Spin-labeled analogs of CMP-NeuAc as NMR probes of the alpha-2,6-sialyltransferase ST6Gal I

Structural data on mammalian proteins are often difficult to obtain by conventional NMR approaches because of an inability to produce samples with uniform isotope labeling in bacterial expression hosts. Proteins with sparse isotope labels can be produced in eukaryotic hosts by using isotope-labeled forms of specific amino acids, but structural analysis then requires information from experiments other than nuclear Overhauser effects. One source of alternate structural information is distance-dependent perturbation of spin relaxation times by nitroxide spin-labeled analogs of natural protein ligands. Here, we introduce spin-labeled analogs of sugar nucleotide donors for sialyltransferases, specifically, CMP-TEMPO (CMP-4-O-[2,2,6,6-tetramethylpiperidine-1-oxyl]) and CMP-4carboxyTEMPO (CMP-4-O-[4-carboxy-2,2,6,6-tetramethylpiperidinine-1-oxyl]). An ability to identify resonances from active site residues and produce distance constraints is illustrated on a (15)N phenylalanine-labeled version of the structurally uncharacterized, alpha-2,6-linked sialyltransferase, ST6Gal I.     

A theoretical study of the photodetachment and intramolecular hydrogen-bonding energies of hydrogen maleate anions

Three low-lying conformers of the hydrogen maleate anions (HMAs) regarding cis-HMA(HB) having the O-...HO intramolecular hydrogen bond (HB), cis-HMA(nHB) without the HB, and trans-HMA are studied by density functional theory (B3LYP) combined with natural bond orbital (NBO) and atoms-in-molecules (AIM) analyses. The photoelectron spectra of cis- and trans-HMA conformers recorded by Woo et al. (J. Phys. Chem. A 2005, 109, 10633) are reassigned on the basis of the present electron propagator theory calculations, indicating the significant energy differences between the Dyson orbitals and canonical molecular orbitals due to the electron-correlation and orbital relaxation effects considered in the electron propagator theory. The NBO associated with the natural resonance theory analyses and AIM electron topological study show that the strong O-...HO in cis-HMA(HB) has the remarkable characteristics of three-center four-electron hyperbond, and the bonding strength of ca. 30 kcal/mol is recommended with the reference calculations of the HO-...HOH complex. The further calculations for the microhydrated cis-HMA(HB) clusters indicate that the O-...HO bonding strength decreases in water solution.     

Mesoporous tungsten titanate as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of biomolecules

In this paper, mesoporous tungsten titanate (WTiO) with different nano-pore structures was utilized as matrix for the analysis of short peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Effect of characteristic features of mesoporous matrices on laser desorption/ionization process was investigated. Experiments showed that the ordered two-dimensional and three-dimensional mesoporous matrices were superior in performance to the non-ordered WTiO matrix. The dramatic enhancement of signal sensitivity by the ordered mesoporous matrices can be reasonably attributed to the ordered structure, which facilitated the understanding on structure-function relationship in mesoporous cavity for laser desorption process of adsorbed biomolecules. With the ordered mesoporous matrix, the short peptides are successfully detected. The presence of trace alkali metal salt effectively increased the analyte ion yields and the MALDI-TOFMS using the inorganic mesoporous matrices displayed a high salt tolerance. The developed technique also showed a satisfactory performance in peptide-mapping and amino-acid sequencing analysis.     

Submicron particles of SBA-15 modified with MgO as carriers for controlled drug delivery

Submicron particles with modified surface were synthesized by a simple one-pot synthesis approach and used as drug carrier for controlled release. Due to the alkalinity of MgO species on the surface, the amount of a model drug, ibuprofen, adsorbed on the modified surface was increased as compared to pure silica SBA-15 although the surface area was decreased by the surface modification. FTIR investigation indicated that the adsorption state of ibuprofen on MgO modified SBA-15 was different from that on pure silica SBA-15 and pure crystal ibuprofen. The result obtained from in vitro release test exhibited that the surface modification greatly decreased the ibuprofen release rate. In first 6 h in vitro release test, only 63% of the adsorbed ibuprofen was released from the MgO/SBA-15 (Si/Mg=20). In contrast, the release of ibuprofen was complete in 1 h from the pure silica SBA-15 under the same release conditions. The surface modified with MgO created affinity with acidic ibuprofen molecules and retarded the release rate from the mesoporous matrix. In addition, the release rate of ibuprofen could be modulated by varying the content of MgO, and was found to decrease with increasing amount of MgO on surface of SBA-15 submicron particles.     

