Influence of the reactant concentrations on the synthesis of ZnO nanoparticles

We report on the synthesis of ZnO nanoparticles from Zn(CH3CO2)2 and NaOH in 2-propanol. Nucleation and growth are fast, and hence at longer times the particle size is controlled by coarsening. The coarsening kinetics are independent of the Zn(CH3CO2)2 concentration between 0.5 and 1.25 mM at a fixed [Zn(CH3CO2)2]:[NaOH] ratio of 0.625. The width of the size distribution was found to increase only slightly with aging time. In addition, at a fixed Zn(CH3CO2)2 concentration of 1 mM, the kinetics are independent of the [Zn(CH3CO2)2]:[NaOH] ratio between 0.476 and 0.625. The presence of water in the reaction mixture was found to only slightly affect the coarsening kinetics for water contents larger than about 20 mM. For lower water concentrations, the nucleation and growth of ZnO were very slow. It can be concluded that the synthesis method described provides a reliable source of ZnO nanoparticles due to its insensitivity to the reactant concentrations and the presence of water.     

Temperature effect on solubilization of n-alkylbenzenes into sodium cholate micelles

The solubilization of n-alkylbenzenes (benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, n-hexylbenzene) into an aqueous micellar solution of sodium cholate was carried out. Solubilizate concentrations at equilibrium were determined spectrophotometrically at 293.2, 298.2, 303.2, 308.2, and 313.2 K. The first stepwise association constants (K(1)) between solubilizate monomers and vacant micelles were evaluated from the equilibrium concentrations and found to increase with increasing hydrophobicity of the solubilizate molecules. From the Gibbs energy change for solubilization at different micelle aggregation numbers and from the molecular structure of the solubilizates, the function of sodium cholate micelles as solubilizer was discussed. Enthalpy and entropy changes of solubilization were calculated from the temperature dependence of the K(1) values, and the solubilization was found to be enthalpy-driven for the solubilizates with shorter alkyl chains. The results obtained were also compared with those for conventional aliphatic micelles.     

无机原料体系合成TS-1影响因素的研究

以廉价的硅溶胶和三氯化钛分别作为硅源和钛源,四丙基溴化铵(TPABr)为模板剂,二乙胺、正丁胺、氨水等作为碱源,在无机体系中合成了TS-1分子筛。采用XRD,IR,UV-vis,SEM,元素分析和N2吸附/脱附等对合成的分子筛进行了表征。详细考察了碱源、硅钛比N2保护、晶种、模板剂用量、硅源及晶化时间等因素对分子筛合成的影响。结果表明,以无机原料合成的TS-1与用传统有机原料合成的TS-1具有同样的特征。碱度的控制是合成的关键,配胶时需N2保护,加入晶种对合成有明显的导向作用,模板剂最低用量有一临界值,硅溶胶作硅源合成的TS-1晶粒比较大。     

Rational design and synthesis of catalytically driven nanorotors

We report the design and synthesis of nanorotors based upon on-wire lithography. Because of their asymmetric structure, the nanorotors exhibit rotation in a H2O2 bath instead of linear motion. By observing the leading edge of rotation and comparing this result to the nanorotor design, we have concluded that the driving force for motion is dynamic catalytic decomposition of H2O2 which propels, rather than pulls, the nanorotor.     

Temperature driven morphological changes of chemically precipitated hydroxyapatite nanoparticles

Hydroxyapatite (HA) is synthesized by a wet chemical route using calcium hydroxide and ortho-phosphoric acid at various temperatures (40, 80, and 100 degrees C). X-ray diffraction of the precipitate particles revealed HA as the predominant phase (>99%) with a small amount of beta-tricalcium phosphate. Fourier transform infrared spectroscopy indicated the presence of carbonate substitution, which decreased with increasing temperature. Transmission electron microscopy observations revealed needle-shaped particles with a high aspect ratio at 40 degrees C, which changed to spheroidal when the precipitation temperature was increased to 100 degrees C. The changes in the morphology with temperature were analyzed taking into account the driving force for the HA precipitation and the supersaturation level of Ca2+ and PO4(3-) ions with respect to HA. The analysis indicated that the supersaturation level of the reactants, especially the concentration of Ca2+ ions, played a predominant role on the precipitate morphology for this classical acid-base reaction.     

