Vadim G. Kessler

Bio: Vadim G. Kessler is an academic researcher from Swedish University of Agricultural Sciences. The author has contributed to research in topics: Alkoxide & Nanoparticle. The author has an hindex of 39, co-authored 284 publications receiving 5262 citations. Previous affiliations of Vadim G. Kessler include Bar-Ilan University & Center for Advanced Materials.

Role of the Ancillary Ligand N,N-Dimethylaminoethanol in the Sensitization of EuIII and TbIII Luminescence in Dimeric β-Diketonates

Abstract: Two types of dimeric complexes [Ln2(hfa)6(i2-O(CH2)2NHMe2)2] and [Ln(thd)2(i2,e2-O(CH2)2NMe2)]2 (Ln ) YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- ) hexafluoroacetylacetonato, thd- ) dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the â-diketonate. In [Tb2(hfa)6(i2-O(CH2)2NHMe2)2], eight-coordinate TbIII ions adopt distorted square antiprismatic coordination environments and are O-bridged by two zwitterionic N,N-dimethylaminoethanol ligands with a Tb1âââTb2 separation of 3.684(1) A. In [Tb(thd)2(i2,e2-O(CH2)2NMe2)]2, the N,N-dimethylaminoethanol acts as chelating-bridging O,N-donor anion and the TbIII ions are seven-coordinate; the Tb1âââTb1A separation amounts to 3.735(2) A within centrosymmetric dimers. The dimeric complexes are thermally stable up to 180 °C, as shown by thermogravimetric analysis, and their volatility is sufficient for quantitative sublimation under reduced pressure. The EuIII and TbIII dimers display metal-centered luminescence, particularly [Eu2(hfa)6(O(CH2)2NHMe2)2] (quantum yield QLn L ) 58%) and [Tb(thd)2(O(CH2)2NMe2)]2 (32%). Consideration of energy migration paths within the dimers, based on the study of both pure and EuIII- or TbIII-doped (0.01-0.1 mol %) LuIII analogues, leads to the conclusion that both the â-diketone and N,N-dimethylaminoethanol ligands contribute significantly to the sensitization process of the EuIII luminescence. The ancillary ligand increases considerably the luminescence of [Eu2(hfa)6(O(CH2)2NHMe2)2], compared to [Ln(hfa)3(H2O)2], through the formation of intra-ligand states while it is detrimental to TbIII luminescence in both â-diketonates. Thin films of the most luminescent compound [Eu2(hfa)6(O(CH2)2NHMe2)2] obtained by vacuum sublimation display photophysical properties analogous to those of the solid-state sample, thus opening perspectives for applications in electroluminescent devices.

Cellulose nanofiber–titania nanocomposites as potential drug delivery systems for dermal applications

Abstract: In this work, new efficient drug delivery systems based on cellulose nanofiber–titania nanocomposites grafted with three different types of model drugs such as diclofenac sodium, penicillamine-D and phosphomycin were successfully synthesized and displayed distinctly different controlled long-term release profiles. Three different methods of medicine introduction were used to show that various interactions between TiO2 and drug molecules could be used to control the kinetics of long-term drug release. All synthesis reactions were carried out in aqueous media. The morphology, chemical structure and properties of the obtained materials were characterized by SEM, TEM and AFM microscopy, nanoparticle tracking analysis, X-ray diffraction, and TGA analysis. According to FT-IR and UV-Vis spectroscopy data, the titania binds to cellulose nanofibers via formation of ester bonds and to drug molecules via formation of surface complexes. The drug release kinetics was studied in vitro for diclofenac sodium and penicillamine-D spectrophotometrically and for phosphomycin using a radiolabeling analysis with 33P-marked ATP as a model phosphate-anchored biomolecule. The results demonstrated that the obtained nanocomposites could potentially be applied in transdermal drug delivery for anesthetics, analgesics and antibiotics.

