use. Always check with a specialist in mobility equipment before buying a van. Weight distribution for the equipment can be a problem for some vans. It may require some repositioning of standard framing to meet the need for balance and stability.
A scooter docking station is available for scooter vans. This is an automatic docking system designed to secure the scooter for transport after the occupant has transferred to the van seat. Many aids are available to help in transferring within the van. Handles for grabbing and assisting can be knock off van cleef clover ring placed at van cleef ring price knock off strategic places in the van.
Scooter vans can allow an unoccupied scooter to be loaded into many of the minivans and SUVs. The availability of power application makes it possible to load and unload. There are many individuals needing assistance for going long distances such as shopping or to a picnic. In this case, it is not necessary to be able to lift an occupied scooter into the van. All that is needed is the lift for transport.
In order to accommodate the scooter occupant as the driver, the lift will need to be installed on knock off van ring the driver side sliding door. This places it close enough to the occupant that it is easy transfer from the scooter to the seat or vice versa. If immediate occupancy is not required, scooter vans may have a trailer hitch mounted lift. This locates the scooter outside the van and leaves the interior of the van intact.
When considering the purchase of scooter vans, make sure the model you choose is a viable model for adapting to scooter use. Always check with a specialist in mobility equipment before buying a van. Weight distribution for the equipment can be a problem for some vans. It may require some repositioning of standard framing to meet the need for balance and stability.
A scooter docking station is available for scooter vans. This is an automatic docking system designed to secure the scooter for transport after the occupant has transferred to the van seat. Many aids are available to help in transferring within the van. Handles for grabbing and assisting can be knock off van cleef clover ring placed at van cleef ring price knock off strategic places in the van.
The fear campaign and Social Security
FILE In this Aug. 2, 2010 file photo, President Barack Obama speaks about Iraq and Afghanistan at the Disabled American Veterans national convention in Atlanta. winds up combat operations in Iraq this month, a gap is widening between the militaries of both countries and their political masters over whether American soldiers should stay beyond the 2011 deadline for all of them to withdraw. war without unraveling Iraq's still precarious security. (AP Photo/Charles Dharapak, File)(Credit: AP)President Barack Obama used the anniversary of Social Security to trumpet Democrats support for the popular program and accuse Republicans of trying to destroy it.
The York Times, today:
Social Security turned 75 last week. . . . But the program is under attack, with some Democrats as well as nearly all Republicans joining the assault. Rumor has it that President Obama deficit commission may call for deep benefit cuts, in particular a sharp rise in the retirement age.
It appears that the Democrats intend to try to win the midterm elections by scaring Americans into believeing that a GOP would endanger their Social Security benefits a tactic which Susie Madrak correctly condemns as of the most cynical political moves I seen. reason for that characterization is obvious: as Madrak explains, echoing Krugman: imminent threat to Social Security right now is from the administration and its pet Catfood Commission. Obama speech this weekend focused on the plan to privatize Social Security, but that plan has zero chance of succeeding: because only a handful of Republicans (such as Paul Ryan) it ever since Bush privatization efforts were defeated, and because Obama retains veto power to prevent it even with a GOP this November. true threat to Social Security is Obama Deficit Commission, which has inexcusably been working in total secrecy throughout the year, cooking up its recommendations to be released in December and likely to be voted on by Congress once the elections are nice and over with.
From the start, that Commission was stacked with people from both parties with a long history of advocating for serious cuts in benefits. The Democratic co Chair, Erskine Bowles, worked a decade ago with Newt Gingrich to try to knock off van cleef emerald ring privatize Social Security when he was Clinton Chief of Staff, and in 1998, was hailed by Business Week as America Friend in the House. Obama appointees include David Cote, CEO of the defense contractor giant Honeywell, and several typical corporatist Democrats with histories of explicitly advocating for cutting Social Security with one of them, Alice Rivlin, showing the level of transparency and responsiveness with which the Commission is working). Needless to say, all GOP van ring knock off are also fully on board with Social Security cuts. operatives who are not going to release a proposal which has no chance of being enacted. They well aware of the need to secure Republican votes if it is to pass, and seem intent on securing the approval of GOP Leader John and his caucus for the recommendations they issue. doesn mean they can achieve that. But given that progressive Democrats will never vote for Social Security cuts, the Commissioners are certainly aware of the need for Republican approval to combine with (and the White House) the only way to secure enactment, and will undoubtedly shape their recommendations accordingly.
Whatever one thinks of these plans to cut Social Security benefits, it just appalling to watch the Democrats try to scare the electorate into voting for them on this basis given that it Obama Deficit Commission which, by design, is far and away the most likely threat to cut those benefits. Because that would take some political capital. That would take some guts.
And liberals, according to this White House, ought to be drug tested if we expecting to see that from this White House right now. Stop complaining and be happy for what you have. . . .
I talked at the top of the show tonight with Gail Collins about how one way to motivate your natural base for an election is to make your base afraid of what the other side has to offer. And that is true. That works. That works on both sides. It works for conservatives about liberals and it works for liberals about conservatives.
But one less soul sucking way to motivate your base and to win an election and to keep winning elections and to, frankly, have history look kindly upon you, is to get your base to cheer for you not just to cheer against someone else, but to see you standing up, not just to bad guys with worse ideas than you, but to see you standing up for what is right because you know it is right, because we know you know it right, even though you also know standing up for it is hard.
That is how you regain the enthusiasm of your base. That is how you win the respect of your base. That is how you win the respect of the country. And admit it: that is how you win your own self respect, too.
It hard to overstate how often one encounters exactly this mindset. If you write about Obama program to assassinate American citizens with no due process, or his horrific killings of civilians around the world, or his campaign violating denials of due process, or the , you invariably be met with this objection: should stop talking about these things so much because you helping the GOP win!!! as though everything is just one big, continuous election and the things which the people who actually wield political power do with that power are irrelevant. All that matters is doing and saying whatever is necessary even if you purport to be a commentator or to ensure your party wins. as Jonathan Alter put it last week:
In other words: yourself to the Real Goal saying and doing whatever is necessary to defeat the dastardly Republicans and keep Democrats in power rather than criticizing van cleef & arpels butterfly ring knock off the political officials who . . . . actually hold power, decrees this It the same reason there are so many blogs devoted to doing little else beyond railing against the latest moronic outbursts of Sarah Palin, or right wing talk radio hosts, or obscure GOP even though they possess no control over the Government: because Democratic apparatchiks want to ignore what Democrats are doing with the power they been given and instead are relying upon exactly the fear mongering tactic of distraction which described. As she says, it the same tactic Karl Rove used for years to gin up victories we may not be good but look over there at those awful, scary liberals and it as common as it is effective. fear based polarization perpetually keeps the electorate distracted away from what political leaders and the permanent factions which control the Government actually do.
