Synthesis of Sulfotyrosine‐Containing Peptides by Incorporating Fluorosulfated Tyrosine Using an Fmoc‐Based Solid‐Phase Strategy

Tyrosine O‐sulfation is a common protein post‐translational modification that regulates many biological processes, including leukocyte adhesion and chemotaxis. Many peptides with therapeutic potential contain one or more sulfotyrosine residues. We report a one‐step synthesis for Fmoc‐fluorosulfated tyrosine. An efficient Fmoc‐based solid‐phase peptide synthetic strategy is then introduced for incorporating the fluorosulfated tyrosine residue into peptides of interest. Standard simultaneous peptide‐resin cleavage and removal of the acid‐labile side‐chain protecting groups affords the crude peptides containing fluorosulfated tyrosine. Basic ethylene glycol, serving both as solvent and reactant, transforms the fluorosulfated tyrosine peptides into sulfotyrosine peptides in high yield.     

Enhancing separation in short‐capillary electrophoresis via pressure‐driven backflow

We present a novel easy‐to‐operate and efficient method to improve the separation efficiency in short‐capillary electrophoresis by introducing steady backflow to counterbalance electro‐osmotic flow without the use of any external pressure. The backflow was easily generated by tapering the capillary end, which was achieved by heating a straight capillary and stretching it with a constant force. We investigated the net fluidic transport rate under different tip lengths and separation voltages. Good run‐to‐run repeatability and capillary‐to‐capillary reproducibility of the present method were obtained with RSD less than 1.5%, indicating the stability of the fluid transport rate in the tapered capillary, which ensures the quantification and repeatability of capillary zone electrophoresis (CZE) analysis. Enhanced separation of the tapered short capillary electrophoresis was demonstrated by CZE analyzing amino acids and positional isomers. Baseline separations were achieved in less than 60 s using a tapered capillary with the effective length of 5 cm, while no separation was achieved using a normal capillary without a tapered tip. The present study provides a promising method to use pressure‐driven backflow to enhance separation efficiency in short‐capillary electrophoresis, which would be of potential value in a wide application for fast analysis of complex samples.     

通过FeOx修饰Pd/Al2O3催化剂提高催化1,3-丁二烯加氢活性和选择性

石油脑裂解制备的烯烃流中通常含有 ～1％ 二烯烃或者炔烃,其含量必须降低到10 ppm以下以避免其对下游聚合催化剂的毒化作用.对这些副产物选择性加氢生成单烯烃是降低其含量最有前景的方法.Pd基催化剂具有高的加氢活性和选择性,是目前最为常用的加氢催化剂,但是它也存在高转化率下选择性较低和容易因积碳而失活的问题.合成Pd基双金属催化剂和对Pd催化剂进行氧化物包裹是目前最为常用的方法,但是这两种方法往往在提高选择性的同时,降低了Pd催化剂的加氢活性.本文利用原子层沉积(ALD)FeOx修饰Pd/Al2O3催化剂,在提高Pd催化剂选择性的同时,1,3-丁二烯选择性加氢活性也得到提高.表征结果发现,该样品中Pd负载量为1％,Fe负载量则随着原子层沉积FeOx周期增加而逐渐增加;催化剂中Pd颗粒大小约为7 nm,其表面并未观察到FeOx覆盖层;Pd,Fe元素分布表明FeOx在Pd颗粒表面生长.CO红外漫反射光谱也发现,随着ALD FeOx周期的增加,CO在Pd颗粒表面的吸附特征峰强度逐渐降低,表明FeOx逐渐覆盖Pd颗粒表面;与此同时,随着FeOx包裹周期的增加,CO吸附在Pd(111)面的特征吸收峰相对于其吸附在边角位的特征峰,降低得更为明显.这表明FeOx优先覆盖Pd(111)面,而选择性地将Pd低配位点暴露,与ALD Al2O3包裹Pd颗粒的结果恰恰相反.X射线光电子能谱分析表明,在所有催化剂中Fe均以+3价形式存在;同时,因为Pd-FeOx间存在强相互作用,所以随着FeOx包裹周期的增加,金属态Pd逐渐向高结合能方向移动,使表面Pd处于缺电子状态.随后,我们对不同FeOx周期包裹Pd催化剂进行了1,3-丁二烯加氢活性测试.在25 oC时Pd/Al2O3催化1,3-丁二烯转化率为6.7％;随着温度升高,转化率逐渐上升,至43 oC时达100％.相反,在26 oC时,30Fe/Pd/Al2O3对1,3-丁二烯的转化率为45％,远高于Pd/Al2O3催化剂;这可能是因为缺电子的Pd或Pd-FeOx界面存在所致.Pd/Al2O3催化剂在较低的转化率(<75％)下,1-丁烯、反式-2-丁烯和顺式-2-丁烯选择性分别为74％,20％和6％;随着转化率的增加(75％～90％),1-丁烯选择性急剧下降,丁烷选择性快速上升,反/顺-2-丁烯选择性也略有增加,表明此时次级反应1-丁烯加氢占主导,同时伴随着1-丁烯异构化反应;当转化率继续增加(>90％),1-丁烯,反/顺-2-丁烯加氢生成丁烷为主要反应,此时丁烷选择性急剧上升,至转化率为99％时,丁烯选择性仅为52％.而当Pd催化剂表面存在FeOx时,丁烯选择性随着FeOx周期增加而逐渐增加,尤其是在较高转化率下(>75％);对于30Fe/Pd/Al2O3催化剂,转化率为99％时,丁烯选择性高达95％.这主要是因为在高转化率下,FeOx将Pd颗粒表面分割成较小的Pd团簇,降低了Pd颗粒表面吸附氢气浓度,抑制了丁烯加氢反应,而次级反应1-丁烯异构化占主导,使得丁烯选择性不变.     

