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Colloidal nanoparticles are being intensely pursued in current nanoscience research. Nanochemists are often frustrated by the well-known fact that no two nanoparticles are the same, which precludes the deep understanding of many fundamental properties of colloidal nanoparticles in which the total structures (core plus surface) must be known. Therefore, controlling nanoparticles with atomic precision and solving their total structures have long been major dreams for nanochemists. Recently, these goals are partially fulfilled in the case of gold nanoparticles, at least in the ultrasmall size regime (1–3 nm in diameter, often called nanoclusters). This review summarizes the major progress in the field, including the principles that permit atomically precise synthesis, new types of atomic structures, and unique physical and chemical properties of atomically precise nanoparticles, as well as exciting opportunities for nanochemists to understand very fundamental science of colloidal nanoparticles (such as the s...

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities

23 Stereocontrol of Lactide ROP 6164 231 Isotactic Polylactides 6164 232 Syndiotactic Polylactides 6166 233 Heterotactic Polylactides 6166 3 Anionic Polymerization 6166 4 Nucleophilic Polymerization 6168 41 Mechanistic Considerations 6168 42 Catalysts 6169 421 Enzymes 6169 422 Organocatalysts 6169 43 Stereocontrol of Lactide ROP 6170 44 Depolymerization 6170 5 Cationic Polymerization 6170 6 Conclusion and Perspectives 6171 7 Acknowledgments 6173 8 References and Notes 6173

Controlled ring-opening polymerization of lactide and glycolide.

4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

On the basis of consideration of the properties of AI, In, Ln, Ti, Zr, Hf, NbO3+, MoO4+, WO4+, MoO22+ MO22+, Fe, Co, Ni alkoxide derivatives the main regularities in poly- and oligomerization properties have been deduced 1) The molecular complexity increases in time (aging) and on action of alcohols. This process is followed by the increase in the melting and boiling points, decrease in solubility in ROH and weakening of colour. In the mass-spectra - in connection with the temperature of transition into the gas phase - increases the stability of products with lower molecular masses. 2) oligomerization occurs on dissolution in aromatic hydrocarbons or on a short thermal treatment (melting, distillation). The oligomerization products possess lower thermal constants, higher solubility in ROH and more intense colour. Their mass- spectra are containing the fragments of higher masses corresponding to oligomers existing apparently also in the condensed phase. The mastering of these regularities permits the monitoring of molecular composition and thus physicochemical properties of the samples which are of importance for their technological application. The presence of oxoalkoxides in the “M(OR)n” samples should be taken into consideration on the preparation of solutions used in the synthesis of powders and films of pure simple and mixed oxides.

What are the Molecules of Which the Samples of Metal Alkoxides do Really Consist

Oxoalkoxoniobates of barium and lithium

The review considers principal mechanisms in solution transformations, hydrolysis and condensation of alkoxysilanes and metal alkoxide complexes and the pathways of further transformations of the thus formed colloid systems. The versatility of silica sol-gel is provided by the possibility to direct the kinetically controlled process towards either polymeric or micellar colloids. The hydrolysis of metal alkoxides is kinetically unhindered and results in formation of Micelles Templated by Self-Assembly of Ligands (MTSALs) under the local equilibrium conditions. The morphology, reactivity, long term stability and biocompatibility of MTSALs can be efficiently controlled by the choice of metal cations, ligands and the conditions of hydrolysis. Application of the MTSAL concept for the synthesis of hierarchically porous materials and the prospects of their use in bioencapsulation and biodelivery for water and soil remediation processes are discussed.

New insight into mechanisms of sol-gel process and new materials and opportunities for bioencapsula- tion and biodelivery

In the pursuit of understanding the factors guiding interactions between polyoxometalates (POMs) and biomolecules, several complexes between Keggin phosphomolybdate and diglycine have been produced at different acidity and salinity conditions, leading to difference in stoichiometry and in crystal structure. Principal factors determining how the POM and dipeptide interact appear to be pH, ionic strength of the medium, and the molar ratio of POM to peptide. An important effect turned out to be even the structure-directing role of the sodium cations coordinating carbonyl functions of the peptide bond. Given the interest in applying POMs in biological systems, these factors are highly relevant to consider. In the view of recent interest in using POMs as nano catalysts in peptide hydrolysis also the potential Keggin POM transformation in phosphate buffered saline medium was investigated leading to insight that nanoparticles of zirconium phosphate (ZrP) can be actual catalysts for breakdown of the peptide bond.

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Vadim G. Kessler

Papers

What are the Molecules of Which the Samples of Metal Alkoxides do Really Consist

Oxoalkoxoniobates of barium and lithium

New insight into mechanisms of sol-gel process and new materials and opportunities for bioencapsula- tion and biodelivery

Factors influencing stoichiometry and stability of polyoxometalate - peptide complexes.

Metal Alkoxides - Precursors for Preparation of Complex Molybdates and Tungstates