Direct amino acid-catalyzed cascade reductive alkylation of arylacetonitriles: high-yielding synthesis of ibuprofen analogs

A novel approach for a one-pot, three-component reductive alkylation (TCRA) reaction of arylacetonitriles-containing electron-withdrawing groups with aldehydes/ketones and 1,4-dihydropyridine via iminium-catalysis has been developed. Many TCRA reaction products have direct applications in agricultural and pharmaceutical chemistry.     

光引发常规乳液聚合制备氨基聚苯乙烯纳米粒子

采用一种简单易行的方法制备了氨基功能化的聚苯乙烯纳米粒子.首先,采用4-乙烯基苄氯与1,3-丙二胺置换反应制备了含有氨基功能基团的可聚合单体N-(3-氨基丙基)对乙烯基苄基亚胺(CVPD).然后,采用乳液聚合,以苯乙烯(St)和CVPD为共聚单体,水溶性的4-(2-羟乙氧基)苯基-(2-羟基-2-丙基)酮(Irgacure 2959)为光引发剂,十六烷基三甲基溴化铵(CTAB)为乳化剂,经紫外光辐照引发,合成了P(St-co-CVPD)二元共聚物的纳米胶乳.体系的乳化剂用量仅为体系总质量的0.1 wt%～0.8 wt%,远小于常用来制备纳米粒子的微乳液体系的乳化剂用量.用透射电子显微镜(TEM)和激光粒度分析仪(DLS)表征了P(St-co-CVPD)纳米粒子的粒径和粒径分布.用红外光谱(FTIR)和核磁共振(NMR)证明了P(St-co-CVPD)纳米粒子上氨基的存在,并通过茚三酮显色反应定量检测了氨基含量.分别研究了单体配比,引发剂浓度,乳化剂用量以及紫外光强度对反应体系的影响.实验结果表明,产物粒子尺寸为30～600 nm,氨基通过共价键连接在粒子上,其含量为1.2×10-5～1.6×10-4 mol/g.该乳液体系聚合反应速率较快,单体转化率在60 min内即可达到80%.所得粒子的氨基含量可以通过单体配比进行调节.粒子尺寸可通过单体配比,引发剂浓度,乳化剂用量以及紫外光强度进行调节.     

温敏聚氨酯膜用于不同尺寸物质的选择性分离

通过湿法转相技术制备了温敏聚氨酯(thermal sensitive polyurethane,TSPU)膜,并用于氯化钠、甘氨酸和胶原蛋白等不同尺寸物质的选择性分离.示差扫描量热分析仪(DSC)和X射线衍射(XRD)分析表明,TSPU具有典型的嵌段结构(即软段和硬段),软段和硬段具有各自的结晶相及相态转变温度(将软段的相转变温度定义为开关温度,Ts).热台偏光显微镜观察表明,当温度低于Ts时,TSPU的软段具有较好的结晶形态,且为球晶型;但当温度超过Ts后,软段的结晶逐渐熔融、消失.运用扫描电镜(SEM)和原子力显微镜(AFM)对TSPU膜的形貌结构进行分析,结果表明,TSPU膜的表面(层)相对致密,且具有细小的微孔结构;截面为非对称的多孔结构,这种形态结构对TSPU膜的选择渗透性起决定性作用.通过测定湿膜干燥后的质量损失来计算膜的孔隙率发现,当温度从Ts-10℃升高到Ts+10℃时,膜的孔隙率从46.7%上升到65.3%,表现出明显的温敏特性.将TSPU膜用于氯化钠、甘氨酸和胶原蛋白分离时发现,尺寸较小的物质如钠离子和氯离子在低温下即可透过,且透过通量随温度的升高而增大.而中等尺寸甘氨酸的透过通量则呈现明显的温度依赖性,即低温时(TTs),由于存在栅栏效应,透过通量较小;高温时(TTs),甘氨酸的透过通量明显增大,显示出了温敏特性.胶原蛋白由于分子尺寸大,即使在开关温度以上,也不能透过TSPU膜.因此,利用TSPU膜的温敏特性,可以实现胶原蛋白、氨基酸、氯化钠等不同尺寸物质的选择性分离.     

硅基芯片表面化学性质对蛋白质固定化的影响

制备蛋白质芯片的关键在于将蛋白质固定到芯片表面并保持其生物学活性.本实验中,我们分别采用物理吸附、直接化学固定、加入间隔臂化学固定和生物亲和作用固定的方法将癌胚抗原(CEA)抗体固定到硅基芯片的二氧化硅表面.基于抗原-抗体的特异性相互作用,利用双抗体夹心酶联免疫法(ELISA)评价各种方法固定抗体的效果.实验结果表明,在修饰有氨基的表面采用戊二醛作为偶联试剂固定CEA抗体具有最高的偶联效率,引入多聚赖氨酸(poly-L-lysine)作为间隔臂可以显著增强固定效果,并可进一步降低非特异性吸附.而利用生物亲和作用固定CEA抗体也可获得较好的固定效果,但是非特异性吸附较严重.     