Transient holographic grating in azo-dye-doped liquid crystals with off-resonant light

Holographic gratings in nematic liquid crystals doped with Disperse Red 1 (DR1) were investigated using a linearly polarised He–Ne laser. Although the electric transitions of the samples were almost off-resonant, the diffraction of the transient holographic grating was found to exhibit a sinusoidal feature with changing the polarisation of recording beams, and the diffraction intensities and response time of the gratings were strongly dependent on DR1 concentration. The results revealed that the diffraction of holographic grating depends on the rate of trans–cis isomerisation of DR1 molecules. Moreover, the temperature dependence of diffraction indicated that the grating formation mechanism was attributed to photoinduced reorientation of photoisomerisation effect.     

单光子计数探测系统的线性性能研究

利用单光子计数技术对微弱光进行探测具有与其他模拟法相比的多个优势,如有好的抗漂移性、高的信噪比、较宽的线性区等。线性性能是探测器的基本性能之一,利用叠加法和距离平方反比法测量单光子计数探测系统的线性范围,当非线性因子为0.05时,利用叠加法实验测得系统线性响应计数率为3.9×10~5 Counts/s,利用距离平方反比法实验测得系统线性响应计数率为5×10~5 Counts/s。结果表明,两种方法测得响应线性度一致性较好。分析了电子学系统的漏计误差对探测器系统线性范围的影响。实验表明,通过缩短电子学系统中甄别器的死区时间(td)可以提高系统的线性范围。     

一种机械式电表读数区域的自动定位方法

针对电表读数区域自动定位这一关键技术的具体应用,提出了一种适合四种类型机械式电表的读数区域自动定位算法;采用同态滤波增加图像前景与背景之间的亮度差异,同时利用改进的Bersen算法,有效的将电表前景与背景分开;利用区域定位对图像进行粗定位,并对粗定位区域纵向投影,根据目标字符的纹理特征和先验知识对目标区域精确定位;经实验证明,该算法对其中四种电表图像的适应性良好。     

移动周期载荷作用下孔隙热弹性地基的动力学响应

根据孔隙热弹性线性理论,本文首先建立了在移动周期载荷作用下孔隙热弹性地基动力学响应分析的数学模型,其中提出了在周期性边界上必须满足的6类适当的条件,即界面位移相等、应力相等、孔隙百分比相等、温度相等以及在外法线方向孔隙发展相等和温度导数相等。在此基础上,分别采用微分求积法(DQM)和有限差分法(FDM)对控制方程进行空间和时间离散,并求解。作为算例,分别研究了在移动周期载荷和极限车载作用下孔隙热弹性地基的动力学响应,考察了车速对沉降、孔隙体积百分比和温度的影响。可以看到,本文提出的处理周期性问题DQM,具有精度高、收敛性好,计算效率高等特点。     

温度对季节性冻土水分迁移的影响研究

寒区季节性冻土冻胀性质对工程实际影响很大。为了了解温度对水分迁移现象的影响,本文通过地温测试仪对野外不同深度处的土层温度进行测量,并在不同时间相应深度取土样,测其含水率,通过比较不同时间不同深度处的含水率的变化情况来分析温度变化对水分迁移现象的影响。在气温回升之前,当地表温度降低时,温度随深度的降低而升高; 随着地表温度不断降低,各深度处的温度也不断下降,温度梯度增加,各深度处地层的含水率变化大,即温度梯度的增加促进了季节性冻土区水分迁移现象的发生。     

Synthesis of a “Butterfly Cage” Based on a Double‐Decker Silsesquioxane

Novel polyhedral structures were prepared with a butterfly‐shape composed of oligosiloxane wings and a double‐decker silsesquioxane (DDSQ) body. The compounds were synthesized in two steps from commercially available alkoxysilanes, and their structures were confirmed using spectroscopic methods and X‐ray crystallography. Not like other phenyl‐substituted cage silsesquioxanes, these butterfly cages show very good solubility in common organic solvents. The crystal structures clearly showed their unique features: a larger space with longer siloxane chains and a very flexible framework. Moreover, these compounds are thermally stable with a Td₅ (5 % weight loss temperature) over 320 °C.