It certainly true that elections are about comparative choices, and it obviously worthwhile and necessary to understand what the out of power party is and what they would do once in power. it at least equally important I say more important to critique what the party that actually controls the government is doing with that control. The fact that the Democratic electoral strategy depends upon distracting attention away from what they done your base afraid of what the other side has to offer, as Maddow put it speaks volumes about that record. It long been repulsive to watch the Republicans try to win elections by scaring people into believe that it Democrats rather than themselves responsible for the nation fiscal woes, or posing threats to Medicare, or subverting the Constitution, or making the country exactly the same watching Obama and the Democrats try to win the election by scaring people into believing that a GOP would threaten Social Security when the real threat comes from the Commission created by Obama to do exactly that. whatever else is true, our political debates remained mired in little beyond distracting appeals to fear. Uygur was the guest host today for Ed Schultz and questioned the Chair of the DCCC, Rep. Chris Van Hollen, about the Democrats plans for Social Security. for yourself if you think Democrats are prepared to cut Social if/when the Deficit Commission recommends those cuts and the is then required to give those recommendations an up or down vote without any amendments allowed:
FILE In this Aug. 2, 2010 file photo, President Barack Obama speaks about Iraq and Afghanistan at the Disabled American Veterans national convention in Atlanta. winds up combat operations in Iraq this month, a gap is widening between the militaries of both countries and their political masters over whether American soldiers should stay beyond the 2011 deadline for all of them to withdraw. war without unraveling Iraq's still precarious security. (AP Photo/Charles Dharapak, File)(Credit: AP)President Barack Obama used the anniversary of Social Security to trumpet Democrats support for the popular program and accuse Republicans of trying to destroy it.
The York Times, today:
Social Security turned 75 last week. . . . But the program is under attack, with some Democrats as well as nearly all Republicans joining the assault. Rumor has it that President Obama deficit commission may call for deep benefit cuts, in particular a sharp rise in the retirement age.
It appears that the Democrats intend to try to win the midterm elections by scaring Americans into believeing that a GOP would endanger their Social Security benefits a tactic which Susie Madrak correctly condemns as of the most cynical political moves I seen. reason for that characterization is obvious: as Madrak explains, echoing Krugman: imminent threat to Social Security right now is from the administration and its pet Catfood Commission. Obama speech this weekend focused on the plan to privatize Social Security, but that plan has zero chance of succeeding: because only a handful of Republicans (such as Paul Ryan) it ever since Bush privatization efforts were defeated, and because Obama retains veto power to prevent it even with a GOP this November. true threat to Social Security is Obama Deficit Commission, which has inexcusably been working in total secrecy throughout the year, cooking up its recommendations to be released in December and likely to be voted on by Congress once the elections are nice and over with.
From the start, that Commission was stacked with people from both parties with a long history of advocating for serious cuts in benefits. The Democratic co Chair, Erskine Bowles, worked a decade ago with Newt Gingrich to try to knock off van cleef emerald ring privatize Social Security when he was Clinton Chief of Staff, and in 1998, was hailed by Business Week as America Friend in the House. Obama appointees include David Cote, CEO of the defense contractor giant Honeywell, and several typical corporatist Democrats with histories of explicitly advocating for cutting Social Security with one of them, Alice Rivlin, showing the level of transparency and responsiveness with which the Commission is working). Needless to say, all GOP van ring knock off are also fully on board with Social Security cuts. operatives who are not going to release a proposal which has no chance of being enacted. They well aware of the need to secure Republican votes if it is to pass, and seem intent on securing the approval of GOP Leader John and his caucus for the recommendations they issue. doesn mean they can achieve that. But given that progressive Democrats will never vote for Social Security cuts, the Commissioners are certainly aware of the need for Republican approval to combine with (and the White House) the only way to secure enactment, and will undoubtedly shape their recommendations accordingly.
Whatever one thinks of these plans to cut Social Security benefits, it just appalling to watch the Democrats try to scare the electorate into voting for them on this basis given that it Obama Deficit Commission which, by design, is far and away the most likely threat to cut those benefits. Because that would take some political capital. That would take some guts.
And liberals, according to this White House, ought to be drug tested if we expecting to see that from this White House right now. Stop complaining and be happy for what you have. . . .
I talked at the top of the show tonight with Gail Collins about how one way to motivate your natural base for an election is to make your base afraid of what the other side has to offer. And that is true. That works. That works on both sides. It works for conservatives about liberals and it works for liberals about conservatives.
But one less soul sucking way to motivate your base and to win an election and to keep winning elections and to, frankly, have history look kindly upon you, is to get your base to cheer for you not just to cheer against someone else, but to see you standing up, not just to bad guys with worse ideas than you, but to see you standing up for what is right because you know it is right, because we know you know it right, even though you also know standing up for it is hard.
That is how you regain the enthusiasm of your base. That is how you win the respect of your base. That is how you win the respect of the country. And admit it: that is how you win your own self respect, too.
It hard to overstate how often one encounters exactly this mindset. If you write about Obama program to assassinate American citizens with no due process, or his horrific killings of civilians around the world, or his campaign violating denials of due process, or the , you invariably be met with this objection: should stop talking about these things so much because you helping the GOP win!!! as though everything is just one big, continuous election and the things which the people who actually wield political power do with that power are irrelevant. All that matters is doing and saying whatever is necessary even if you purport to be a commentator or to ensure your party wins. as Jonathan Alter put it last week:
In other words: yourself to the Real Goal saying and doing whatever is necessary to defeat the dastardly Republicans and keep Democrats in power rather than criticizing van cleef & arpels butterfly ring knock off the political officials who . . . . actually hold power, decrees this It the same reason there are so many blogs devoted to doing little else beyond railing against the latest moronic outbursts of Sarah Palin, or right wing talk radio hosts, or obscure GOP even though they possess no control over the Government: because Democratic apparatchiks want to ignore what Democrats are doing with the power they been given and instead are relying upon exactly the fear mongering tactic of distraction which described. As she says, it the same tactic Karl Rove used for years to gin up victories we may not be good but look over there at those awful, scary liberals and it as common as it is effective. fear based polarization perpetually keeps the electorate distracted away from what political leaders and the permanent factions which control the Government actually do.
