Systematic name
\n2-(4-{2-[3,5-bis(pent-1-yn-1-yl)phenyl]ethynyl}-2,5-bis(3,3-dimethylbut-1-yn-1-yl)phenyl)-1,3-dioxolane
\nOther names
\n1,3-dioxolane, 2-[2,5-bis(3,3-dimethyl-1-butyn-1-yl)-4-[2-(3,5-di-1-pentyn-1-ylphenyl)ethynyl]phenyl]
\nNanoKid
\nNanoPutian
\n618904-86-2<\/a>\u00a0 cas<\/p>\n

NanoPutians<\/b>\u00a0are a series of organic molecules whose\u00a0structural formulae<\/a>\u00a0resemble human forms.[1]<\/a><\/sup>\u00a0 James Tour<\/a>\u00a0et al. (Rice University<\/a>) designed and synthesized these compounds in 2003 as a part of a sequence of\u00a0 chemical education<\/a>\u00a0for young students.[2]<\/a><\/sup>\u00a0The compounds consist of two\u00a0 benzene<\/a>\u00a0rings connected via a few carbon atoms as the body, four\u00a0 acetylene<\/a>\u00a0units each carrying an alkyl group at their ends which represents the hands and legs, and a\u00a0 1,3-dioxolane<\/a>\u00a0ring as the head. Tour and his team at Rice University used the NanoPutians in their NanoKids educational outreach program. The goal of this program was to educate children in the sciences in an effective and enjoyable manner. They have made several videos featuring the NanoPutians as anthropomorphic animated characters.
\n $\"\"$ <\/p>\n<\/div>\n
Construction of the structures depends on\u00a0 Sonogashira coupling<\/a>\u00a0and other synthetic techniques. By replacing the 1,3-dioxolane group with an appropriate ring structure, various other types of putians have been synthesized, e.g. NanoAthlete, NanoPilgrim, and NanoGreenBeret. Placing\u00a0 thiol<\/a>\u00a0functional groups at the leg enables them to “stand” on a\u00a0 gold<\/a>\u00a0surface.<\/div>\n
“NanoPutian” is a\u00a0 portmanteau<\/a>\u00a0of\u00a0 nanometer<\/a>, a unit of length commonly used to measure chemical compounds, and\u00a0 lilliputian<\/a>, a fictional population of humans in the novel\u00a0 Gulliver’s Travels<\/a>.<\/p>\n
$\"\"$ <\/p>\n<\/div>\n
Background<\/div>\n
NanoKids Educational Outreach Program]<\/h3>\n
While there are no chemical uses for the NanoKid or any of its subsidiaries,\u00a0 James Tour<\/a>\u00a0has turned the NanoKid into a lifelike character to educate children in the sciences. The goals of the outreach program, as described on the NanoKids website, are:<\/div>\n
\n
\u201cTo significantly increase students\u2019 comprehension of chemistry, physics, biology, and materials science at the molecular level.”<\/li>\n
“To provide teachers with conceptual tools to teach nanoscale science and emerging molecular technology.”<\/li>\n
“To demonstrate that art and science can combine to facilitate learning for students with diverse learning styles and interests.”<\/li>\n
“To generate informed interest in nanotechnology that encourages participation in and funding for research in the field.\u201d [3]<\/a><\/sup><\/li>\n<\/ul>\n
To accomplish these goals, several video clips, CDs, as well as interactive computer programs were created. Tour and his team invested over $250,000 into their project. In order to raise the funds for this endeavor, Tour used unrestricted funds from his professorship and small grants from Rice University, the\u00a0 Welch Foundation<\/a>, the nanotech firm\u00a0 Zyvex<\/a>, and\u00a0 Texas A&M University<\/a>. Tour also received $100,000 in 2002 from the Small Grants for Exploratory Research program, a division of the\u00a0 National Science Foundation<\/a>.[4]<\/a><\/sup><\/div>\n
