A novel high selectivity chemiluminescence sensor for fenvalerate based on double-sided hollow molecularly imprinted materials

Novel fenvalerate double-sided hollow molecularly imprinted microspheres (fenvalerate-DHMIMs) were fabricated by in situ polymerization with the help of mesoporous silica microspheres (MSMs) in this paper for the very first time. Scanning electron microscope was employed to characterize the surface morphology of the fenvalerate-DHMIMs. Taking advantage of the quenching effect of fenvalerate on the luminol-H(2)O(2)-NaOH chemiluminescence system, a new model was established to determine fenvalerate by a highly selective flow injection chemiluminescence method. The traditional flow-through cell was replaced by a novel Y-shaped column. The chemiluminescence intensity was linear with fenvalerate concentration over the range of 5.0 × 10(-8) to 2.0 × 10(-5) g mL(-1) and the detection limit was 2.2 × 10(-8) g mL(-1). The relative standard deviation (RSD) for the determination of 2.0 × 10(-6) g mL(-1) fenvalerate was 1.4% (n = 11). The proposed method was applied to the determination of fenvalerate in real samples with satisfactory results.     

A simple colorimetric detection of DNA methylation

In this work, we describe a simple colorimetric method to detect DNA methylation. Adenomatous polyposis coli (APC) with a small CpG region containing methylated cytosine (methylated APC) was synthesized and tested. Methylated APC was first captured and enriched by anti-5-methylcytosine monoclonal antibody conjugated magnetic microspheres (MMPs). Then a probe partly complementary to the APC sequence was added, resulting in the formation of DNA duplexes. The microsphere-captured probe was then released by heat denaturation and added into unmodified gold nanoparticle (AuNP) solution. Colorimetric detection was performed by salt-induced aggregation. The limit of detection is 80 fmol. Semi-quantitative analysis was done with a UV/Vis spectrophotometer by recording the absorbance of AuNP solution at 520 nm. Thus, this method provides a simple, rapid and quantitative tool for DNA methylation detection.     

Relative and Absolute Configuration of Vatiparol (1 mg): A Novel Anti‐inflammatory Polyphenol

Bioactive natural products offer multiple opportunities for the discovery of novel chemical entities with potential pharmaceutical, nutraceutical and agrochemical applications. Many new organic compounds with novel scaffolds are isolated in small quantities and established methods often fail to determine the structure and bioactivity of such novel natural products. To meet this challenge, we present here a new methodology combining RDC (residual dipolar coupling)‐based NMR spectroscopy in microtubes, with a motif‐inspired biological assessment strategy. Using only one milligram (ca. 1.5 μmol) of sample, the new protocol established the bioactivity as well as the relative and absolute configuration of vatiparol obtained from Vatica parvifolia. Vatiparol is unique in its unprecedented carbon skeleton and selective inhibitory effect on the expression of monocyte chemo‐attractant protein‐1 (MCP‐1, also known as CCL2). The plausible biosynthetic pathway of vatiparol is briefly discussed. The approach introduced here promises to be widely applicable to the determination of the structure and bioactivity of structurally unknown organic samples available in very limited amounts.     

ZnSe掺Cu与Zn空位缺陷的稳定性、电子结构与光学性质

采用基于密度泛函理论框架下的第一性原理平面波超软雁势方法, 对ZnSe闪锌矿结构本体、掺入p型杂质Cu(Zn_0.875Cu_0.125Se)及Zn空位(Zn_0.875Se)超晶胞进行结构优化处理. 计算并详细分析了缺陷体系的形成能和三种体系下ZnSe材料的态密度、能带结构、集居数、介电和吸收光谱. 结果表明: 在Zn空位与Cu掺杂ZnSe体系中, 由于空位及杂质能级的引入, 禁带宽度有所减小, 吸收光谱产生红移; 单空位缺陷结构不易形成, Zn_0.875Se结构不稳定, Cu掺杂ZnSe结构相对更稳定.     