It certainly true that elections are about comparative choices, and it obviously worthwhile and necessary to understand what the out of power party is and what they would do once in power. it at least equally important I say more important to critique what the party that actually controls the government is doing with that control. The fact that the Democratic electoral strategy depends upon distracting attention away from what they done your base afraid of what the other side has to offer, as Maddow put it speaks volumes about that record. It long been repulsive to watch the Republicans try to win elections by scaring people into believe that it Democrats rather than themselves responsible for the nation fiscal woes, or posing threats to Medicare, or subverting the Constitution, or making the country exactly the same watching Obama and the Democrats try to win the election by scaring people into believing that a GOP would threaten Social Security when the real threat comes from the Commission created by Obama to do exactly that. whatever else is true, our political debates remained mired in little beyond distracting appeals to fear. Uygur was the guest host today for Ed Schultz and questioned the Chair of the DCCC, Rep. Chris Van Hollen, about the Democrats plans for Social Security. for yourself if you think Democrats are prepared to cut Social if/when the Deficit Commission recommends those cuts and the is then required to give those recommendations an up or down vote without any amendments allowed:
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step Solution Processing of Ag
AbstractWe report on one step hybridization of silver, gold and palladium nanoparticles from solution onto exfoliated two dimensional (2D) Ti3C2 titanium carbide (MXene) nanosheets. The produced hybrid materials can be used as substrates for surface enhanced Raman spectroscopy (SERS). An approximate analytical approach is also developed for the calculation of the surface plasmon resonance (SPR) frequency of nanoparticles immersed in a medium, near the interface of two dielectric media with different dielectric constants. We obtained a good match with the experimental data for SPR wavelengths, 440nm and 558nm, respectively for silver and gold nanoparticles. In the case of palladium, our calculated SPR wavelength for the planar geometry was 160nm, demonstrating that non spherical palladium nanoparticles coupled with 2D MXene yield a broad, significanlty red shifted SPR band with a peak at 230nm. We propose a possible mechanism of the plasmonic hybridization of nanoparticles with MXene. The as prepared noble metal nanoparticles on MXene show a highly sensitive SERS detection of methylene blue (MB) with calculated enhancement factors on the order of 105. These findings open a pathway for extending visible range SERS applications of novel 2D hybrid materials in sensors, catalysis, and biomedical applications.IntroductionOwing to their physicochemical properties, 2D materials such as graphene, layered metal oxides, sulfides, and nitrides have attracted much attention in SERS1. Graphene has recently been studied the most due to its unique 2D structure, superior mechanical strength, and attractive electronic and optical properties2. The surface plasmon resonances (SPRs) of graphene, however, are found to be in the infrared and THz range, limiting its electromagnetically modified (EM) enhancement in the visible range SERS3. Nevertheless, attempting to get compensation from chemically modified (CM) enhancement, graphene has been hybridized by ex situ and in situ methods with various nanomaterials including polymers, metal oxides and metal nanoparticles (NPs). For this, numerous hydrothermal, wet chemical, electrochemical deposition, and photoreduction methods have been applied4,5,6,7,8,9. This can be useful not only in SERS, but also in biomedical, imaging, and sensing (even at a single molecule level) applications.In order to benefit from both EM and CM enhancements in the visible SERS applications, new 2D material hybrids are necessary. Some members of the MXene family, recently discovered early transition metal 2D carbides/nitrides10,11, are predicted to possess SPRs from infrared to ultraviolet (UV) range. MXenes are composed of layered P63/mmc symmetry hexagonal Mn+1XnTx structures, where M is a transition metal or a combination of such, X is either C and/or N, Tx stands for the functional terminations (such as O, OH and F), and n=1, 2 or 312. The plasmonic properties of MXenes are therefore dependent on the layers' size, number and stacking order, as well as functional terminations13,14,15. To date, layered MXene nanosheets have been proposed for many applications including super capacitors, batteries, hydrogen storage and hybrid devices16,17. Particularly, exfoliated 2D hybrids with nanoparticles and polymers can be used as building blocks for fabricating novel functional hybrid materials18,19. Among them, the most notable is a MXene Cu2O composite for catalytic applications, as well as a MXene poly vinyl alcohol (PVA) composite film, and a sandwich like structure of MXene/carbon nanotube (CNT) paper for application as highly capacitive battery anodes for energy storage20,21,22. The tunability of their chemical and physical properties renders MXenes very promising for hybridization with nanomaterials. Nevertheless, no MXene based plasmonic nanostructures of any kind have been reported so far. On the other hand, hybridizing NPs has exhibited advantageous properties for SERS in the past decade due to their high surface to volume ratio, surface control, and excellent plasmonic properties23,24,25. The single delocalized d electrons as well as surface roughness of NPs can selectively enhance electromagnetic radiation at specific excitation wavelengths. The enhancement factor can be further tuned by NP surface functionalization and grouping9,26. There have been numerous studies on colloidal solutions of NPs hybridized by graphene, 2D metal sulfides, and others27. Yoshimura et al. developed a soft processing (or soft solution processing) method with the aim to fabricate materials of desired shape, size, composition, and structure in solutions within a shorter time frame28,29,30,31. The method has already succeeded in producing large scale functionalized 2D carbon based materials for electrochemical and catalytic applications5,32. In this work, we extend this approach to achieve a one step environmentally benign hybridization of silver, gold and palladium NPs (Ag, Au and Pd) with Ti3C2Tx MXene in an aqueous solution, without an external reducing agent or surfactant, as illustrated in Fig. 1. We suggest a NP growth model and explain the plasmonic hybridization of NPs with MXene. We demonstrate the SERS applicability of the as synthesized materials on methylene blue (MB), a well known dye used as a probe molecule.ResultsFigure 2 shows ultra violet and visible (UV Vis) spectroscopy results on delaminated Ti3C2Tx MXene (0.04mg/mL concentration) and colloidal MXene NP hybrid suspensions derived from it. It can be seen from the photographs (inset of Fig. The broad UV absorption spectrum of the delaminated MXene in dilute aqueous medium exhibits peaks at 225 and 275nm in Fig. 2. This is expected because the surface of MXene was functionalized with different groups after etching out the A element from its precursor ternary transition metal carbide (so called MAX phase) during synthesis, and the flakes were delaminated by dimethyl sulfoxide (DMSO). The MXene colloid also exhibits high absorption in the UV region within the range from 225 to 325nm. This absorption may correspond to the band gap energy of the oxidized MXene, which was also predicted by theoretical calculations16,17. This indicates the presence of NPs (Ag and Au, respectively) in the colloidal solution. The SPR band for Pd NPs is usually observed in ultraviolet region33.To visualize the morphology of the as synthesized NPs on MXene, we performed transmission electron microscopy (TEM) analysis. Moreover, to highlight the constitution of these NPs, we simultaneously performed energy dispersive X ray (EDX) mapping and spectroscopy (EDS) on the same areas as analyzed by TEM. The cross section of layered MXene structure (Fig. 3a) and the distributed NPs (Ag, Au and Pd) on MXene flakes are shown in the TEM micrographs in Fig. 3b d, respectively. The bare MXene sample consists of single and few layer MXene flakes (Fig. 3a) with lateral sizes around 2 3m (Supplementary Fig. S1a). The corresponding high resolution TEM images of MXene indicate thickness from one to few nanometers (Supplementary Fig. S1b). The EDS spectrum and EDX mapping reveal that the delaminated MXene consists of only Ti and C with no Al (Supplementary Fig. S1), suggesting successful etching. From the high resolution TEM micrographs (Supplementary Figs S2 S4), it is clear that the NPs were directly attached to the MXene. The size and shape of the NPs vary for different metals synthesized in this study. The Ag and Au NPs are rounded with sizes varying from 10 70 and 40 50nm, respectively. The size of Ag NPs on MXene is harder to control because the highly reactive Ag+ ions are likely to undergo rapid reduction under the ultrasonication even when using a low precursor concentration (0.1mM AgNO3 solution). Nevertheless, under the same experimental conditions, a more homogenous size distribution of Au NPs (40 50nm in average) was obtained, suggesting a slower reduction of Au3+ ions. S4), suggesting that the reduction step was different from that of the Ag and Au. The distribution and elemental EDX mapping analysis for each MXene NP hybrid confirmed the presence of the synthesized metal nanoparticles on MXene (Supplementary Figs S2 S4).To assess the structure of the metal NPs on the MXene, we performed X ray diffraction (XRD) analysis before (Fig. 4a) and after hybridization of MXene (Fig. 4b d) with Ag, Au, and Pd, as shown in Fig. 4. The XRD patterns of the delaminated MXene have very weak peaks comparable to vca alhambra earrings fake those previously reported12. The disappearance of the non basal peak at 60 (2) suggests the full delamination of MXene and no crystallographic stacking of MXene sheets12. We also found intense peaks corresponding to the (111), (200), (220) and (311) planes of the Au and Ag NPs, which further confirm the successful hybridization. The nm range thickness of the planar NPs hinders the detection of reflected light from planes other than the (111). These observations are consistent with the shape analysis performed by TEM, in Fig. 3.Figure 4The powder X ray diffraction patterns of (a) delaminated MXene nanosheets, and after hybridization with (b) Ag, (c) Au and (d) Pd nanoparticles.The surface chemical bonding of the MXene and MXene hybrids were examined by X ray photoelectron spectroscopy (XPS). The individual core level high resolution XPS deconvolution spectra have been background corrected using the Shirley algorithm prior to curve resolution, presented in Fig. 5.As seen from the high resolution XPS spectra of Ti 2p, the O and C contribution mainly comes from the TiOx and carbon of TiC, respectively. Moreover, the peaks at 454.9eV (sp3) and 461.2eV (sp1) represent a contribution from Ti C bonds, and the peaks at 456.6eV and 462.7eV correspond to Ti O bonds. Figure 5b shows the 3d Ag core level spectrum with doublet peaks of Ag 3d5/2 and 3d3/2 of the two chemically distinguished spin orbit pairs observed at 368.4eV and 374.4eV, respectively. The low binding energy component (at 368.4eV) is a characteristic peak for electron emission from the Ag nanocore. The difference in binding energy (6eV) of this doublet clearly shows evidence of the Ag atoms present in the drop coated film. 5c) shows peaks at 84.7eV and 88.4eV in which the difference in binding energy (3.7eV) indicates a reduced form of Au0, further confirming the presence of Au nanoparticles in the sample. 5d). The back scattered light from planar Pd nanoparticles is, however, screened by the MXene flakes, causing the low signal to noise ratio. We also inspected the XPS deconvolution core level spectra of Ti 2p, C 1s and O 1s of MXene and MXene hybrids. A survey spectrum of MXene revealed the presence of Ti, C and O atoms (Supplementary Fig. S5). The C 1s and O 1s spectra of MXene suggest that after the delamination process, the MXene surface was predominantly functionalized with OH groups, the contributions from graphitized carbon, and carbides (Supplementary Figs S7 and S8, respectively). The functional groups of the delaminated MXene and MXene hybrids were further analyzed by Fourier transmission infrared (FTIR) spectroscopy in the attenuated total reflection (ATR) mode, as displayed in Fig. 6. The IR spectrum of the delaminated MXene has a vibrational mode at 3742cm1, which, due to the absence of atmospheric moisture (the samples were blow dried in N2 flow prior to the measurements), is assigned to the OH functional group out of plane vibrations of MXene. This is verified by first principles calculations of Ti3C2(OH)2 in the Ti3C2 block34. These are assigned to the OH/H2O adsorbed on the NPs surface, since these bands were not observed in the case of delaminated MXene flakes.DiscussionThe hybridization of exfoliated 2D nanosheets is potent not only in tailoring the physicochemical properties of hybridized species, but also in showing catalytic activity in concert with coupling between the 2D materials and NPs. Au NPs were previously deposited on delaminated MXene flakes with sodium borohydrate (NaBH4) as a reducing agent35. Moreover, it was observed that a homogeneous size distribution was achieved without a reducing agent by direct addition of Au salt in dark conditions or by photocatalytic assistance of UV irradiation35. Metal NPs (Pt) were also deposited directly on MXene flakes36. Herein, we propose a general in situ reduction method of noble metal NPs on MXene flakes by direct addition of metal salts in ambient air. Firstly, the effect of sonication on the hybridization of MXene flakes was systematically tested by performing treatments both with and without ultrasonication. The ex situ TEM analysis revealed that a homogeneous deposition of NPs (on individual MXene flakes) and subsequently, highly dispersed MXene hybrids (case of Au) were accomplished by ultrasonication. In the case when ultrasonication was not used, non uniformly deposited NPs on stacked MXene flakes (>4 nanosheets) were observed (Supplementary Fig. S9). Thus, we conclude that the ultrasonic mixing helped to obtain a more uniform NPs distribution on finer dispersed MXene nanosheets. 