The main characters in the videos are animated versions of the NanoKid. They star in several videos and explain various scientific concepts, such as the\u00a0 periodic table<\/a>,\u00a0 DNA<\/a>, and\u00a0 covalent bonding<\/a>.<\/div>\n
Rice conducted several studies into the effectiveness of using the NanoKids materials. These studies found mostly positive results for the use of the NanoKids in the classroom. A 2004-2005 study in two schools districts in Ohio and Kentucky found that using NanoKids led to a 10-59% increase in understanding of the material presented. Additionally, it was found that 82% of students found that NanoKids made learning science more interesting.[5]<\/a><\/sup><\/p>\n
$\"\"$ <\/p>\n
$\"ChemSpider$ <\/div>\n
Synthesis of NanoKid<\/h2>\n
Upperbody of NanoKid<\/h3>\n
To create the first NanoPutian, dubbed the NanoKid,\u00a0 1,4-dibromobenzene<\/a>\u00a0was\u00a0 iodinated<\/a>\u00a0in\u00a0 sulfuric acid<\/a>. To this product, \u201carms\u201d, or 3,3-Dimethylbutyne, were then added through\u00a0 Sonogashira coupling<\/a>. Formylation of this structure was then achieved through using the\u00a0 organolithium reagent<\/a>\u00a0 n-butyllithium<\/a>\u00a0followed by quenching with\u00a0 N,N-dimethylformamide<\/a>\u00a0(DMF) to create the aldehyde. 1,2-Ethanediol was added to this structure to protect the aldehyde using\u00a0 p-toluenesulfonic acid<\/a>\u00a0as a\u00a0 catalyst<\/a>. Originally, Chanteau and Tour aimed to couple this structure with alkynes, but this resulted in very low yields of the desired products. To remedy this, the\u00a0 bromide<\/a>\u00a0was replaced with iodide<\/a>\u00a0through lithium-halogen exchange and quenching by using 1,2-diiodoethane. This created the final structure of the upper body for the NanoKid.[1]<\/a><\/sup><\/div>\n
\n
$\"Center\"$ <\/a><\/dd>\n<\/dl>\n
Lowerbody of NanoKid<\/h3>\n
The synthesis of NanoPutian\u2019s lower body begins with\u00a0 nitroaniline<\/a>\u00a0as a starting material. Addition of Br_{2<\/sub>\u00a0in\u00a0}acetic acid<\/a>\u00a0places two equivalents of\u00a0 bromine<\/a>\u00a0on the\u00a0 benzene<\/a>\u00a0ring. NH_{2<\/sub>\u00a0is an\u00a0}electron donating group<\/a>, and NO_{2<\/sub>\u00a0is an\u00a0}electron withdrawing group<\/a>, which both direct bromination to the meta position relative to the NO_{2<\/sub>\u00a0substituent. Addition of [[NaNO_{2<\/sub>]], [[H_{2<\/sub>SO_{4<\/sub>]], and\u00a0}}}}EtOH<\/a>\u00a0removes the NH_{2<\/sub>\u00ac substituent. The\u00a0}Lewis acid<\/a>\u00a0SnCl_{2<\/sub>, a\u00a0}reducing agent<\/a>\u00a0in THF\/EtOH solvent, replaces NO_{2<\/sub>\u00a0with NH_{2<\/sub>, which is subsequently replaced by iodine upon the addition of NaNO_{2<\/sub>, H_{2<\/sub>SO_{4<\/sub>, and KI to yield 3,5-dibromoiodobenzene. In this step, the\u00a0}}}}}Sandmeyer reaction<\/a>\u00a0converts the primary amino group (NH_{2<\/sub>) to a diazonium leaving group (N_{2<\/sub>), which is subsequently replaced by iodine. Iodine serves as an excellent coupling partner for the attachment of the stomach, which is executed through Sonogashira