Temperature driven annealing of perforations in bicellar model membranes

Bicellar model membranes composed of 1,2-dimyristoylphosphatidylcholine (DMPC) and 1,2-dihexanoylphosphatidylcholine (DHPC), with a DMPC/DHPC molar ratio of 5, and doped with the negatively charged lipid 1,2-dimyristoylphosphatidylglycerol (DMPG), at DMPG/DMPC molar ratios of 0.02 or 0.1, were examined using small angle neutron scattering (SANS), (31)P NMR, and (1)H pulsed field gradient (PFG) diffusion NMR with the goal of understanding temperature effects on the DHPC-dependent perforations in these self-assembled membrane mimetics. Over the temperature range studied via SANS (300-330 K), these bicellar lipid mixtures exhibited a well-ordered lamellar phase. The interlamellar spacing d increased with increasing temperature, in direct contrast to the decrease in d observed upon increasing temperature with otherwise identical lipid mixtures lacking DHPC. (31)P NMR measurements on magnetically aligned bicellar mixtures of identical composition indicated a progressive migration of DHPC from regions of high curvature into planar regions with increasing temperature, and in accord with the "mixed bicelle model" (Triba, M. N.; Warschawski, D. E.; Devaux, P. E. Biophys. J.2005, 88, 1887-1901). Parallel PFG diffusion NMR measurements of transbilayer water diffusion, where the observed diffusion is dependent on the fractional surface area of lamellar perforations, showed that transbilayer water diffusion decreased with increasing temperature. A model is proposed consistent with the SANS, (31)P NMR, and PFG diffusion NMR data, wherein increasing temperature drives the progressive migration of DHPC out of high-curvature regions, consequently decreasing the fractional volume of lamellar perforations, so that water occupying these perforations redistributes into the interlamellar volume, thereby increasing the interlamellar spacing.     

Absolute asymmetric synthesis driven by circularly polarized light

Circularly polarized light (CPL) is an inherently chiral entity and is regarded as one of the possible deterministic signals that led to the evolution of homochirality in earth. Thus, CPL as an external physical field has been widely used in a technique known as absolute asymmetric synthesis, because a product enriched in one enantiomer is formed from racemic precursor molecules without the intervention of a chiral catalyst. In this review, we retrospect the historical research of CPL-induced absolute asymmetric synthesis, including chiral organic molecules, helical polymers, supramolecular assemblies, noble metal nanostructures. However, based on these results, we concluded that the chiral photon-matter interaction is very faint due to the arrangement of molecular bonds giving rise to chiral features, is over a smaller distance than the helical pitch of CPL, leading extremely small enantiomeric excess for product. Therefore, we highlight the recently emerged technology called superchiral field, in which the superchiral far-field and near-field could enhance the dissymmetry of optical field and near-field, respectively. In sum, we hope this review could bring some enlightenment to researchers and further improve the enantioselectivity of CPL-induced absolute asymmetric synthesis.     

The concept of internal solubilization in peptide synthesis: ethylene glycol-based protecting groups

A novel, ethylene glycol-based protecting group is designed and synthesized for use in solid phase peptide synthesis. Ether and ester type protected amino acids are prepared. The acid stability of the new protecting group showed complete Fmoc/t-Bu compatibility. The new derivatives are tested in solid phase peptide synthesis, with a ‘difficult’ sequence to examine the disruption of peptide aggregation.     

Facile synthesis, aggregation behavior, and cholesterol solubilization ability of avicholic acid

[reaction: see text] Avicholic acid, a major constituent of the bile of several avian species, was synthesized in eight steps from readily available chenodeoxycholic acid in 9% overall yield using Breslow's remote functionalization strategy in a key step. Micelle formation and equilibrium cholesterol solubilization properties were studied for avicholate in aqueous solution.     

Temperature driven morphological changes of hydrothermally prepared copper oxide nanoparticles

The size and shape of nanocrystals have a strong effect on the optical, electrical and catalytic properties. Therefore, controlling the size, shape and structure of nanocrystals is technically important. The controlled synthesis of CuO nanostructures was achieved using a hydrothermal process by simply controlling the precipitation reaction temperature between copper nitrate trihydrate and sodium hydroxide. The Scanning Electron Microscopy (SEM), EDS, XRD, and FTIR analysis revealed that the synthesized product at 200 °C is of pure copper oxide particles. From Scherrer formula, the prepared CuO particles varied approximately 3–7 nm in size simply by varying the reaction temperature. The synthesized particles exhibited a regular flake like morphology and had a uniform size distribution. The morphology and size depend on the reaction conditions. Copyright © 2008 John Wiley & Sons, Ltd.     