7, involving Ag DMSO complexes. We note that based on preliminary results of35 another salt reduction process without the DMSO complexes could possibly occur on the MXene flakes, either by or without photocatalytic activation. Nevertheless, we hypothesize hereby a mechanism involving DMSO intercalants attached to the few nm thick delaminated MXene flakes12 serving as reduction/nucleation sites for the NPs37. As metal ions (0.1mM Ag+) are added into the MXene colloidal solution under sonication, the formation of [Ag+ DMSO] complex monomers occurs in the MXene solution (stage 1). The [Ag+ DMSO] complexes cause an immediate color change by forming Ag+ DMSO (monomer) strong surface bonds with the OH functional groups of MXene. Thereafter, a fast electron transfer causes the formation of Ag+ [DMSO] from oxygen's lone pair electron ([S (CH3)2]) (stage 2). In the next step (stage 3), the charge transfer between Ag1 MXene complexes initializes the MXene Ag DMSO dimerization. Since the bond with the OH functional group is stronger, this MXene Ag dimeric complexes then undergo a further reduction and form stable (Ag0)n nano clusters (stage 4). This cluster formation leads to van cleef small earrings fake further nucleation and subsequent growth to form stable Ag NPs on the MXene surface (stage 5). Eventually, this MXene localized surface reduction mechanism yields plasmonic 2D substrates decorated by NPs that are highly dispersed in aqueous solution. The coverage of the NP can be further tuned by chemical manipulation of the OH functional groups on the MXene substrate.Next, to understand the nature of the noble metal NPs plasmon peaks observed by the UV vis spectroscopy, as shown in Fig. 2, we calculated in the limits of quasistatic approximation the SPR frequency of an Ag or Au sphere placed near the interface of two dielectric media with dielectric constants denoted as a and b. The case of Pd is discussed separately. We apply the imaging method38 to reduce the problem of the NP immersed in a medium near the MXene (b) sheet to a problem of two NPs in a homogeneous medium. For solving this reduced problem, we involve the approximate analytical approach developed for two spheres39. We consider a NP of a radius (R) in the range of 5 to 35nm where the developed quasistatic approximation is valid. Considering the charge distribution coefficient of the image NP, , (Supplementary information), we obtain the following relation:where y is the minimal distance between NP and MXene, () is the dielectric function of the NP depending on frequency . Eventually, inserting experimental values of dielectric constants15,40 in equation (1), we obtain a good match with the experimental data for SPR wavelengths, 440nm and 558nm, respectively for Ag and Au, in the case of a reasonable value of y/R0.015. Our calculations (Supplementary information) also show that the SPR linewidths of Fig.As seen from Fig. 3, the case of Pd structures deposited on MXene flakes drastically differs from that of the Ag and Au NPs. According to the TEM analysis results, we model these Pd nanostructures by highly oblate spheroids (disc shaped particles). By using Pd optical constants41 and our calculated value of the effective refractive index (Supplementary information), we obtain a SPR peak in the UV range at 160nm. The more sophisticated planar NP geometry and coupling can indeed yield a more red shifted SPR value, evident in Fig. 2. Nevertheless, when we model Pd NPs by spheres of the same size as those of the Ag and Au NPs, we obtain an SPR of 375nm, which is in accordance with the literature42. The absence of such a peak in Fig. 8a) and after NP hybridization (Fig. 8b d) by soaking the glass deposited samples in a 106M ethanol solution of MB and subsequently drying it. In order to improve the signal to noise ratio of the detected Raman signal, we use a hybridization of NPs with increased particle size and amount by adding a 5 fold raised (0.5mM) concentration of each precursor metal salt during the hybridization process. This could result in a fast reduction of the precursor, causing non uniform and larger size NP coating (possibly aggregated) on the MXene surface. Characteristic Raman peaks of partially oxidized Ti3C2Tx10,16 can be seen in Fig. 8a. The oxidation could have occurred due to reaction with ethanol or MB, or from the high laser power (35mW). Nevertheless, no Raman spectral features of MB can be seen in Fig. 8a even though MB molecules were adsorbed on MXene. This clearly comes from the absence of the NPs on the MXene surface, which are necessary for enhancing the Raman signal of MB. The characteristic peaks of MB around 443 and 1615cm1 which have been assigned to C N C skeletal bending and C C stretching, respectively, are evident in the SERS spectra for the three NP hybrids (with varying intensities), indicating that the molecules were adsorbed onto the substrates43. The SERS characteristic bands for clover diamond earrings fake (C S C) and (C S) at 559cm1 and 1181cm1, respectively, are observed suggesting that the chemisorbed MB molecules were attached to the MXene hybrids surface via sulphur metal bond, enriching C S bond intensities. 8c,d. The produced 2D MXene hybrid substrates are hence expected to exhibit high SERS enhancement. As a reference, 1% of liquid MB (in ethanol) was used to acquire a Raman spectrum for the calculations of the enhancement factors of 2D MXene hybrids samples (Supplementary Fig. S10). This suggests possible SERS applications of the proposed material.Figure 8(a) Raman spectrum of Ti3C2Tx after soaking in MB dispersed in ethanol and subsequent drying.In conclusion, herein we report a strategy for synthesis of noble metal nanoparticle MXene hybrids by one step soft solution processing. Through TEM and simultaneous EDX mapping analysis, we show that a uniform coating of Ag, Au and Pd NPs on MXene nanosheets was accomplished. The plasmonic nature of these novel 2D hybrid nanostructured substrates was demonstrated by surface enhanced Raman scattering (SERS). The advantage of this method is the in situ controlled synthesis approach, as well as the EM and CM combined nature, favorable for the SERS enhancement. Moreover, the simplicity of the solution based approach and the absence of reducing agents and expensive instrumentation allow exploration of other MXene NP hybrids and for applications including optical sensors (colorimetric detection), electrochemistry, catalysis and interface studies.MethodsSynthesis of aqueous MXene nanosheets colloidal solutionThe MXene powder of Ti3C2Tx was prepared by etching with a fluoride salt (LiF in HCl) at 35C for 24h from Ti3AlC2 (MAX phase). The obtained MXene powder was used for the production of colloidal suspension of MXene nanosheets by delamination of powder and subsequent bath sonication (Bransonic M3800 Ultrasonic bath, 110W and Frequency 40kHz). For delamination, 0.3g of MXene powder was mixed