coupling with\u00a0}}trimethylsilylacetylene<\/a>\u00a0to yield 3,5-dibromo(trimethylsilylethynyl)benzene. Attachment of the legs replaces the Br substituents with 1-pentyne through another Sonogashira coupling to produce 3,5-(1\u2032-Pentynyl)-1-(trimethylsilylethynyl) benzene. To complete the synthesis of the lower body, the TMS protecting group is removed by selective deprotection through the addition of K_{2<\/sub>CO_{3<\/sub>, MeOH, and CH_{2<\/sub>Cl_{2<\/sub>\u00a0to yield 3,5-(1\u2032-Pentynyl)-1-ethynylbenzene.}}}}[1]<\/a><\/sup><\/div>\n
\n
$\"Center\"$ <\/a><\/dd>\n<\/dl>\n
Attachment of Upperbody to Lowerbody of NanoKid<\/h3>\n
To attach the upper body of the NanoKid to the lower body, the two components were added to a solution of\u00a0 bis(triphenylphosphine)palladium(II) dichloride<\/a>,\u00a0 copper(I) iodide<\/a>,TEA<\/a>, and\u00a0 THF<\/a>. This resulted in the final structure of the NanoKid.[1]<\/a><\/sup><\/div>\n
\n
$\"Center\"$ <\/a><\/dd>\n<\/dl>\n
Derivatives of NanoKid<\/h2>\n
Synthesis of NanoProfessionals[]<\/h3>\n
The series of NanoProfessionals were created using the NanoKid as the starting material. This was done by adding an excess amount of a 1,2- or 1,3- diol to the NanoKid in the presence of a catalytic amount of\u00a0 p-toluenesulfonic acid<\/a>\u00a0and microwave oven-irradiation. The use of\u00a0 microwave irradiation<\/a>\u00a0reduced the reaction times. These reactions resulted in an\u00a0 acetal<\/a>\u00a0exchange, which changed the structure of the head of the NanoKid to create the different head structures of the NanoProfessionals, which include: NanoAthlete, NanoPilgrim, NanoGreenBeret, NanoJester, NanoMonarch, NanoTexan, NanoScholar, NanoBaker, and NanoChef. By creating a series of different figures, the ultimate product was a recognizably diverse population of NanoPutians.[2]<\/a><\/sup><\/div>\n
Although the majority of the figures are depicted in their\u00a0 equilibrium<\/a>\u00a0conformations, some of the NanoPutians include nonequilibrium conformations in order to make them more recognizable to nonchemists. Many liberties were taken in the visual depiction of the head dressings of the NanoPutians.[2]<\/a><\/sup><\/div>\n
The entire population of NanoPutians (with the exception of the NanoChef) were generated in one microwave oven reaction and confirmed by\u00a0 mass spectrometry<\/a>\u00a0and\u00a0^1<\/sup>H NMR<\/a>.[1]<\/a><\/sup><\/div>\n
\n
$\"Center\"$ <\/a><\/dd>\n<\/dl>\n
Below is a table listing the diols needed to convert the NanoKid into various NanoProfessionals. The diols used to create NanoPilgrim and NanoTexan were made through reductive\u00a0 pinacol coupling<\/a>\u00a0of the 1,4- and 1,5-diketones with SmI_{2<\/sub>\u00a0and Mg\/TiCl_{4<\/sub>. To create the diols used to make the NanoMonarch and the NanoScholar, catalytic OsO_{4<\/sub>\u00a0was used to dihydroxylate the respective cycloalkenes. The diastereomeric ratios were determined through\u00a0^{1<\/sup>H NMR using the diastereotopic acetal protons.}}}}[1]<\/a><\/sup><\/div>\n
\n
$\"Right\"$ <\/a><\/dd>\n<\/dl>\n
Synthesis of the NanoKid in Upright Form]<\/h3>\n
\n
$\"\"$ <\/a><\/p>\n
\n
$\"\"$ <\/a><\/div>\n
Stick Figure NanoPutian in its Energy Minimized Conformation. Determined Using Spartan.<\/p><\/div>\n<\/div>\n<\/div>\n
