激光产生的钒硫簇离子的统计分布与结构探讨

以脉冲激光在高真空中溅射钒粉和硫粉的混合物，产生了一系列钒硫原子簇正负离子。根据对其实验记录的激光等离子体质谱进行分析，发现钒硫原子簇的化学键基本上是共价型的，对应于相同钒原子数目的正负离子的相对丰度分别符合于不同形式的对数正态分布。正离子的相对丰度随硫原子数的增加呈对数衰减，由此可以确定各种大小簇合物的簇骼与几何构型；负离子的相对丰度则基本上呈正常的正态分布，说明在簇骼上结合了不同数量硫原子的负离子之结构稳定性大致相近。在实验中还观察到一类硫原子含量较高的簇离子，其中的部分硫原子可能在本身成键形成环状的硫集团后，又与原来的簇骼结合，因而在硫原子数较多时它们的相对丰度符合另一条对数正态分布曲线。     

Kinetics of Heterogeneous Isotopic Exchange Reaction in Finite Bath

A general method to find the rate constant and particle self-diffusion coefficient is suggested for a heterogeneous isotopic exchange reaction which is controlled by surface mass reaction or controlled by a combination of surface mass reaction and intraparticle diffusion. The values of the kinetic parameter, ξ₁ (ratio of the forward surface mass reaction rate to the intraparticle diffusion rate), particle self-diffusion coefficient D and rate constant k are obtained by the proposed method for the isotopic exchange reaction systems CaCO₃(s)/Ca²⁺(aq) and CaC₂O₄(s)/Ca²⁺(aq).     

Theoretical study on structures and stability of C4P isomers

The structures, energetics, spectroscopies, and stabilities of doublet C(4)P isomeric species are explored at the DFT/B3LYP, QCISD, and CCSD(T) (singlet-point) levels. A total of 12 minimum isomers and 27 interconversion transition states are located. At the CCSD(T)/6-311G(2df)//QCISD/6-311G(d)+ZPVE level, the lowest-lying isomer is a floppy CCCCP 1 (0.0 kcal/mol) mainly featuring a cumulenic structure |C=C=C=C=P*|, which differs much from the analogous C4N radical (|*C-C[triple bond]C-C[triple bond]N|). The quasi-linearity and the low bending mode of 1 are in contrast to the previous prediction. The second energetically followed isomer PC-cCCC 3 (14.9 kcal/mol) possesses a CCC ring-bonded to CP. The two low-lying isomers are separated by a high-energy ring-closure/open transition state (26.5 kcal/mol) and thus are very promising candidates for future laboratory and astrophysical detection. Furthermore, four high-energy isomers, that is, two bent isomers CCPCC 2 (68.4 kcal/mol) and CCPCC 2' (68.5 kcal/mol) and two cagelike species 10 (56.0 kcal/mol) and 11 (67.9 kcal/mol), are also stabilized by considerable barriers. The present work is the first detailed potential energy survey of CnP clusters and can provide useful information for the investigation of larger CnP radicals and for understanding the isomerism of P-doped C vaporization processes.     

ADSORPTION OF 2,4-D ON MODIFIED HYPERCROSSLINKED POLYSTYRENE （NDA-99） AND XAD-4 RESIN

The adsorption behavior of pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution has been investigated using a hypercrosslinked polystyrene adsorbent (NDA-99) modified by dimethylamine group as well as a nonionic macroporous adsorbent (XAD-4). The Langmuir and Freundlich isotherm models were employed to fit the experimental data to describe adsorption mechanism. It shows that NDA-99 resin exhibits an adsorption affinity for 2,4-D higher than XAD-4 resin owing to its exceptional micropore structure and the amine group of the hypercrosslinked matrix.Further studies indicate that the hydrogen bonding interaction and the stronger π-π conjugation play a significant role in the course of the adsorption of 2,4-D on NDA-99 resin, which is in agreement with the IR spectroscopic results and the △E values of HOMO (the highest occupied molecular orbit) of adsorbent and LUMO (the lowest unoccupied molecular orbit) of adsorbate calculated from the MINDO/3 model.     

The distribution coefficient of oil and curing agent in PP/EPDM TPV

The distribution coefficients of oil and curing agent in PP/EPDM TPV were calculated by measuring the melting point of the PP phase using differential scanning calorimetry (DSC). The PP/EPDM TPV was prepared by using a twin screw extruder and a peroxide curing agent was used. The peroxide induces the degradation of PP, resulting in the decrease of T_m. The oil in PP phase also decreases the Tm. Based on the T_m difference among pure PP and PP/EPDM TPV before and after extraction by cylcohexane, the calculated oil distribution coefficient is 0.537. The addition sequence of PP, oil, and curing agent has a significant effect on the T_m and the calculated curing agent distribution coefficient is 0.52. Both of the coefficients are less than 1. Based on the calculation of the two coefficients, a rationale design of thermoplastic vulcanizate (TPV) can be made by proper control of raw materials, addition sequence, and processing parameters. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of a diverse library of mechanism-based cysteine protease inhibitors