Nano titania aided clustering and adhesion of beneficial bacteria to plant roots to enhance crop growth and stress management

Abstract: A novel use of Titania nanoparticles as agents in the nano interface interaction between a beneficial plant growth promoting bacterium (Bacillus amyloliquefaciens UCMB5113) and oilseed rape plants (Brassica napus) for protection against the fungal pathogen Alternaria brassicae is presented. Two different TiO2 nanoparticle material were produced by the Sol-Gel approach, one using the patented Captigel method and the other one applying TiBALDH precursor. The particles were characterized by transmission electron microscopy, thermogravimetric analysis, X-ray diffraction, dynamic light scattering and nano particle tracking analysis. Scanning electron microscopy showed that the bacterium was living in clusters on the roots and the combined energy-dispersive X-ray spectroscopy analysis revealed that titanium was present in these cluster formations. Confocal laser scanning microscopy further demonstrated an increased bacterial colonization of Arabidopsis thaliana roots and a semi-quantitative microscopic assay confirmed an increased bacterial adhesion to the roots. An increased amount of adhered bacteria was further confirmed by quantitative fluorescence measurements. The degree of infection by the fungus was measured and quantified by real-time-qPCR. Results showed that Titania nanoparticles increased adhesion of beneficial bacteria on to the roots of oilseed rape and protected the plants against infection.

Structure of the hydrated, hydrolysed and solvated zirconium(IV) and hafnium(IV) ions in water and aprotic oxygen donor solvents. A crystallographic, EXAFS spectroscopic and large angle X-ray scattering study.

Abstract: The tetrameric hydrolysis products of zirconium(IV) and hafnium(IV), the zirconyl(IV) and hafnyl(IV) ions, [M4(OH)8(OH2)168+], often labelled MO2+·5H2O, are in principle the only zirconium(IV) and hafnium(IV) species present in aqueous solution without stabilising ligands and pH larger than zero. These complexes are furthermore kinetically very stable and do not become protonated even after refluxing in concentrated acid for at least a week. The structures of these complexes have been determined in both solid state and aqueous solution by means of crystallography, EXAFS and large angle X-ray scattering (LAXS). Each metal ion in the [M4(OH)8(OH2)16]8+ complex binds four hydroxide ions in double hydroxo bridges, and four water molecules terminally. The M–O bond distance to the hydroxide ions are markedly shorter, ca. 0.12 A, than to the water molecules. The hydrated zirconium(IV) and hafnium(IV) ions only exist in extremely acidic aqueous solution due to their very strong tendency to hydrolyse. The structure of the hydrated zirconium(IV) and hafnium(IV) ions has been determined in concentrated aqueous perchloric acid by means of EXAFS, with both ions being eight-coordinated, most probably in square antiprismatic fashion, with mean Zr–O and Hf–O bond distances of 2.187(3) and 2.160(12) A, respectively. The dimethyl sulfoxide solvated zirconium(IV) and hafnium(IV) ions are square antiprismatic in both solid state and solution, with mean Zr–O and Hf–O bond distances of 2.193(1) and 2.181(6) A, respectively, in the solid state. Hafnium(IV) chloride does not dissociate in N,N′-dimethylpropyleneurea, dmpu, a solvent with good solvating properties but with a somewhat lower permittivity (e = 36.1) than dimethyl sulfoxide (e = 46.4), and an octahedral HfCl4(dmpu)2 complex is formed.

The sol–gel synthesis of cotton/TiO2 composites and their antibacterial properties

Abstract: Presentwork is devoted to investigation of structure and functional properties of hybrid nanomaterials based on the TiO2-modified cellulose fibers of cotton. The titania hydrosol was successfully prepared using the titanium tetraisopropoxide as precursor and the nitric acid as peptizing agent via the low-temperature sol–gel synthesis in aqueous medium and applied to cotton fabric. For cross-linking of titania nanoparticles to cotton the 1,2,3,4-butanetetracarboxylic acid (BTCA) was used as a spacer. The morphology and composition of the surface pure and TiO2 modified cotton fibers were investigated by the scanning electron microscopy (SEM). The cotton/TiO2 composite was characterized by the dielectric permittivity. For the estimation of total titania concentration, all samples were calcined at 650 °C. The antimicrobial activity of the treated TiO2 cotton fibers was investigated against Escherichia coli as a model Gram-negative bacteria after exposure to UV-irradiation for 10 min

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities

Abstract: 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...

Controlled ring-opening polymerization of lactide and glycolide.

Abstract: 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

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

Abstract: 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

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

Abstract: 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