3-Butyn-1-ol was reacted with\u00a0 methanesulfonyl chloride<\/a>\u00a0and\u00a0 triethanolamine<\/a>\u00a0to produce its\u00a0 mesylate<\/a>. The mesylate was displaced to make thiolacetate. The thiol was coupled with 3,5-dibromo(trimethylsilylethynyl)benzene to create a free alkyne. The resulting product, 3,5-(4\u2019-thiolacetyl-1\u2019-butynyl)-1-(trimethylsilylethynyl)-benzene, had its trimethylsilyl group removed using\u00a0 tetra-n-butylammonium fluoride<\/a>\u00a0(TBAF) and AcOH\/Ac_{2<\/sub>O in THF. The free alkyne was then coupled with the upper body product from the earlier synthesis. This resulted in a NanoKid with protected thiol feet.}[1]<\/a><\/sup><\/div>\n
To make the NanoKid \u201cstand\u2019, the acetyl protecting groups were removed through the use of\u00a0 ammonium hydroxide<\/a>\u00a0in THF to create the free thiols. A gold-plated substrate was then dipped into the solution and incubated for four days.\u00a0 Ellipsometry<\/a>\u00a0was used to determine the resulting thickness of the compound, and it was determined that the NanoKid was upright on the substrate.[1]<\/a><\/sup><\/div>\n
\n
$\"Center\"$ <\/a><\/dd>\n<\/dl>\n
Synthesis of NanoPutian Chain<\/h3>\n
Synthesis of the upper part of the NanoPutian chain begins with 1,3-dibromo-2,4-diiodobenzene as the starting material. Sonogashira coupling with 4-oxytrimethylsilylbut-1-yne produces 2,5-bis(4-tert-butyldimethylsiloxy-1\u2032-butynyl)-1,4-di-bromobenzene. One of the bromine substituents is converted to an aldehyde through an S_{N<\/sub>2 reaction with the strong base, n-BuLi, and THF in the aprotic polar solvent, DMF to produce 2,5-bis(4-tert-butyldimethylsiloxy-1\u2032-butynyl)-4-bromobenzaldehyde. Another Sonogashira coupling with 3,5-(1\u2032-Pentynyl)-1-ethynylbenzene attaches the lower body of the NanoPutian. The conversion of the aldehyde group to a diether \u201chead\u201d occurs in two steps. The first step involves addition of ethylene glycol and\u00a0}trimethylsilyl chloride<\/a>\u00a0(TMSCl) in CH_{2<\/sub>Cl_{2<\/sub>\u00a0solvent. Addition of TBAF in THF solvent removes the silyl protecting group.}}[1]<\/a><\/sup><\/div>\n
\n
$\"Center\"$ <\/a><\/dd>\n
$\"Right\"$ <\/a><\/dd>\n<\/dl>\n
<\/div>\n
References<\/h2>\n
\n
^\u00a0 ^{a<\/b><\/i><\/sup><\/a>\u00a0}^{b<\/b><\/i><\/sup><\/a>\u00a0}^{c<\/b><\/i><\/sup><\/a>\u00a0}^{d<\/b><\/i><\/sup><\/a>\u00a0}^{e<\/b><\/i><\/sup><\/a>\u00a0}^{f<\/b><\/i><\/sup><\/a>\u00a0}^{g<\/b><\/i><\/sup><\/a>\u00a0}^{h<\/b><\/i><\/sup><\/a>\u00a0}^{i<\/b><\/i><\/sup><\/a>\u00a0Chanteau, S. H.; Tour, J. M. (2003).\u00a0}“Synthesis of Anthropomorphic Molecules:\u00a0 The NanoPutians”<\/a>.\u00a0The Journal of Organic Chemistry<\/i>\u00a068<\/b>\u00a0(23): 8750\u20138766.doi<\/a>:10.1021\/jo0349227<\/a>.\u00a0 PMID<\/a>\u00a0 14604341<\/a>.\u00a0 edit<\/a><\/li>\n
^\u00a0 ^{a<\/b><\/i><\/sup><\/a>\u00a0}^{b<\/b><\/i><\/sup><\/a>\u00a0}^{c<\/b><\/i><\/sup><\/a>\u00a0Chanteau, S. H.; Ruths, T.; Tour, J. M. (2003).\u00a0}“Arts and Sciences Reunite in Nanoput: Communicating Synthesis and the Nanoscale to the Layperson”<\/a>.\u00a0Journal of Chemical Education<\/i>\u00a080<\/b>\u00a0(4): 395.\u00a0doi<\/a>:10.1021\/ed080p395<\/a>.\u00a0 edit<\/a><\/li>\n
