Nanosized aluminum nitride hollow spheres formed through a self-templating solid-gas interface reaction

Nanosized aluminum nitride hollow spheres were synthesized by simply heating aluminum nanoparticles in ammonia at 1000 °C. The as-synthesized sphere shells are polycrystalline with cavity diameters ranging from 15 to 100 nm and shell thickness from 5 to 15 nm. The formation mechanism can be explained by the nanoscale Kirkendall effect, which results from the difference in diffusion rates between aluminum and nitrogen. The Al nanoparticles served as both reactant and templates for the hollow sphere formation. The effects of precursor particle size and temperature were also investigated in terms of product morphology. Room temperature cathode luminescence spectrum of the nanosized hollow spheres showed a broad emission band centered at 415 nm, which is originated from oxygen related luminescence centers. The hollow structure survived a 4-h heat treatment at 1200 °C, exhibiting excellent thermal stability.     

Fire retardant synergism between melamine and triphenyl phosphate in poly(butylene terephthalate)

The fire retardant efficiency of melamine (MA) and triphenyl phosphate (TPP) in poly(butylene terephthalate) (PBT) was studied by the limiting oxygen index (LOI) and the UL94 test. On adding 10 wt. % MA and 20 wt. % TPP, LOI increased from 20.9 to 26.6 and the UL94 V-0 rating was achieved. SEM and DSC analyses show that the fire retardants are compatible with PBT and facilitate crystallization of PBT. The occurrence of an interaction between MA + TPP and PBT was elucidated by TGA, dynamic FTIR, and pyrolysis/GC/MS. MA + TPP changes the degradation path of PBT and modifies the compositions of the gas and condensed-phase products.     

Encoding method for OBOC small molecule libraries using a biphasic approach for ladder-synthesis of coding tags

In the "one-bead one-compound" (OBOC) combinatorial library method, each compound bead displays only one compound entity. Hundreds of thousands to millions of compound beads can be synthesized rapidly and screened simultaneously. Positive compound beads are then isolated for structural analysis. To fully exploit the power of OBOC combinatorial small molecule libraries, a robust and high throughput encoding method is needed to decode the positive compound beads. In this paper, we report on the development of a novel encoding strategy that combines the concepts of ladder-synthesis and chemical encoding on bilayer beads. In these encoded libraries, small molecule compounds are displayed on the bead surface, and cleavable coding tags consisting of a series of truncated molecules reside in the bead interior. Such a library can be easily constructed using the biphasic approach (J. Am. Chem. Soc.2002, 124, 7678) to topologically segregate the functionalities of the beads during library synthesis. The ladder members and coding tags are then released for MALDI-TOF-MS analysis. To simplify the interpretation of the mass spectra, we purposely add bromine into the cleavable linker so that the cleavage products generate a characteristic isotope fingerprint. The chemical structure of library compounds can be determined by analyzing the mass differences between adjacent peaks on the mass spectra. This encoding strategy also provides valuable information on the quality of the testing compound on the surface of the bead. To validate this methodology, a model OBOC small molecule library with 12,288 members was synthesized on TentaGel beads and screened against streptavidin. The chemical structures of the compound on each positive bead were unambiguously identified.     

Remote substituent effects on bond dissociation energies of para-substituted aromatic silanes

UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified.     

用硼酸作催化剂一锅法合成双（二氢化嘧啶酮-4-基）苯

A simple effective synthesis of bis(dihydropyrimidinone-4-yl)benzene derivatives, using boric acid as catalyst,from isophthalic aldehyde or terephthalic aldehyde, 1,3-dicarbonyl compounds and urea or thiourea in glacial acetic acid was described. As the expansion of the classical Biginelli reaction, this method has the advantage of excellent yields 83%-94% and short reaction time 0.5-1.5 h.     

Preparation of nickel-mesoporous materials and their application to the hydrodechlorination of chlorinated organic compounds

Mesoporous materials have attracted considerable attention for use as a catalyst or a catalyst support due to their remarkable textural properties such as high surface area and large pore volume with a narrow pore size distribution. Many efforts have been made to design mesoporous materials for use in heterogeneous catalyst systems. Recent progress and results regarding the preparation of nickel-mesoporous materials and their application to the hydrodechlorination of chlorinated organic compounds were discussed in this review. Mesoporous materials were used as a support for nickel catalyst or a nickel-incorporated mesoporous catalytic material in this work. Two research areas were described and discussed in this review. One is the preparation of mesoporous alumina-supported nickel catalysts and their application to the hydrodechlorination of 1,2-dichloropropane and o-dichlorobenzene. The other is the preparation of mesoporous silica-supported nickel catalysts and their application to the hydrodechlorination of 1,1,2-trichloroethane and chlorobenzene.     

Adenanthusone,a New Ursane Type Nortriterpenoid from Isodon adenanthus

A new ursane‐type nortriterpenoid, adenanthusone (=(11α,12α)‐4‐demethyl‐11,12‐epoxy‐3,13‐dihydroxy‐2‐oxoursa‐3,20(30)‐diene‐28‐oic acid γ‐lactone; 1 ) was isolated from Isodon adenanthus. Its structure was determined by NMR spectra and X‐ray crystallographic diffraction analysis. The biogenetic implication of the nortriterpene is discussed.     

Modelling of the pressure-velocity correlation in turbulence diffusion

Most current computations of trubulent flows with second-moment closure adopt the diffusion models which neglect the effect of pressure-velocity correlation. In the present paper the importance of this correlation effect is elucidated the neglect of this effect accounts for some major defects in the wide application of the second-moment closures. Through the relation between and , established by Lumley, we propose here a new turbulence diffusion model which takes into consideration the pressure effect. Applications of this new model in the computation of shearless turbulence mixing layer and plane and round-jet flows show that the spreading rate of these flows can be satisfactorily captured.     

Molecular Recognition of Bridged Bis(β-cyclodextrin)s Linked by Phenylenediseleno Tether on the Primary or Secondary Side with Fluorescent Dyes

A Novel β-cyclodextrin dimer,2,2′-o-phenylenediseleno-bridgedbis(β-cyclodextrin)(2),has been synthesized by reaction ofmono-[2-O-(p-tolylsulfonyl)]-β-cyclodextrin and poly(o-phenylenediselenide).The complexation stability constants(K_s)and Gibbs free energy changes(-ΔG°)of dimer 2 with fourfluorescence dyes,that is,ammonium 8-anilino-1-naphthalene-sulfonate(ANS),sodium 6-(p-toluidino)-2-naphthalenesul-fonate(TNS),Acridine Red(AR)and Rhodamine B(RhB)have been determined in aqueous phosphate buffer solution(pH=7.2,0.1 mol·L~(-1)at 25℃ by means of fluorescence spec-