The recent advances in nanotechnology and the corresponding increase in the use of nanomaterials in products in every sector of society have resulted in uncertainties regarding environmental impacts. The objectives of this review are to introduce the key aspects pertaining to nanomaterials in the environment and to discuss what is known concerning their fate, behavior, disposition, and toxicity, with a particular focus on those that make up manufactured nanomaterials. This review critiques existing nanomaterial research in freshwater, marine, and soil environments. It illustrates the paucity of existing research and demonstrates the need for additional research. Environmental scientists are encouraged to base this research on existing studies on colloidal behavior and toxicology. The need for standard reference and testing materials as well as methodology for suspension preparation and testing is also discussed.

Nanomaterials in the environment: Behavior, fate, bioavailability, and effects

Since the discovery of organic azides by Peter Griess more than 140 years ago, numerous syntheses of these energy-rich molecules have been developed. In more recent times in particular, completely new perspectives have been developed for their use in peptide chemistry, combinatorial chemistry, and heterocyclic synthesis. Organic azides have assumed an important position at the interface between chemistry, biology, medicine, and materials science. In this Review, the fundamental characteristics of azide chemistry and current developments are presented. The focus will be placed on cycloadditions (Huisgen reaction), aza ylide chemistry, and the synthesis of heterocycles. Further reactions such as the aza-Wittig reaction, the Sundberg rearrangement, the Staudinger ligation, the Boyer and Boyer-Aube rearrangements, the Curtius rearrangement, the Schmidt rearrangement, and the Hemetsberger rearrangement bear witness to the versatility of modern azide chemistry.

Organic Azides: An Exploding Diversity of a Unique Class of Compounds

Asymmetric 1,3-Dipolar Cycloaddition Reactions

One of the initial steps in the development of therapeutic agents is the identification of lead compounds that bind to the receptor or enzyme target of interest. Many analogs of these lead compounds are then synthesized to define the key recognition elements for maximal activity. In general, many compounds must be evaluated in both the lead identification and optimization steps. Increasing burdens have been placed on these efforts due to the large number of new therapeutic targets that continue to be identified thorough modern molecular biology methods.1 To address this demand, very powerful chemical and biological methods have been developed for the generation of large combinatorial libraries of peptides2 and oligonucleotides3 that are then screened against a receptor or enzyme to identify high-affinity ligands or potent inhibitors, respectively. While these studies have clearly demonstrated the power of library synthesis and screening strategies, peptides and oligonucleotides generally have poor oral activities and rapid in vivo clearance;4 therefore their utility as bioavailable therapeutic agents is often limited. Due to the favorable pharmacokinetic properties of many small organic molecules (<600-700 molecular weight),5 the design, synthesis, and evaluation of libraries of these compounds6 has rapidly become a major frontier in organic chemistry. Lorin A. Thompson was born in Lexington, KY, in 1970. He received the Bachelor of Science degree from the University of North Carolina, Chapel Hill, in 1992 where he worked under the guidance of Joseph Desimone. He is currently pursuing his doctorate in the laboratory of Jonathan Ellman at UC Berkeley where he is the 1994 Glaxo-Wellcome fellow. His research interests include the development of synthetic methodology for organic library construction.

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Synthesis and Applications of Small Molecule Libraries.

1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis

The reaction of 9-vinylacridine (1) with C,N-diarylnitrones (3) in xylene under reflux afforded 5-(9-acridinyl)-2,3-diarylisoxazolidines (4) and/or 9-acridinyl styryl ketones (5). On heating isoxazolidines 4 were readily converted into the styryl ketones 5 with the elimination of anilines: this is a new type of thermal decomposition of isoxazolidine ring. However, thermal decomposition of 3-(9-acridinyl)-2,5-diarylisoxazolidines (9) which were prepared from N-(9-acridinylmethylene)aniline N-oxide (7) and styrene (8), did not observed. On the other hand, the reaction of 9-ethynylacridine (2) with nitrones 3 in ethanol under the influence of hydrochloric acid proceeded smoothly to give the reversed 4-(9-acridinyl)-4-isoxazolines (11), which on heating were converted into the corresponding 4-oxazolines 12.

Compounds Related to Acridine. XIII. Reactions of 9-Vinyl- and 9-Ethynylacridine with C,N-Diarylnitrones

The reactions of benzylideneacenaphthenones with sulfonium ylides were studied extensively. Although the reactions of benzylidene- and p-methylbenzylideneacenaphthenone with dimethylsulfonium methylide gave only resinous materials, the p-chlorobenzylidene derivative condensed with the ylide to afford the corresponding spiroxirane compound in a good yield. In the reactions with dimethyloxosulfonium methylide and carbonyl-stabilized sulfonium ylides such as ethyl (dimethylsulfuranilidene) acetate and dimethylsulfonium phenacylide, benzylidene-acenaphthenones gave the corresponding spirocyclopropyl ketones in good yields. The products obtained in the latter reactions were established to be cis-cyclopropyl compounds on the basis of NMR spectral studies. On the other hand, ethoxycarbonylmethyleneacenaphthenone condensed with carbonyl-stabilized sulfonium ylides to give trans-cyclopropyl ketones. On the basis of these results, the reaction mechanism was discussed. Also, bis-2,2′-methyleneacenaphthenone reacted ...

Studies of Acenaphthene Derivatives. XX. The Reactions of Benzylideneacenaphthenones with Sulfonium Ylides

Reactions of 2-methylene-3-phenacylbenzothiazoline and 3-benzyl-2-methylenebenzothiazoline, generated in situ from the corresponding 2-methylbenzothiazolium bromide and triethylamine, with methylenecyclopropenes gave a variety of products, cross-conjugated systems, spiro-cyclopentafurans and/or cyclopentabenzothiazines, depending on the nature of substituents of the methylenecyclopropenes. The reaction pathways for the formation of products are also described.

Reactions of 2-methylenebenzothiazolines with methylenecyclopropenes.

Les cycloadditions dipolaires 1,3 de pyridiniomethanures et d'α-furoyl thiazoliomethanure (ylures d'azomethine) sur des maleimides ou le maleate de dimethyle se font par une approche endo des antiylures sur les dipolarophiles: obtention de pyrrolo [3,4-a] indolizinediones, de pyrrolo [3',4'-3,4] pyrrolo [2,1-b] thiazoledione et de pyrrolo [2,1-b] thiazoledicarboxylate

Stereoselective (3 + 2) cycloaddition reaction of pyridinium and thiazolium methylides to electron-deficient olefinic dipolarophiles

In the cycloaddition of heteroaromatic N-ylides to symmetrically substituted trans olefins, the anti ylide exclusively participates if the ylide is carbonyl-stabilized, while the syn ylide does if it has a substituent of non-carbonyl type. The cycloadducts isomerize into thermodynamically more stable isomers through a retro reaction.

Otohiko Tsuge

Papers

Compounds Related to Acridine. XIII. Reactions of 9-Vinyl- and 9-Ethynylacridine with C,N-Diarylnitrones

Studies of Acenaphthene Derivatives. XX. The Reactions of Benzylideneacenaphthenones with Sulfonium Ylides

Reactions of 2-methylenebenzothiazolines with methylenecyclopropenes.

Stereoselective (3 + 2) cycloaddition reaction of pyridinium and thiazolium methylides to electron-deficient olefinic dipolarophiles

Stereochemical features of cycloaddition of heteroaromatic n-ylides. selective participation of the anti and syn ylides