工业色谱法分离制备7-木糖基-10-去乙酰紫杉醇酶解产物10-去乙酰紫杉醇

基于工业色谱法分离制备抗癌药物紫杉醇的半合成前体10-去乙酰紫杉醇(10-DAP)。7-木糖基-10-去乙酰紫杉醇(10-DAXP)在我国特有红豆杉品系(中华红豆杉)枝叶中含量丰富,以其为原料可制备紫杉醇最理想的半合成前体——10-DAP。本研究以部分纯化后的7-木糖基-10-去乙酰紫杉烷为原料,通过β-木糖苷酶水解该粗提物中的主要成分10-DAXP及其两个微量类似物7-木糖基-10-去乙酰三尖杉宁碱(10-DAXC)和7-木糖基-10-去乙酰紫杉醇C(10-DAXP C),脱去其C-7位上的木糖基,水解产物采用大孔吸附树脂吸附,正相快速柱分离和反相制备色谱分离,可获得高纯度的目标物10-DAP,产物纯度为96%,整个工艺的收率大于75%。该方法适合以10-DAXP为原料大规模制备紫杉醇的半合成前体化合物10-DAP,为工业化生产紫杉醇开辟了一条新途径。     

发射光谱研究多针对板电晕放电O活性原子特性

利用发射光谱技术在大气压下测量了空气中多针对板负直流电晕放电和正电晕流光放电产生的O(3p5 P→3s 5 S02777.4nm)活性原子发射光谱。在负电晕放电中,研究了放电功率、电极间距、N2含量和相对湿度等因素对O活性原子产生过程的影响;在正电晕流光放电阶段,研究了O活性原子相对密度在放电反应空间的分布特点。结果表明:O活性原子产量随放电功率的增加而增大,随电极间距增大而减少,随相对湿度和氮气含量的增加,其产量先增大后减少;O活性原子相对密度沿针尖轴向呈先增大后减小的趋势。     

Anisotropic isoparametric hypersurfaces in Euclidean spaces

In this paper, by Nomizu’s method and some technical treatment of the asymmetry of the F-Weingarten operator, we obtain a classification of complete anisotropic isoparametric hypersurfaces, i.e., hypersurfaces with constant anisotropic principal curvatures, in Euclidean spaces, which is a generalization of the classical case for isoparametric hypersurfaces in Euclidean spaces. On the other hand, by an example of local anisotropic isoparametric surface constructed by B. Palmer, we find that in general anisotropic isoparametric hypersurfaces have both local and global aspects as in the theory of proper Dupin hypersurfaces, which differs from classical isoparametric hypersurfaces.     

Optimal constant weight covering codes and nonuniform group divisible 3-designs with block size four

Let K _q (n, w, t, d) be the minimum size of a code over Z _q of length n, constant weight w, such that every word with weight t is within Hamming distance d of at least one codeword. In this article, we determine K _q (n, 4, 3, 1) for all n ≥ 4, q = 3, 4 or q = 2 ^m  + 1 with m ≥ 2, leaving the only case (q, n) = (3, 5) in doubt. Our construction method is mainly based on the auxiliary designs, H-frames, which play a crucial role in the recursive constructions of group divisible 3-designs similar to that of candelabra systems in the constructions of 3-wise balanced designs. As an application of this approach, several new infinite classes of nonuniform group divisible 3-designs with block size four are also constructed.     

Synthesis of three novel anionic gemini surfactants and comparative studies of their assemble behavior in the presence of bovine serum albumin

Three novel anionic sulfonate gemini surfactants, sodium 4,4'-(10,19-dioxo-9,11,18,20-tetraazaoctacosane-9,20-diyl) dibenzenesulfonate (Surfactant I), sodium 4,4'-(12,21-dioxo-11,13,20,22-tetraazadotriacontane-11,22-diyl) dibenzenesulfonate (Surfactant II), and sodium 4,4'-(14,23-dioxo-13,15,22,24-tetraazahezatriacontane-13,24-diyl) dibenzenesulfonate (Surfactant III), with different lengths of hydrophobic tail have been synthesized, and their assembly behavior in the presence of bovine serum albumin (BSA) has been studied using spectral methods and molecular modeling methods at physiological pH and 298 K. Critical micelle concentrations (CMCs) of the three surfactants have been determined by surface tension measurements. Despite the obvious decrease of CMC with the increase of tail length, fluorescence spectra have shown much closer CAC in the presence of BSA. Surfactant II shows the highest CAC of 3.19 × 10(-5) mol L(-1) compared with the other two. The polarity of the microenvironment in BSA-surfactant systems has been investigated using pyrene as the probe. In addition, far-UV CD spectra studied the change of the secondary structure content of BSA caused by the three surfactants. The features of the assembly behavior were discussed by three concentration regions. Surfactant II could unfold the protein much more efficiently than the other two surfactants at low concentration, but at high concentration, the change of the secondary structure and the formation of hydrophobic microenvironment show a direct relationship to the length of the hydrophobic tail with the increase of the surfactant concentration.