AbstractWe report on one step hybridization of silver, gold and palladium nanoparticles from solution onto exfoliated two dimensional (2D) Ti3C2 titanium carbide (MXene) nanosheets. The produced hybrid materials can be used as substrates for surface enhanced Raman spectroscopy (SERS). An approximate analytical approach is also developed for the calculation of the surface plasmon resonance (SPR) frequency of nanoparticles immersed in a medium, near the interface of two dielectric media with different dielectric constants. We obtained a good match with the experimental data for SPR wavelengths, 440nm and 558nm, respectively for silver and gold nanoparticles. In the case of palladium, our calculated SPR wavelength for the planar geometry was 160nm, demonstrating that non spherical palladium nanoparticles coupled with 2D MXene yield a broad, significanlty red shifted SPR band with a peak at 230nm. We propose a possible mechanism of the plasmonic hybridization of nanoparticles with MXene. The as prepared noble metal nanoparticles on MXene show a highly sensitive SERS detection of methylene blue (MB) with calculated enhancement factors on the order of 105. These findings open a pathway for extending visible range SERS applications of novel 2D hybrid materials in sensors, catalysis, and biomedical applications.IntroductionOwing to their physicochemical properties, 2D materials such as graphene, layered metal oxides, sulfides, and nitrides have attracted much attention in SERS1. Graphene has recently been studied the most due to its unique 2D structure, superior mechanical strength, and attractive electronic and optical properties2. The surface plasmon resonances (SPRs) of graphene, however, are found to be in the infrared and THz range, limiting its electromagnetically modified (EM) enhancement in the visible range SERS3. Nevertheless, attempting to get compensation from chemically modified (CM) enhancement, graphene has been hybridized by ex situ and in situ methods with various nanomaterials including polymers, metal oxides and metal nanoparticles (NPs). For this, numerous hydrothermal, wet chemical, electrochemical deposition, and photoreduction methods have been applied4,5,6,7,8,9. This can be useful not only in SERS, but also in biomedical, imaging, and sensing (even at a single molecule level) applications.In order to benefit from both EM and CM enhancements in the visible SERS applications, new 2D material hybrids are necessary. Some members of the MXene family, recently discovered early transition metal 2D carbides/nitrides10,11, are predicted to possess SPRs from infrared to ultraviolet (UV) range. MXenes are composed of layered P63/mmc symmetry hexagonal Mn+1XnTx structures, where M is a transition metal or a combination of such, X is either C and/or N, Tx stands for the functional terminations (such as O, OH and F), and n=1, 2 or 312. The plasmonic properties of MXenes are therefore dependent on the layers' size, number and stacking order, as well as functional terminations13,14,15. To date, layered MXene nanosheets have been proposed for many applications including super capacitors, batteries, hydrogen storage and hybrid devices16,17. Particularly, exfoliated 2D hybrids with nanoparticles and polymers can be used as building blocks for fabricating novel functional hybrid materials18,19. Among them, the most notable is a MXene Cu2O composite for catalytic applications, as well as a MXene poly vinyl alcohol (PVA) composite film, and a sandwich like structure of MXene/carbon nanotube (CNT) paper for application as highly capacitive battery anodes for energy storage20,21,22. The tunability of their chemical and physical properties renders MXenes very promising for hybridization with nanomaterials. Nevertheless, no MXene based plasmonic nanostructures of any kind have been reported so far. On the other hand, hybridizing NPs has exhibited advantageous properties for SERS in the past decade due to their high surface to volume ratio, surface control, and excellent plasmonic properties23,24,25. The single delocalized d electrons as well as surface roughness of NPs can selectively enhance electromagnetic radiation at specific excitation wavelengths. The enhancement factor can be further tuned by NP surface functionalization and grouping9,26. There have been numerous studies on colloidal solutions of NPs hybridized by graphene, 2D metal sulfides, and others27. Yoshimura et al. developed a soft processing (or soft solution processing) method with the aim to fabricate materials of desired shape, size, composition, and structure in solutions within a shorter time frame28,29,30,31. The method has already succeeded in producing large scale functionalized 2D carbon based materials for electrochemical and catalytic applications5,32. In this work, we extend this approach to achieve a one step environmentally benign hybridization of silver, gold and palladium NPs (Ag, Au and Pd) with Ti3C2Tx MXene in an aqueous solution, without an external reducing agent or surfactant, as illustrated in Fig. 1. We suggest a NP growth model and explain the plasmonic hybridization of NPs with MXene. We demonstrate the SERS applicability of the as synthesized materials on methylene blue (MB), a well known dye used as a probe molecule.ResultsFigure 2 shows ultra violet and visible (UV Vis) spectroscopy results on delaminated Ti3C2Tx MXene (0.04mg/mL concentration) and colloidal MXene NP hybrid suspensions derived from it. It can be seen from the photographs (inset of Fig. The broad UV absorption spectrum of the delaminated MXene in dilute aqueous medium exhibits peaks at 225 and 275nm in Fig. 2. This is expected because the surface of MXene was functionalized with different groups after etching out the A element from its precursor ternary transition metal carbide (so called MAX phase) during synthesis, and the flakes were delaminated by dimethyl sulfoxide (DMSO). The MXene colloid also exhibits high absorption in the UV region within the range from 225 to 325nm. This absorption may correspond to the band gap energy of the oxidized MXene, which was also predicted by theoretical calculations16,17. This indicates the presence of NPs (Ag and Au, respectively) in the colloidal solution. The SPR band for Pd NPs is usually observed in ultraviolet region33.To visualize the morphology of the as synthesized NPs on MXene, we performed transmission electron microscopy (TEM) analysis. Moreover, to highlight the constitution of these NPs, we simultaneously performed energy dispersive X ray (EDX) mapping and spectroscopy (EDS) on the same areas as analyzed by TEM. The cross section of layered MXene structure (Fig. 3a) and the distributed NPs (Ag, Au and Pd) on MXene flakes are shown in the TEM micrographs in Fig. 3b d, respectively. The bare MXene sample consists of single and few layer MXene flakes (Fig. 3a) with lateral sizes around 2 3m (Supplementary Fig. S1a). The corresponding high resolution TEM images of MXene indicate thickness from one to few nanometers (Supplementary Fig. S1b). The EDS spectrum and EDX mapping reveal that the delaminated MXene consists of only Ti and C with no Al (Supplementary Fig. S1), suggesting successful etching. From the high resolution TEM micrographs (Supplementary Figs S2 S4), it is clear that the NPs were directly attached to the MXene. The size and shape of the NPs vary for different metals synthesized in this study. The Ag and Au NPs are rounded with sizes varying from 10 70 and 40 50nm, respectively. The size of Ag NPs on MXene is harder to control because the highly reactive Ag+ ions are likely to undergo rapid reduction under the ultrasonication even when using a low precursor concentration (0.1mM AgNO3 solution). Nevertheless, under the same experimental conditions, a more homogenous size distribution of Au NPs (40 50nm in average) was obtained, suggesting a slower reduction of Au3+ ions. S4), suggesting that the reduction step was different from that of the Ag and Au. The distribution and elemental EDX mapping analysis for each MXene NP hybrid confirmed the presence of the synthesized