A new synthesis method for benzo[f]quinolin‐3‐carbonyl urea and thiourea derivatives in aqueous media catalyzed by TEBAC

A clean and simple synthesis procedure for benzo[f]quinolin‐3‐carbonyl urea and thiourea derivatives was developed based on the reaction between N‐arylidenenaphthalen‐2‐amine and barbituric acid or thiobarbituric acid in aqueous media catalyzed by triethylbenzylammonium chloride (TEBAC). It was interesting that the structures of products in solvent of DMSO‐d₆ solution were different from those of the crystal states, which keep the enol form. The products were characterized by ¹H NMR, and ¹³C NMR, and the crystal state was confirmed by X‐ray diffraction study of 3e . In addition, water was chosen as green solvent.     

若丹明B荧光增强二硫化碳高阶受激喇曼散射

 利用若丹明B乙醇溶液的荧光改变了二硫化碳的一至三阶Stokes喇曼谱线的强度分布,选择性地增强了三阶Stokes喇曼谱线。在泵浦功率密度为~560MW^.cm^-2时,对染料摩尔浓度分别为~10^-5、cm^-5散射池和~10^-4、1cm散射池进行实验,观察到二硫化碳的三阶Stokes喇曼谱线与染料激光形成的共振增强现象及、二阶Stokes喇曼谱线的部分或完全耗尽。     

自由大气紫外光学通信的研究

本文对紫外日盲区光谱在近距离、保密通信中的应用进行了探讨 ,并建立了紫外光学通信原理实验系统。所描述的系统是以日盲区紫外光作为信息载体的 ,用被调制的低压汞蒸汽紫外放电灯作为发射器件 ,以日盲型滤光片和光电倍增管或日盲型紫外光电倍增管作为接收器件 ,以达到在任何时间和在任何气候下完成窄频带模拟或低速数字信号的传输。由于近地表大气臭氧层的吸收 ,所以传输距离被限制在一个较小的范围内 ,构成了短距离的、秘密的、安全的和抗干扰的通信系统 ,并且不需要传统意义上的天线。由于地球大气上层臭氧的吸收作用 ,阳光中的日盲区 (2 0 0～ 2 80 nm)辐射几乎无法到达地球表面 ,因此 ,采用这个波段的光学通信系统几乎不会受到太阳光的干扰。典型的大气臭氧浓度高度分布大约在距地表 2 5 km处达到最高值 ,在海平面处有一个较低的值。相对较低的浓度值来说 ,虽然紫外辐射传输有限 ,但是具有足够远的距离 ,同时可达到安全、秘密和抗干扰的目的     

光栅投影轮廓测量的系统标定技术

针对在光栅投影轮廓测量术中系统标定可操作性不强、精度不高的问题进行了全面的分析 ,在此基础上提出一种新的系统结构 ,并推导了物相关系。由于去掉了传统结构的平行和垂直两个约束条件 ,测量系统中摄像机和投影装置可以采取任意相对位置 ,操作十分灵活。对新系统提出了方便实用的标定方法 ,在其中引入了摄像机定标技术。应用该测量系统和标定技术进行实例检测 ,测量结果证明 :与传统方法相比 ,可操作性和检测精度得到了提高     

High-Accuracy Measurement of the Dispersion of Chirped Fiber Gratings

1　Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｆｉｂｅｒｇｒａｔｉｎｇｓａｒｅｐｒｏｖｅｄｔｏｂｅｏｎｅｏｆｔｈｅｍｏｓｔｉｍｐｏｒｔａｎｔｒｅｃｅｎｔｄｅｖｅｌｏｐｍｅｎｔｓｉｎｔｈｅｆｉｅｌｄｏｆｏｐｔｉｃａｌｆｉｂｅｒｔｅｌｅｃｏｍｍｕｎｉｃａｔｉｏｎｓａｎｄｓｅｎｓｉｎｇ .Ｔｈｅｙａｒｅｌｉｋｅｌｙｔｏｈａｖｅａｐｐｌｉｃａｔｉｏｎｉｎｔｗｏｍａｉｎａｒｅａｓ:ｄｉｓｐｅｒｓｉｏｎｃｏｍｐｅｎｓａｔｉｏｎｉｎｌｏｎｇ ｈａｕｌｆｉｂｅｒｎｅｔｗｏｒｋｓ[1,2 ]ａｎｄｗａｖｅｌｅｎｇｔｈｒｏｕｔｉｎｇｉｎｗ…     

基于计算机视觉的光学目标自动定位系统

本文运用计算机视觉检测技术,提出了一种新的光学目标自动定位系统,导出了自动定位数学模型,分析了定位精度.运用计算机视觉定位技术开发的ZYZ-620PCB自动定位钻机.定位钻孔精度优于25μm.实践表明,计算机视觉光学目标自动定位系统具有高精度、快速实时的优点,在工业领域必将有广泛的应用前景.