Carbon-Filled Polymer Paste Ion-Selective Probes

Abstract

Inexpensive, disposable, carbon-filled polymer paste electrodes activated by a superficial layer of electro-active powder are reported. Sensors for silver, copper, lead and cadmium, halides, nitrate, pH and redox were thus prepared.     

Tailoring the Properties of Optical Force Probes for Polymer Mechanochemistry

The correlation of mechanical properties of polymer materials with those of their molecular constituents is the foundation for their holistic comprehension and eventually for improved material designs and syntheses. Over the last decade, optical force probes (OFPs) were developed, shedding light on various unique mechanical behaviors of materials. The properties of polymers are diverse, ranging from soft hydrogels to ultra-tough composites, from purely elastic rubbers to viscous colloidal solutions, and from transparent glasses to super black dyed coatings. Only very recently, researchers started to develop tailored OFP solutions that account for such material requirements in energy (both light and force), in time, and in their spatially detectable resolution. We here highlight notable recent examples and identify future challenges in this emergent field.     

Structure of Polymer Brushes in Cylindrical Tubes: A Molecular Dynamics Simulation

Summary: Molecular dynamics simulations of a coarse‐grained bead‐spring model of flexible macromolecules tethered with one end to the surface of a cylindrical pore are presented. Chain length N and grafting density σ are varied over a wide range and the crossover from “mushroom” to “brush” behavior is studied for three pore diameters. The monomer density profile and the distribution of the free chain ends are computed and compared to the corresponding model of polymer brushes at flat substrates. It is found that there exists a regime of N and σ for large enough pore diameter where the brush height in the pore exceeds the brush height on the flat substrate, while for large enough N and σ (and small enough pore diameters) the opposite behavior occurs, i.e. the brush is compressed by confinement. These findings are used to discuss the corresponding theories on polymer brushes at concave substrates.

Snapshot picture of a brush grafted inside of a cylinder, for , , displaying different chains in distinct colors in order to be able to distinguish them. Top shows a side view of the cylinder, and the lower part a view of the cross‐section. Note that the particles forming the cylindrical wall are not displayed.     

Development of Lysosome-Targeted Fluorescent Probes for Cys by Regulating the Boron-dipyrromethene (BODIPY) Molecular Structure

Our previous discovery suggested that substituents on the 1,7 positions delicately modulate the sensing ability of the meso-arylmercapto boron-dipyrromethene (BODIPY) to biothiols. In this work, the impact of delicate modulations on the sensing ability is investigated. Therefore, 1,7-dimethyl, 3,5-diaryl substituted BODIPY is designed and developed and its conformationally restricted species with a meso-arylmercapto moiety ( DM-BDP-SAr and DM-BDP-R-SAr ) as selective fluorescent probes for Cys. Moreover, the lysosome-target probes ( Lyso-S and Lyso-D ) based on DM-BDP-SAr carrying one or two morpholinoethoxy moieties were developed. They were able to detect Cys selectively in vitro with low detection limits. Both Lyso-S and Lyso-D localized nicely in lysosomes in living HeLa cells and exhibited red fluorescence for Cys. Moreover, a novel fluorescence quenching mechanism was proposed from the calculations by density functional theory (DFT). The probes may go through intersystem crossing (from singlet excited state to triplet excited state) to result in fluorescence quenching.     

无机聚合絮凝剂的结构研究

本文用广角度Ｘ射线散射（ＷＡＸＳ）和径向分布函数（ＲＤＦ）方法对聚合硅硫酸铝钾ＴＸ２０３絮凝剂的结构进行了分析。ＷＡＸＳ和ＲＤＦ分析指出：该絮凝剂是一种有序尺寸（Ｄ）约为２２～２５Ａ非晶固体。它是由有序周期（ｒ、）≌１２－１４Ａ的中程有序畴组成的,而这些有序畴又是由三种结构单元,即四面体「ＳＯ４」,「ＡｌＯ４」（０＝Ｏ,ＯＨ）和八面体「ＡｌＯ６」（Ｏ＝Ｏ,ＯＨ）组成的。Ｄ／ｒ１＝２～３,因此ＴＸ２     

VPO催化剂上丙烷选择氧化反应机理的分子探针研究

ＶＰＯ催化剂上丙烷选择氧化反应机理的分子探针研究赵如松，徐铸德（浙江大学化学系，杭州３１００２７）关键词ＶＰＯ催化剂，丙烷，选择氧化，分子探针，反应机理最近研究［１－２］表明，Ｃ３０在ＶＰＯ催化剂上可直接选择氧化成丙烯酸和乙酸。这种工艺与现行烯烃为原...     