^<\/a><\/b>\u00a0\u201cWelcome to Nanokids.\u201d Accessed May 6, 2013.\u00a0 http:\/\/nanokids.rice.edu\/<\/a>.<\/li>\n
^<\/a><\/b>\u00a0\u201cC&EN: EDUCATION – \u2018NANOKIDS\u2019 TRY TO GET INTO MIDDLE SCHOOL.\u201d Accessed May 10, 2013.\u00a0 http:\/\/pubs.acs.org\/cen\/education\/8214\/8214nanokids.html<\/a>.<\/li>\n
^<\/a><\/b>\u00a0\u201cNanoKids – Mission.\u201d Accessed May 6, 2013.\u00a0 http:\/\/cohesion.rice.edu\/naturalsciences\/nanokids\/mission.cfm?doc_id=3039<\/a>.<\/li>\n<\/ol>\n
<\/div>\n
External link<\/h2>\n
http:\/\/cohesion.rice.edu\/naturalsciences\/nanokids\/index.cfm<\/a><\/h2>\n
\n
http:\/\/pubs.acs.org\/cen\/education\/8214\/8214nanokids.html<\/a><\/li>\n<\/ul>\n
<\/div>\n
In 2003, there was a paper published which looked like it was going to be a good candidate for the Ig Nobel Prize. It was \u201c Synthesis of Anthropomorphic Molecules: The\u00a0NanoPutians<\/b><\/a>\u201d by Professor James Tour, a chemistry professor at Rice University\u2019s Institute for Nanoscale Science and Technology. The word \u201cNanoPutian\u201d is a portmanteau of \u201cnano\u201d, which means a billionth and the \u201cLilliputian\u201d from the novel Gulliver\u2019s Travels.
\nThe Tour group designed and synthesized a number of human-shaped organic molecules in this paper. Shown in Figure 1 is a molecule named NanoKid, which was chosen by the group as a basic skeleton. The 3-D model looks like the figure on the right and the structural formula used by chemists is shown on the left. The structural formula might look more human, since the oxygen atoms look kind of like the eyes.<\/p>\n
$\"\"$ $\"\"$
\nFig 1 NanoKid<\/div>\n
The functional group used for the head part of NanoKid is called acetal. This group is easily exchangeable to make NanoPutians of various occupations (Figure 2). Let\u2019s not be too picky about the bond angles of NanoMonarch and NanoTexan.<\/p>\n
$\"\"$
\nFig 2 various NanoPutians<\/div>\n
Unfortunately, NanoBalletDancer seems to be the only one having a different posture (Figure 3). Personally, I would be interested in making NanoPitcher or NanoGermanSuplex!<\/p>\n
$\"\"$
\nFig 3 NanoBalletDancer<\/div>\n
The Tour Group also synthesized NanoPutians standing on gold surface with thiol functional groups on their feet, a NanoPutian couple dancing (Figure 4), and even a polymer of NanoPutians (Figure 5).<\/p>\n
$\"\"$
\nFig 4 NanoPutian Couple<\/div>\n
$\"\"$
\nFog 5 NanoPutian polymer<\/div>\n
NanoPutians aren\u2019t actually the first example of human-shaped molecule. For example, the molecule shown in Figure 6 has appeared as a joke in a journal published on April Fool\u2019s Day. The molecule shown in Figure 7 has been introduced once as Buddha molecule. Nevertheless, NanoPutians were probably the first case where human-shaped molecules were synthesized systematically(?) to be published as a full paper.<\/p>\n
$\"\"$ $\"\"$
\nFig 6 human-shaped molecule Fig 7 molecular Buddha<\/div>\n
The Role of NanoPutians<\/b>
\nBesides being human-shaped, the NanoPutian molecules have neither notable properties nor potential usefulness for future. The synthesis is also too straightforward to make any significant methodological contribution to chemical science.