Toward reactant encapsulation for substrate-selectivity

A synthetic tris-(bis-(aminomethyl)pyridine) receptor was prepared in excellent yields via reversible imine condensation strategy. Catalytic activity in Henry reactions of the corresponding copper(II) complex was studied. Capitalizing on previous works by Anslyn with related receptors, the dramatic increase in basicity induced by this type of complex on diketo-derivatives was used to perform a nucleophilic addition of a deprotonated substrate onto an electrophile within the cavity. Hence, a Lewis acid stabilized nitronate was reacted with various aldehydes. A notable preference for small reactants easily accommodated in the cavity over encumbered ones was observed, thus representing an example of substrate-selectivity.     

High throughput synthesis of polyesters using entropically driven ring-opening polymerizations

Copolyesters were synthesized in a high throughput (HT) manner and in high yield on ca. a 90 mg scale using entropically driven ring-opening polymerizations (ED-ROPs). This synthetic approach is a valuable addition to the HT polymer synthesis arsenal in that it allows condensation-type polymers with relatively large repeat units, such as those in poly(ethylene terephthalate) and poly(butylene terephthalate), to be obtained easily. The synthetic procedure involved taking mixtures of the appropriate macrocyclic oligoesters and heating them together under neat conditions at 250-300 degrees C for 2 h in the presence of 0.1 mol % of di- n-butyltin oxide or tetra- n-butylammonium tetrafluoroborate. In most cases Mw values were >25,000 and, as expected for ED-ROPs, the polydispersity indices were close to 2.0. Higher molecular weights could be obtained by using longer reaction times, but this might lead to product decomposition. The method worked well for esters formally derived from aliphatic or aromatic acids and alcohols, but less well for esters derived from phenols. Attempts were also made to synthesize copolymers by mixing together the two homopolymers and heating with a catalyst. These reactions were successful in a few instances, but generally, they were not. This is probably because the homopolymers did not mix well. An aluminum reaction block with 36 wells lined with Teflon cups, that fitted snugly in a cylindrical Buchi oven, was the most successful method for carrying out syntheses in an HT manner.     

A photochemical synthesis of functionalized trans-cyclooctenes driven by metal complexation

Described is a scalable procedure for driving photochemical sytheses of trans-cyclooctene derivatives through metal complexation. During photoirradiation, reaction mixtures are continuously pumped through a column of a AgNO3-impregnated silica gel. The trans-cyclooctene derivative is selectively retained by the AgNO3-impregnated silica, but the cis-isomer elutes from the column back to the reaction flask, where it is photoisomerized and recirculated through the column. The method provides access to a range of usefully functionalized derivatives of trans-cyclooctene, including a derivative of 5-aza-trans-cyclooctene that underwent transannular cyclization upon treatment with bromine. The alkene stereochemistry is transferred with high fidelity to the hexahydropyrrolizine framework in the transannular cyclization.     

One-pot synthesis, encapsulation, and solubilization of size-tuned quantum dots with amphiphilic multidentate ligands

We report one-pot synthesis, encapsulation, and solubilization of high-quality quantum dots (QDs) based on the use of amphiphilic and multidentate polymer ligands. In this "all-in-one" procedure, the resulting QDs are first capped by the multidentate ligand and are then spontaneously encapsulated and solubilized by a second layer of the same multidentate polymer upon exposure to water. In addition to providing better control of nanocrystal nucleation and growth kinetics (including resistance to Ostwald ripening), this procedure allows for in situ growth of an inorganic passivating shell on the nanocrystal core, enabling one-pot synthesis of both type-I and type-II core-shell QDs with tunable light emission from visible to near-infrared wavelengths.     

A reactant promoted solvent free synthesis of 3,4-dihydropyrimidin-2(1H)-thione analogues using ammonium thiocyanate

This is the first-time ammonium thiocyanate (NH₄SCN) has been used as a self-promoting reactant for the synthesis of 3,4-dihydropyrimidin-2(1H)-thiones. This report describes a greener, efficient and economic protocol for one pot three-component synthesis of Biginelli compounds using various aldehydes, β-ketoesters and ammonium thiocyanate. Ammonium thiocyanate being a weak acid, accelerate the rate of reaction to obtain Biginelli compounds in solvent-free condition at 110 °C. The key advantages of the present method are high yields, short reaction time, solvent free condition, easy workup and ability to tolerate a variety of functional groups. Ammonium thiocyanate is readily available, cheaper, safer and industrial acceptable material which gives economical as well as ecological rewards to the present method.     