metal nanoparticles on MXene (Supplementary Figs S2 S4).To assess the structure of the metal NPs on the MXene, we performed X ray diffraction (XRD) analysis before (Fig. 4a) and after hybridization of MXene (Fig. 4b d) with Ag, Au, and Pd, as shown in Fig. 4. The XRD patterns of the delaminated MXene have very weak peaks comparable to vca alhambra earrings fake those previously reported12. The disappearance of the non basal peak at 60 (2) suggests the full delamination of MXene and no crystallographic stacking of MXene sheets12. We also found intense peaks corresponding to the (111), (200), (220) and (311) planes of the Au and Ag NPs, which further confirm the successful hybridization. The nm range thickness of the planar NPs hinders the detection of reflected light from planes other than the (111). These observations are consistent with the shape analysis performed by TEM, in Fig. 3.Figure 4The powder X ray diffraction patterns of (a) delaminated MXene nanosheets, and after hybridization with (b) Ag, (c) Au and (d) Pd nanoparticles.The surface chemical bonding of the MXene and MXene hybrids were examined by X ray photoelectron spectroscopy (XPS). The individual core level high resolution XPS deconvolution spectra have been background corrected using the Shirley algorithm prior to curve resolution, presented in Fig. 5.As seen from the high resolution XPS spectra of Ti 2p, the O and C contribution mainly comes from the TiOx and carbon of TiC, respectively. Moreover, the peaks at 454.9eV (sp3) and 461.2eV (sp1) represent a contribution from Ti C bonds, and the peaks at 456.6eV and 462.7eV correspond to Ti O bonds. Figure 5b shows the 3d Ag core level spectrum with doublet peaks of Ag 3d5/2 and 3d3/2 of the two chemically distinguished spin orbit pairs observed at 368.4eV and 374.4eV, respectively. The low binding energy component (at 368.4eV) is a characteristic peak for electron emission from the Ag nanocore. The difference in binding energy (6eV) of this doublet clearly shows evidence of the Ag atoms present in the drop coated film. 5c) shows peaks at 84.7eV and 88.4eV in which the difference in binding energy (3.7eV) indicates a reduced form of Au0, further confirming the presence of Au nanoparticles in the sample. 5d). The back scattered light from planar Pd nanoparticles is, however, screened by the MXene flakes, causing the low signal to noise ratio. We also inspected the XPS deconvolution core level spectra of Ti 2p, C 1s and O 1s of MXene and MXene hybrids. A survey spectrum of MXene revealed the presence of Ti, C and O atoms (Supplementary Fig. S5). The C 1s and O 1s spectra of MXene suggest that after the delamination process, the MXene surface was predominantly functionalized with OH groups, the contributions from graphitized carbon, and carbides (Supplementary Figs S7 and S8, respectively). The functional groups of the delaminated MXene and MXene hybrids were further analyzed by Fourier transmission infrared (FTIR) spectroscopy in the attenuated total reflection (ATR) mode, as displayed in Fig. 6. The IR spectrum of the delaminated MXene has a vibrational mode at 3742cm1, which, due to the absence of atmospheric moisture (the samples were blow dried in N2 flow prior to the measurements), is assigned to the OH functional group out of plane vibrations of MXene. This is verified by first principles calculations of Ti3C2(OH)2 in the Ti3C2 block34. These are assigned to the OH/H2O adsorbed on the NPs surface, since these bands were not observed in the case of delaminated MXene flakes.DiscussionThe hybridization of exfoliated 2D nanosheets is potent not only in tailoring the physicochemical properties of hybridized species, but also in showing catalytic activity in concert with coupling between the 2D materials and NPs. Au NPs were previously deposited on delaminated MXene flakes with sodium borohydrate (NaBH4) as a reducing agent35. Moreover, it was observed that a homogeneous size distribution was achieved without a reducing agent by direct addition of Au salt in dark conditions or by photocatalytic assistance of UV irradiation35. Metal NPs (Pt) were also deposited directly on MXene flakes36. Herein, we propose a general in situ reduction method of noble metal NPs on MXene flakes by direct addition of metal salts in ambient air. Firstly, the effect of sonication on the hybridization of MXene flakes was systematically tested by performing treatments both with and without ultrasonication. The ex situ TEM analysis revealed that a homogeneous deposition of NPs (on individual MXene flakes) and subsequently, highly dispersed MXene hybrids (case of Au) were accomplished by ultrasonication. In the case when ultrasonication was not used, non uniformly deposited NPs on stacked MXene flakes (>4 nanosheets) were observed (Supplementary Fig. S9). Thus, we conclude that the ultrasonic mixing helped to obtain a more uniform NPs distribution on finer dispersed MXene nanosheets. 7, involving Ag DMSO complexes. We note that based on preliminary results of35 another salt reduction process without the DMSO complexes could possibly occur on the MXene flakes, either by or without photocatalytic activation. Nevertheless, we hypothesize hereby a mechanism involving DMSO intercalants attached to the few nm thick delaminated MXene flakes12 serving as reduction/nucleation sites for the NPs37. As metal ions (0.1mM Ag+) are added into the MXene colloidal solution under sonication, the formation of [Ag+ DMSO] complex monomers occurs in the MXene solution (stage 1). The [Ag+ DMSO] complexes cause an immediate color change by forming Ag+ DMSO (monomer) strong surface bonds with the OH functional groups of MXene. Thereafter, a fast electron transfer causes the formation of Ag+ [DMSO] from oxygen's lone pair electron ([S (CH3)2]) (stage 2). In the next step (stage 3), the charge transfer between Ag1 MXene complexes initializes the MXene Ag DMSO dimerization. Since the bond with the OH functional group is stronger, this MXene Ag dimeric complexes then undergo a further reduction and form stable (Ag0)n nano clusters (stage 4). This cluster formation leads to van cleef small earrings fake further nucleation and subsequent growth to form stable Ag NPs on the MXene surface (stage 5). Eventually, this MXene localized surface reduction mechanism yields plasmonic 2D substrates decorated by NPs that are highly dispersed in aqueous solution. The coverage of the NP can be further tuned by chemical manipulation of the OH functional groups on the MXene substrate.Next, to understand the nature of the noble metal NPs plasmon peaks observed by the UV vis spectroscopy, as shown in Fig. 2, we calculated in the limits of quasistatic approximation the SPR frequency of an Ag or Au sphere placed near the interface of two dielectric media with dielectric constants denoted as a and b. The case of Pd is discussed separately. We apply the imaging method38 to reduce the problem of the NP immersed in a medium near the MXene (b) sheet to a problem of two NPs in a homogeneous medium. For solving this reduced problem, we involve the approximate analytical approach developed for two spheres39. We consider a NP of a radius (R) in the range of 5 to 35nm where the developed quasistatic approximation is valid. Considering the charge distribution coefficient of the image NP, , (Supplementary information), we obtain the following relation:where y is the minimal distance between