\nThen how did this research get funded and get to be published on Journal of Organic Chemistry? It turns out that the synthesis was a part of the\u00a0chemistry education program<\/a>\u00a0at Rice University aimed at introducing nanotechnology to young students. In fact, it has also been on the\u00a0 cover page of Journal of Chemical Education<\/a>\u00a0too. It\u2019s funny though, to imagine the faces of the journal editors when they first read the paper.
\nBut come to think of it, molecules like dodecahedrane and\u00a0 kekulene<\/a>\u00a0might not be so different in terms of not having much to appeal other than their structural beauty. Even \u201ctotal synthesis of biologically active natural products\u201d, the most respected subfield of organic chemistry, has been criticized on its meaning recently. In a way, the NanoPutian research seems to me as a voice saying \u201csynthetic targets should be selected more freely\u201d and almost as an antithesis against the state of organic chemistry today.<\/p>\n
Anyway, this paper was introduced by general media and was also one of the topics that received most feedbacks on my homepage. There were those who dismissed it as a meaningless play by chemists, but in terms of directing public interest toward organic chemistry wasn\u2019t it a hundred times more effective than ordinary researches? I think it was an excellent work for the education of young chemists as well.
\nProfessor Tour\u2019s playful sense of molecular design can be seen in his research of NanoCars too, which I will introduce in a separate column. This is a wonderful work which can impress both serious scientists and general public.<\/p>\n
$\"\"$
\nnanohippie<\/p>\n
$\"\"$
\nnanorobot<\/p>\n
\n
NanoSports:<\/strong><\/div>\n $\"\"$ <\/a> $\"\"$ <\/a><\/div>\n
Nano\u2019Tainment:<\/strong><\/div>\n<\/strong> $\"\"$ <\/a> $\"\"$ <\/a> $\"\"$ <\/a> $\"\"$ <\/a><\/div>\n<\/div>\n
<\/div>\n<\/div>\n
– See more at: http:\/\/organicchemistrysite.blogspot.in\/#sthash.KDZiGxlJ.dpuf<\/p>\n","protected":false},"excerpt":{"rendered":"
Systematic name 2-(4-{2-[3,5-bis(pent-1-yn-1-yl)phenyl]ethynyl}-2,5-bis(3,3-dimethylbut-1-yn-1-yl)phenyl)-1,3-dioxolane Other names 1,3-dioxolane, 2-[2,5-bis(3,3-dimethyl-1-butyn-1-yl)-4-[2-(3,5-di-1-pentyn-1-ylphenyl)ethynyl]phenyl] NanoKid NanoPutian 618904-86-2\u00a0 cas NanoPutians\u00a0are a series of organic molecules whose\u00a0structural formulae\u00a0resemble human forms.[1]\u00a0James Tour\u00a0et al. (Rice University) designed and synthesized these compounds in 2003 as a part of a sequence of\u00a0chemical education\u00a0for young students.[2]\u00a0The compounds consist of two\u00a0benzene\u00a0rings connected via a few carbon atoms as the body,… Continue reading NANOPUTIANS<\/span><\/a><\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[3],"tags":[18,89,143,144,55],"_links":{"self":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts\/1131"}],"collection":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/comments?post=1131"}],"version-history":[{"count":1,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts\/1131\/revisions"}],"predecessor-version":[{"id":1132,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/posts\/1131\/revisions\/1132"}],"wp:attachment":[{"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/media?parent=1131"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/categories?post=1131"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/amcrasto.theeurekamoments.com\/wp-json\/wp\/v2\/tags?post=1131"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}