Laser driven synthesis of BHCl2 from BCl3 and H2

Mixtures of BCl₃ and H₂ have been irradiated by a pulsed CO₂ laser yielding BCHl₂ and HCl as the only products. Approximately 50% conversion of the reagents was obtained with a quantum efficiency of 122 10.6 μ photons per BCHl₂ molecule. The product yield is observed to scale with laser power as (P/P₀)^1.26.     

Electron driven processes in ices: Surface functionalization and synthesis reactions

The ability to control and orientate chemical reactivity in the condensed phase is a major challenge of modern research. Upon interaction with condensed molecules electrons drive bond cleavage thus generating a population of very reactive species in the condensed medium. These reactive species may interact either within the volume leading to the synthesis of new molecules or with the substrate surface by forming strong chemical bonds. The former reaction is known as electron induced synthesis and the latter one as electron induced surface functionalization.High-energy electrons achieve only a low chemical specificity due to the large number of dissociating open channels. In contrast, electrons with energies below ionization threshold of the irradiated matter are capable of high selectivity because of the dissociative electron attachment mechanism.In this review recent studies of electron interaction with condensed molecules on hydrogenated diamond substrates will be described. In particular electron induced functionalization of diamond surfaces by CH₂CN groups, decarboxylation reactions in condensed films of pure organic acids RCOOH (R = H, CH₃, C₂H₅, CF₃), carbamic acid formation in CO₂:NH₃, HCOOH:NH₃ and CF₃COOH:NH₃ binary ice mixtures, and glycine formation in a CH₃COOD:NH₃ mixture are presented and discussed.     

Quantum dynamics of vibrationally activated OH-CO reactant complexes

The MP2 complete basis set (CBS) limit for the binding energy of the two low-lying water octamer isomers of D2d and S4 symmetry is estimated at -72.7+/-0.4 kcal/mol using the family of augmented correlation-consistent orbital basis sets of double through quintuple zeta quality. The largest MP2 calculation with the augmented quintuple zeta (aug-cc-pV5Z) basis set produced binding energies of -73.70 (D2d) and -73.67 kcal/mol (S4). The effects of higher correlation, computed at the CCSD(T) level of theory, are estimated at <0.1 kcal/mol. The newly established MP2/CBS limit for the water octamer is reproduced quite accurately by the newly developed all atom polarizable, flexible interaction potential (TTM2-F). The TTM2-F binding energies of -73.21 (D2d) and -73.24 kcal/mol (S4) for the two isomers are just 0.5 kcal/mol (or 0.7%) larger than the MP2/CBS limit.     

Temperature dependence of the interaction of cholate and deoxycholate with fluid model membranes and their solubilization into mixed micelles

The interaction of bile salts with model membranes composed of soybean phosphatidylcholine (SPC) and synthetic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) was investigated using high sensitivity isothermal titration calorimetry (ITC). The partitioning and incorporation of the bile salts sodium cholate (NaC) and sodium deoxycholate (NaDC) from an aqueous phase (pure water or 0.1 M NaCl) into fluid bilayer vesicles was studied as a function of temperature and ionic strength. The thermodynamic parameters of partitioning were determined with a model taking electrostatic interactions into account. In addition, the solubilization of SPC and POPC vesicles with NaC and NaDC as a function of temperature was also studied by ITC and the phase diagrams for the vesicle to micelle transition at two different temperatures were established. Unsaturated phospholipids require higher amounts of detergent to be transformed into micelles compared to saturated phospholipids. In addition, the width of the coexistence region of mixed micelles and mixed vesicles is larger for phosphatidylcholines with unsaturated chains. A comparison of NaDC with NaC shows the higher solubilization effectiveness of NaDC in agreement with its lower cmc. Furthermore, increasing the ionic strength decreases the amount of bile salt necessary for the formation of mixed micelles, which is also expected from the decrease of the cmc with ionic strength due to the shielding of the charges of the bile salts.     

Topologically driven tandem radical cyclization-based strategy for the synthesis of oxa- and aza-cages

Tandem radical cyclization-based strategy for the synthesis of oxa- and aza-cage compounds is described. The aryl iodides 1 and N-tosyl propargylated amine 8 lead to oxa- and aza-cages, respectively, after two tandem 5-exo-trig radical cyclizations. The alcohols 11 on reaction with ⁿBu₃SnH and AIBN give rise to the oxa-cages 14 bearing the tributyltin moiety after three tandem 5-exo-trig cyclizations. On the other hand, reaction of the propargyl ether 16 under similar conditions furnishes the oxa-cage 17 by a 5-exo-trig, 4-exo-trig, 5-exo-trig tandem radical cyclization sequence.