NP and MXene, () is the dielectric function of the NP depending on frequency . Eventually, inserting experimental values of dielectric constants15,40 in equation (1), we obtain a good match with the experimental data for SPR wavelengths, 440nm and 558nm, respectively for Ag and Au, in the case of a reasonable value of y/R0.015. Our calculations (Supplementary information) also show that the SPR linewidths of Fig.As seen from Fig. 3, the case of Pd structures deposited on MXene flakes drastically differs from that of the Ag and Au NPs. According to the TEM analysis results, we model these Pd nanostructures by highly oblate spheroids (disc shaped particles). By using Pd optical constants41 and our calculated value of the effective refractive index (Supplementary information), we obtain a SPR peak in the UV range at 160nm. The more sophisticated planar NP geometry and coupling can indeed yield a more red shifted SPR value, evident in Fig. 2. Nevertheless, when we model Pd NPs by spheres of the same size as those of the Ag and Au NPs, we obtain an SPR of 375nm, which is in accordance with the literature42. The absence of such a peak in Fig. 8a) and after NP hybridization (Fig. 8b d) by soaking the glass deposited samples in a 106M ethanol solution of MB and subsequently drying it. In order to improve the signal to noise ratio of the detected Raman signal, we use a hybridization of NPs with increased particle size and amount by adding a 5 fold raised (0.5mM) concentration of each precursor metal salt during the hybridization process. This could result in a fast reduction of the precursor, causing non uniform and larger size NP coating (possibly aggregated) on the MXene surface. Characteristic Raman peaks of partially oxidized Ti3C2Tx10,16 can be seen in Fig. 8a. The oxidation could have occurred due to reaction with ethanol or MB, or from the high laser power (35mW). Nevertheless, no Raman spectral features of MB can be seen in Fig. 8a even though MB molecules were adsorbed on MXene. This clearly comes from the absence of the NPs on the MXene surface, which are necessary for enhancing the Raman signal of MB. The characteristic peaks of MB around 443 and 1615cm1 which have been assigned to C N C skeletal bending and C C stretching, respectively, are evident in the SERS spectra for the three NP hybrids (with varying intensities), indicating that the molecules were adsorbed onto the substrates43. The SERS characteristic bands for clover diamond earrings fake (C S C) and (C S) at 559cm1 and 1181cm1, respectively, are observed suggesting that the chemisorbed MB molecules were attached to the MXene hybrids surface via sulphur metal bond, enriching C S bond intensities. 8c,d. The produced 2D MXene hybrid substrates are hence expected to exhibit high SERS enhancement. As a reference, 1% of liquid MB (in ethanol) was used to acquire a Raman spectrum for the calculations of the enhancement factors of 2D MXene hybrids samples (Supplementary Fig. S10). This suggests possible SERS applications of the proposed material.Figure 8(a) Raman spectrum of Ti3C2Tx after soaking in MB dispersed in ethanol and subsequent drying.In conclusion, herein we report a strategy for synthesis of noble metal nanoparticle MXene hybrids by one step soft solution processing. Through TEM and simultaneous EDX mapping analysis, we show that a uniform coating of Ag, Au and Pd NPs on MXene nanosheets was accomplished. The plasmonic nature of these novel 2D hybrid nanostructured substrates was demonstrated by surface enhanced Raman scattering (SERS). The advantage of this method is the in situ controlled synthesis approach, as well as the EM and CM combined nature, favorable for the SERS enhancement. Moreover, the simplicity of the solution based approach and the absence of reducing agents and expensive instrumentation allow exploration of other MXene NP hybrids and for applications including optical sensors (colorimetric detection), electrochemistry, catalysis and interface studies.MethodsSynthesis of aqueous MXene nanosheets colloidal solutionThe MXene powder of Ti3C2Tx was prepared by etching with a fluoride salt (LiF in HCl) at 35C for 24h from Ti3AlC2 (MAX phase). The obtained MXene powder was used for the production of colloidal suspension of MXene nanosheets by delamination of powder and subsequent bath sonication (Bransonic M3800 Ultrasonic bath, 110W and Frequency 40kHz). For delamination, 0.3g of MXene powder was mixed
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What did Ms. Calment do, that you I can duplicate for health longevity. She remained healthy and with all her marbles, until she kicked the bucket at 122. Nice, right?
She was born in Arles (Guiness Book of Records) imitation van cleef clover earrings in 1875, and cashed in her chips in Arles in 1997. She said she knew Vincent van Gogh, who she thought peculiar, the town thought was a professional wacko.
Calment smoked intensely until five years before age 122 164 days. Would you give up the ghost even Days, before your time, if you were healthy and in your right mind? It all precious time, right? Ask an 80 year old, if he/she would give away five good Days?
Weird fact: her maiden name was Calment, and she married her cousin, who was Fernand Calment. She lived an upper class life, and never indulged in chronic stress. I cannot change it, I ignore it like a dead, smelly cat. She was to the end.
Briefly, what so great about Olive Oil, extra virgin (first pressing) or not? Even 1 2 teaspoons daily for a week, causes a
positive chemical effect in your body? What kind?
It an and free radicals Olive Oil (not Popeye sweetheart), helps assimilate Vitamins A, D, K.
It contains healthy acids your body cannot manufacture.
latest research (Google it) indicates EVOO helps control your blood pressure, improves respiration and circulation. It allegedly inhibits heart disease, and some forms of the big C.
Some scientists offer evidence EVOO slows aging. The big action is its Vitamin E protect you from the negative effects of Free Radicals. Like death. Yes, really.
We like Calment favorite natural condiment because it tastes delicious, and has less calories than any other oil. It is healthier than vegetable oil, and some experts claim it stabilizes dieting success.
Port wine is a sweet dessert beverage. International experts claim Port fights and repairs damaged cells. Want more? (skin seeds) of the grape prevent (maybe), heart attacks.
in the grape used for Port, accelerates healing, acts as an But wait, there more. It ages in a cask for three years, and has a dose of Brandy for sweetness.
Port wine has 20% more alcohol than other wines. More calories, but healthier. Remember this line: Port aids, flight, and luv van cleef and arpels earrings alhambra fake at first sight! Now you never forget the benefits of Port.
Oh yeah, Ruby Port from Portugal is the best. It is with seeds vines at the bottom. Strain it or choke to Brainiacs: free radicals are atoms with an odd, unpaired number of electrons. They attack the nearest stable (heathy) molecule, and steal its electron. Destabilizes, and knocks it off.
what gets results! suggest (ask your primary physician or imitation van cleef turquoise earrings Reflexologist, first) you test Jeanne Louise Calment longevity diet. You be the judge of its effect on your mind body connection. Bernard Wechsler.
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