A Novel and Efficient Catalyst to One‐Pot Synthesis of 2‐Amino‐4H‐Chromenes by Methanesulfonic Acid

Methanesulfonic acid efficiently catalyzes the one‐pot, three component reaction of an aromatic aldehyde, malonitrile and α or β‐naphthol to yield 2‐amino‐4H‐chromenes in very good yields.     

Determination of primary amino acids in wines by high performance liquid magneto-chromatography

Eight amino acids (ethanolamine, glycine, alanine, β-aminobutyric acid, leucine, methionine, histidine and asparagine) were identified and quantified in Spanish wines by high performance liquid magneto-chromatography (HPLMC) with UV-V spectrophotometry. For this method, the amino acids are first complexed with mono(1,10-phenanthroline)-Cu(II) to confer them paramagnetic properties, and then separated by application of a low magnetic field intensity (5.5 mT) to the stationary phase contained in the chromatographic column. Principal components analysis of the results obtained grouped together the wine samples according to their denomination of origin: “Ribera del Duero”, “Rueda” or “Rioja” (Spain). Through cluster analysis, a series of correlations was also observed among certain amino acids, and between these groupings and the type of wine. These clusters were found to reflect the role played by the amino acids as primary or secondary nutrients for the bacteria involved in alcoholic and malolactic fermentation.     

Solvent-free synthesis of unsaturated amino esters in a ball-mill

The ball-milling technique was used under solvent-free conditions to perform a Horner-Wadsworth-Emmons reaction in the presence of a mild carbonate base. Starting from a phosphonate-substituted glycine, this method gave access to Boc-protected unsaturated amino esters in excellent yield and selectivity in many cases. The scope of the reaction was delineated.     

Synthetic Studies on Palau'amine. Construction of the Cyclopentane Core via an Asymmetric 1,3-Dipolar Cycloaddition

The cyclopentane core of palau’amine has been constructed in optically pure form through the use of an asymmetric azomethine ylid [1,3]-dipolar cycloaddition reaction.     

Substituted naphthoquinones as novel amino acid sensitive reagents for the detection of latent fingermarks on paper surfaces

In this paper, we present our preliminary studies into naphthoquinones as novel reagents for the detection of latent fingermarks on paper. Latent fingermarks deposited on paper substrates were treated with solutions of selected naphthoquinones in ethyl acetate/HFE-7100, with subsequent heating. The selected compounds were 1,4-dihydroxy-2-naphthoic acid, 1,2-naphthoquinone-4-sulfonate, 2-methoxy-1,4-naphthoquinone and 2-methyl-1,4-naphthoquinone. All of the tested compounds yielded purple-brown visible fingermarks, which also exhibited photoluminescence when illuminated with a high intensity filtered light source at 555 nm and viewed through red goggles. Indirect heat using an oven at 150 °C for 1 h was found to be superior to direct heat with an iron, which while providing faster development lead to increased levels of background colouration. Luminescence spectrophotometry revealed differences in photoluminescence characteristics for fingermarks developed with the different naphthoquinones, with excitation over the range 530-590 nm. Luminescence spectrophotometry of developed lysine, glycine and serine spots on paper was used to confirm that the naphthoquinones were reacting with amino acids in the latent fingermark.     

Systematic cyanobacterial membrane proteome analysis by combining acid hydrolysis and digestive enzymes with nano-liquid chromatography–Fourier transform mass spectrometry

The identification of membrane proteins is currently under-represented since the trans-membrane domains of membrane proteins have a hydrophobic property. Membrane proteins have mainly been analyzed by cleaving and identifying exposed hydrophilic domains. We developed the membrane proteomics method for targeting integral membrane proteins by the following sequential process: in-solution acid hydrolysis, reverse phase chromatographic separation, trypsin or chymotrypsin digestion and nano-liquid chromatography–Fourier transform mass spectrometry. When we employed total membrane proteins of Synechocystis sp. PCC 6803, 155 integral membrane proteins out of a predictable 706 were identified in a single application, corresponding to 22% of a genome. The combined methods of acid hydrolysis-trypsin (AT) and acid hydrolysis-chymotrypsin (AC) identified both hydrophilic and hydrophobic domains of integral membrane proteins, respectively. The systematic approach revealed a more concrete data in mapping the repertoire of cyanobacterial membrane and membrane-linked proteome.