Novel Color-Shifting Mobility Sensitive Fluorescent Probes for Polymer Characterization

1-Methyl-7-dimethylamino quinolinium tetrafluoroborate, a highly stable, highly fluorescent color-shifting mobility sensitive fluorescent probe was employed for detecting the glass transition and phase transitions, notably crystallization, in polymers and polymer blends. Glass transitions in amorphous and semi-crystalline polymers were detected by a change in gradient in emission wavelength λ_max versus T plots. Crystallization resulted in discrete blue shifts in λ_max versus T plots. Selective probing of PMMA in a PS/PMMA blend, down to a PMMA content of 1%, was demonstrated. Dielectric relaxation spectroscopy has established a clear link between the mobility of dipoles in PMMA and the emission wavelength of the fluorescent probe.     

拉伸分子动力学方法研究高分子单链的吸附现象

采用拉伸分子动力学方法研究聚乙烯单链从一个强吸附表面被拉伸的动力学过程.当聚乙烯单链被拉伸时,从理想弹簧测量到的平均力与形变的曲线上出现了一个力的平台,这与实验结果非常一致.在研究这个平台力与拉伸速度的关系时发现,当速度v<0.001 nm/ps时,不随速度的变化而变化;当速度v>0.001 nm/ps时,随着拉伸速度的增加而迅速上升,这表明拉伸速度0.001 nm/ps是平衡态拉伸和非平衡态拉伸的临界点,并与链长无关.按顺序拉伸和释放这条链,观察到有趣的力回滞现象,并与实验结果进行了比较.     

纳米粒子填充聚合物体系中凝聚结构和渗流转变的分子动力学模拟

通过粗粒化模型,采用分子动力学模拟的方法研究了纳米粒子填充聚合物体系中粒子的凝聚过程.结果表明:纳米粒子和基体粒子间的相互作用决定了团聚体的结构,且作用力越大则团聚体的分形维数越高,当粒子的相互作用强度(εNP)为1.0时,模拟体系中团聚体的分形维数为2.05,与聚酰亚胺炭黑体系透射电镜照片结果一致.对渗流过程的模拟结果表明,相互作用力的增大会导致渗流时间的增加,渗流转变速率减慢,与动态电渗流实验的实测结果相符合.     

Improved Cathepsin Probes for Sensitive Molecular Imaging

Cysteine cathepsin proteases are found under normal conditions in the lysosomal compartments of cells, where they play pivotal roles in a variety of cellular processes such as protein and lipid metabolism, autophagy, antigen presentation, and cell growth and proliferation. As a consequence, aberrant localization and activity contribute to several pathologic conditions such as a variety of malignancies, cardiovascular diseases, osteoporosis, and other diseases. Hence, there is a resurgence of interest to expand the toolkit to monitor intracellular cathepsin activity and better ascertain their functions under these circumstances. Previous fluorescent activity-based probes (ABPs) that target cathepsins B, L, and S enabled detection of their activity in intact cells as well as non-invasive detection in animal disease models. However, their binding potency is suboptimal compared to the cathepsin inhibitor on which they were based, as the P1 positive charge was capped by a reporter tag. Here, we show the development of an improved cathepsin ABP that has a P1 positive charge by linking the tag on an additional amino acid at the end of the probe. While enhancing potency towards recombinant cathepsins, the new probe had reduced cell permeability due to additional peptide bonds. At a second phase, the probe was trimmed; the fluorophore was linked to an extended carbobenzoxy moiety, leading to enhanced cell permeability and superb detection of cathepsin activity in intact cells. In conclusion, this work introduces a prototype design for the next generation of highly sensitive ABPs that have excellent detection of cellular cathepsin activity.     

