Binding of high-mannose-type oligosaccharides and synthetic oligomannose clusters to human antibody 2G12: implications for HIV-1 vaccine design

Human antibody 2G12 broadly neutralizes human immunodeficiency virus type 1 (HIV-1) isolates and shows protective activity against viral challenge in animal models. Previous mutational analysis suggested that 2G12 recognized a novel cluster of high-mannose type oligosaccharides on HIV-1 gp120. To explore the carbohydrate antigen for HIV-1 vaccine design, we have studied the binding of 2G12 to an array of HIV-1 high-mannose type oligosaccharides by competitive ELISAs and found that Man9GlcNAc is 210- and 74-fold more effective than Man5GlcNAc and Man6GlcNAc in binding to 2G12. The results establish that the larger high-mannose oligosaccharide on HIV-1 is the favorable subunit for 2G12 recognition. To mimic the putative epitope of 2G12, we have created scaffold-based multivalent Man9 clusters and found that the galactose-scaffolded bi-, tri-, and tetra-valent Man9 clusters are 7-, 22-, and 73-fold more effective in binding to 2G12 than the monomeric Man9GlcNAc2Asn. The experimental data shed light on further structural optimization of epitope mimics for developing a carbohydrate-based HIV-1 vaccine.     

Study on open tubular capillary affinity liquid chromatography

A novel mode of affinity chromatography (AC) based on an open tubular capillary column (OTAC) is demonstrated. The OTAC column is prepared by immobilizing Cibacron blue F3GA onto the inner surface of a 50-microm-i.d. capillary column. The AC experiment is performed on a capillary electrophoresis instrument by using its pressure system as the driving force. Bovine serum albumin and lysozyme (Lys) are successfully separated with stepwise gradient elution. The relative standard deviation (RSD) for the elution time of the retained Lys is 0.08%, and good repeatability of its peak area and peak height with an RSD value lower than 2.12% for 10 consecutive runs is observed. The loading capacity and detection limit for the retained Lys are approximately 36 ng and 8.6 ng, respectively. It is also found that the amount of protein adsorbed is unaffected by the flow rate of the loading buffer, and OTAC can be used for the fast determination of biopolymers. Some of the advantages of OTAC over conventional modes of open tubular capillary liquid chromatography are that the detection sensitivity and loading capacity of a sample can be greatly improved, because the relatively large inner diameter of the capillary can be adopted and the whole capillary column can be used to adsorb the solute in OTAC.     

简法合成甲地孕酮

本文报道了合成甲地孕酮的简便方法,即以17α-乙酰氧基-黄体酮(3)为原料,将其烯醇醚(4)经Mannich反应,或将△~(3,5)-3,17α-二乙酰氧基-黄体酮(2)与二乙氧基甲烷反应,生成6-次甲基-17α-乙酰氧基-黄体酮(5),然后将5用钯/碳酸钙作催化剂转位得目的物甲地孕酮(6b),总收率分别为56%和50%(均以17α-羟基-黄体酮(1)为起始物)。     

Photoisomerization and photodissociation of aniline and 4-methylpyridine

Photoisomerization and photodissociation of aniline and 4-methylpyridine at 193 nm were studied separately using multimass ion imaging techniques. Photofragment translational energy distributions and dissociation rates were measured. Our results demonstrate that more than 23% of the ground electronic state aniline and 10% of 4-methylpyridine produced from the excitation by 193 nm photons after internal conversion isomerize to seven-membered ring isomers, followed by the H atom migration in the seven-membered ring, and then rearomatize to both methylpyridine and aniline prior to dissociation. The significance of this isomerization is that the carbon, nitrogen, and hydrogen atoms belonging to the alkyl or amino groups are involved in the exchange with those atoms in the aromatic ring during the isomerization.     

Total synthesis of crotophorbolone

As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C₂₀ and C₄.

Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids.     