We report improvements of our method for the solid-phase synthesis of mechanism-based mercaptomethyl ketone inhibitors of cysteine proteases (Lee, A.; Huang, L.; Ellman, J. A. J. Am. Chem. Soc. 1999, 121, 9907-9914). Specifically, Fmoc-protected chloromethyl ketones were used, rather than the Alloc-protected counterparts. In addition, we further demonstrated that diverse polar functionality can be incorporated at the R1', R1, and R2 sites, in contrast to our previous efforts, where primarily hydrophobic groups were incorporated at these positions. On the basis of these results, a 2016-membered library of potential mercaptomethyl ketone inhibitors was prepared that incorporated diverse functionality. The library was screened against cathepsin B, which is implicated in cancer, resulting in the identification of single-digit nanomolar inhibitors. Because of the diverse functionality incorporated in this library, it should be a rich source of potent inhibitors against many other cysteine proteases.     

Quantitative interrogation of protein co-aggregation using multi-color fluorogenic protein aggregation sensors

Co-aggregation of multiple pathogenic proteins is common in neurodegenerative diseases but deconvolution of such biochemical process is challenging. Herein, we developed a dual-color fluorogenic thermal shift assay to simultaneously report on the aggregation of two different proteins and quantitatively study their thermodynamic stability during co-aggregation. Expansion of spectral coverage was first achieved by developing multi-color fluorogenic protein aggregation sensors. Orthogonal detection was enabled by conjugating sensors of minimal fluorescence crosstalk to two different proteins via sortase-tag technology. Using this assay, we quantified shifts in melting temperatures in a heterozygous model protein system, revealing that the thermodynamic stability of wild-type proteins was significantly compromised by the mutant ones but not vice versa. We also examined how small molecule ligands selectively and differentially interfere with such interplay. Finally, we demonstrated these sensors are suited to visualize how different proteins exert influence on each other upon their co-aggregation in live cells.

A little leak will sink a great ship! We prepared a series of multi-color protein aggregation sensors and developed a dual-color thermal shift assay to simultaneously and quantitatively report on protein co-aggregation of two different proteins.     

Oxidation of heme to beta- and delta-biliverdin by Pseudomonas aeruginosa heme oxygenase as a consequence of an unusual seating of the heme

The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO.     

Hyperpolarized 129Xe NMR investigation of multifunctional organic/inorganic hybrid mesoporous silica materials

An extensive study has been made on a series of multifunctional mesoporous silica materials, prepared by introducing two different organoalkoxysilanes, namely 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEPTMS) and 3-cyanopropyltriethoxysilane (CPTES) during the base-catalyzed condensation of tetraethoxysilane (TEOS), using the variable-temperature (VT) hyperpolarized (HP) 129Xe NMR technique. VT HP-129Xe NMR chemical shift measurements of adsorbed xenon revealed that surface properties as well as functionality of these AEP/CP-functionalized microparticles (MP) could be controlled by varying the AEPTMS/CPTES ratio in the starting solution during synthesis. Additional chemical shift contribution due to Xe-moiety interactions was observed for monofunctional AEP-MP and CP-MP as well as for bifunctional AEP/CP-MP samples. In particular, unlike CP-MP that has a shorter organic backbone on the silica surface, the amino groups in the AEP chain tends to interact with the silanol groups on the silica surface causing backbone bending and hence formation of secondary pores in AEP-MP, as indicated by additional shoulder peak at lower field in the room-temperature 129Xe NMR spectrum. The exchange processes of xenon in different adsorption regions were also verified by 2D EXSY HP-129Xe NMR spectroscopy. It is also found that subsequent removal of functional moieties by calcination treatment tends to result in a more severe surface roughness on the pore walls in bifunctional samples compared to monofunctional ones. The effect of hydrophobicity/hydrophilicity of the organoalkoxysilanes on the formation, pore structure and surface property of these functionalized mesoporous silica materials are also discussed.     

A new class of aromatic polybenzoxazoles containing ortho-phenylenedioxy groups

A series of poly(o-hydroxy amide)s having both ether and ortho-catenated phenylene unit in the main chain were synthesized via the low-temperature solution polycondensation of 4,4^′-(1,2-phenylenedioxy)dibenzoyl chloride and 4,4^′-(4-tert-butyl-1,2-phenylenedioxy)dibenzoyl chloride with three bis(o-aminophenol)s including 4,4^′-diamino-3,3^′-dihydroxybiphenyl, 3,3^′-diamino-4,4^′-dihydroxybiphenyl, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The poly(o-hydroxy amide)s exhibited inherent viscosities in the range of 0.23-0.96 dl/g. Most of the poly(o-hydroxy amide)s were soluble in polar organic solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) and could afford flexible and tough films by solution casting. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded polybenzoxazoles. However, the polybenzoxazoles were organic-insoluble except for those with the hexafluoroisopropylidene group. The polybenzoxazoles exhibited glass-transition temperatures (T_g) in the range of 200-232 °C by DSC and softening temperatures (T_s) of 250-256 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 500 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 546-606 °C in air and 574-631 °C in nitrogen.