Molecular Probes for Imaging Fibrosis and Fibrogenesis

Fibrosis, or the accumulation of extracellular matrix molecules that make up scar tissue, is a common result of chronic tissue injury. Advances in the clinical management of fibrotic diseases have been hampered by the low sensitivity and specificity of noninvasive early diagnostic options, lack of surrogate end points for use in clinical trials, and a paucity of noninvasive tools to assess fibrotic disease activity longitudinally. Hence, the development of new methods to image fibrosis and fibrogenesis is a large unmet clinical need. Herein, an overview of recent and selected molecular probes for imaging of fibrosis and fibrogenesis by magnetic resonance imaging, positron emission tomography, and single photon emission computed tomography is provided.     

金属配位模板聚合物的分子识别特性的研究

以Ｃｏ（Ⅱ）和敌鼠配合物为模板,４－乙烯吡啶为功能基单体,乙二醇二甲基丙烯酸酯为交联剂,采用分子印迹技术,合成了具有类似于金属螯合抗体结合位点的金属配位模板聚合物。系统研究了金属离子对模板聚合物靠拢性结构敌鼠的调节作用。     

生物小分子巯基化合物荧光探针研究进展

细胞内的小分子巯基化合物在诸多生理过程中扮演重要角色.分子荧光探针具有灵敏度高、选择性好、生物相容性好、实时原位监测等优点.因此,构建可以选择性检测巯基化合物的荧光探针具有重要的生物学和医学意义.根据荧光探针与巯基化合物的反应类型总结了近几年来小分子巯基化合物荧光探针的设计策略和研究进展.     

双甘氨肽分子印迹聚合物微球的吸附性能研究

以双甘氨肽(Gly-Gly)为印迹分子,丙烯酰胺(AM)、二甲基丙烯酸乙二醇酯(EDMA)分别作为功能单体和交联剂,在低温条件下采用乳液聚合于水相中制备了双甘氨肽分子印迹聚合物微球(Gly-Gly-MIPMs)。通过静态、动态平衡吸附和薄层色谱(TLC)分离实验,研究了Gly-Gly-MIPMs的选择吸附性能,并进行了Scatchard模型分析。结果表明,Gly-Gly-MIPMs对Gly-Gly分子具有较好的特异性吸附,最大单位饱和吸附量0.428mmol/g,印迹因子2.19。     

Molecular Dynamics Study of Star Polymer Melts under Start-up Shear

Chinese Journal of Polymer Science - It has been established that star polymers with a large number of arms display both the conventional chain relaxation and a slower interchain relaxation due to...     

碳酸酐酶靶向探针的研究进展

碳酸酐酶作为一类在肿瘤中高表达的酶, 参与肿瘤组织中乏氧、 微酸性等环境的调节, 已成为肿瘤诊断与治疗的一类重要靶点. 本文简要概述了碳酸酐酶的生物学功能, 并总结了目前针对碳酸酐酶所构建的不同类型的分子探针, 以及其在肿瘤成像与治疗应用中的研究进展. 最后, 对靶向碳酸酐酶探针研究所面临的挑战和未来可能的研究方向进行了展望.     

偶氮苯聚合物(PGMAA-20)膜光栅结构的分子取向机制

设计合成及表征了一种含偶氮苯聚合物(PGMAA 20)材料.利用两束S偏振光作为泵浦光在PGMAA 20膜上刻写光栅并观察光栅的衍射信号;然后再用相衬显微镜直接观察偶氮苯薄膜上的光栅结构,并以分子取向机制为基础对光栅形成和消除过程提出了新解释,这种观点被实验观察结果进一步证实.     

具有梯形结构钴(Ⅱ)配位聚合物的合成及晶体结构

Co(NO₃)₂, N-carbazolyacetic acid and 4,4′-bipyridyl can give rise to a novel coordination polymer [CO₂(Cabo)₂(NO₃)₂(4,4′-bipy)₂]_n using a fritted U-tube. Single crystal X-ray diffraction displays in the complex, each Co(Ⅱ) is six-coordinated by two N atoms from different 4,4′-bipyridyl ligands, two O atoms of the bridge from two N-carbazolyacetic acid and two O atoms of one nitrate anion to form a distorted octahedral. Two O atoms of the carboxyl group act as bridge to link two Co(Ⅱ) atoms. The resulting structure is a ladder polymer. CCDC: 211713.