纳米晶复合Nd2Fe14B/α-Fe合金制备与磁性能的研究

采用熔体快淬及晶化处理工艺制备Nd11Fe71Co8V1.5Cr1B7.5纳米晶合金。经21m·s-1快淬及640℃ 4min晶化处理后,制成的粘结磁体的磁性能最佳,为:Br=0.64T,JHc=903.5kA·m-1,(BH)max=71kJ·m-3。添加Cr元素可提高内禀矫顽力,从而提高最大磁能积。     

Synthesis and crystallization kinetics of the novel ion exchanger Na<Subscript>4</Subscript>Ti<Subscript>4</Subscript>Si<Subscript>3</Subscript>O<Subscript>10</Subscript> for cesium removal

Thermodynamics and crystallization kinetics of the hydrothermal synthesis of Na₄Ti₄Si₃O₁₀ (NaTS) were systemically studied by both experiments and model simulation. Experimental results showed that the curve of crystallinity with time was a characteristic signmoid in the shape that indicated the crystallization of Na₄Ti₄Si₃O₁₀ was a typical spontaneous nucleation process on the laboratory scale. Crystallization of NaTS belongs to the liquid-liquid transformation mechanism and the reaction is endothermic (ΔH = 15.3 kJ/mol). A mathematic model of crystallization kinetics was developed to simulate the synthesis of NaTS. Runge-Kutta and simplex methods were adopted to solve the partial differential equations. Model results fitted well with the experimental data and showed that the synthesis process belongs to spontaneous nucleation and crystal growth. Moreover, the very small crystal growth constant (5.6·10⁻⁷) and gel dissolution constant (7.0·10⁻⁷) indicate they are the rate-limiting steps of the whole synthesis process.     

Effects of double substitution on the thermodynamic stabilities of nitrogen radicals

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Nucleation mechanisms and speciation of metal oxide clusters

The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. We present a new computational methodology that identifies the reaction mechanism for the formation of metal-oxide clusters and provides a speciation model from first-principles and in an automated manner. As a first example, we apply our method to the formation of octamolybdate. In our model, we include variables such as pH, temperature and ionic force because they have a determining effect on driving the reaction to a specific product. Making use of graphs, we set up and solved 2.8 × 10⁵ multi-species chemical equilibrium (MSCE) non-linear equations and found which set of reactions fitted best with the experimental data available. The agreement between computed and experimental speciation diagrams is excellent. Furthermore, we discovered a strong linear dependence between DFT and empirical formation constants, which opens the door for a systematic rescaling.

The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. The POMSimulator deals with that complexity in an automated manner.     

Transparent conducting oxides: texture and microstructure effects on charge carrier mobility in MOCVD-derived CdO thin films grown with a thermally stable, low-melting precursor

A series of low-melting, thermally stable cadmium metal-organic chemical vapor deposition (MOCVD) precursors have been synthesized, structurally and spectroscopically characterized, and implemented in growth of highly conductive and transparent CdO thin films. One member of the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N-diethyl-N',N'-dimethyl-ethylenediamine)cadmium(II), Cd(hfa)(2)()(N,N-DE-N',N'-DMEDA), represents a particularly significant improvement over previously available Cd precursors, owing to the low melting point and robust thermal stability. High-quality CdO films were grown by MOCVD on glass and single-crystal MgO(100) between 300 and 412 degrees C. Film growth parameters and substrate surface have large effects on microstructure and electron carrier transport properties. Enhanced mobilities observed for highly biaxially textured films grown on MgO(100) vs glass are attributed, on the basis of DC charge transport and microstructure analysis, to a reduction in neutral impurity scattering and/or to a more densely packed grain microstructure. Although single-grained films grown on MgO(100) exhibit greater mobilities than analogues with discrete approximately 100 nm grains and similar texture, this effect is attributed, on the basis of charge transport and Hall effect measurements as well as optical reflectivity analysis, to differences in carrier concentration rather than to reduced grain boundary scattering. Unprecedented conductivities and mobilities as high as 11,000 S/cm and 307 cm(2)/V.s, respectively, are obtained for epitaxial single-grained films (X-ray diffraction parameters: fwhm(omega) = 0.30 degrees, fwhm(phi) = 0.27 degrees ) grown in situ on MgO(100) at a relatively low temperature (400 degrees C).