Investigation of Molecular Diffusion at Block Copolymer Thin Films Using Maximum Entropy Method-Based Fluorescence Correlation Spectroscopy and Single Molecule Tracking

Fluorescence correlation spectroscopy (FCS) has been widely used to investigate molecular diffusion behavior in various samples. The use of the maximum entropy method (MEM) for FCS data analysis provides a unique means to determine multiple distinct diffusion coefficients without a priori assumption of their number. Comparison of the MEM-based FCS method (MEM-FCS) with another method will reveal its utility and advantage as an analytical tool to investigate diffusion dynamics. Herein, we measured diffusion of fluorescent probes doped into nanostructured thin films using MEM-FCS, and validated the results with single molecule tracking (SMT) data. The efficacy of the MEM code employed was first demonstrated by analyzing simulated FCS data for systems incorporating one and two diffusion modes with broadly distributed diffusion coefficients. The MEM analysis accurately afforded the number of distinct diffusion modes and their mean diffusion coefficients. These results contrasted with those obtained by fitting the simulated data to conventional two-component and anomalous diffusion models, which yielded inaccurate estimates of the diffusion coefficients. Subsequently, the MEM analysis was applied to FCS data acquired from hydrophilic dye molecules incorporated into microphase-separated polystyrene-block-poly(ethylene oxide) (PS-b-PEO) thin films characterized under a water-saturated N₂ atmosphere. The MEM analysis revealed distinct fast and slow diffusion components attributable to molecules diffusing on the film surface and inside the film, respectively. SMT studies of the same materials yielded trajectories for mobile molecules that appear to follow the curved PEO microdomains. Diffusion coefficients obtained from the SMT data were consistent with those obtained for the slow diffusion component detected by MEM-FCS. These results highlight the utility of MEM-FCS and SMT for gaining complementary information on molecular diffusion processes in heterogeneous material systems.

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Low band‐gap D–A conjugated copolymers based on anthradithiophene and diketopyrrolopyrrole for polymer solar cells and field‐effect transistors

Two conjugated copolymers PADT‐DPP and PADT‐FDPP based on anthradithiophene and diketopyrrolopyrrole, with thiophene and furan as the π‐conjugated bridge, respectively, were successfully synthesized and characterized. The number‐averaged molecular weights of the two polymers are 38.7 and 30.2 kg/mol, respectively. Polymers PADT‐DPP and PADT‐FDPP exhibit broad absorption bands and their optical band gaps are 1.44 and 1.50 eV, respectively. The highest occupied molecular orbital energy level of PADT‐DPP is located at ?5.03 eV while that of PADT‐FDPP is at ?5.16 eV. In field‐effect transistors, PADT‐DPP and PADT‐FDPP displayed hole mobilities of 4.7 × 10^?3 and 2.7 × 10^?3 cm²/(V s), respectively. In polymer solar cells, PADT‐DPP and PADT‐FDPP showed power conversion efficiency (PCE) of 3.44% and 0.29%, respectively. Atomic force microscopy revealed that the poor efficiency of PADT‐FDPP should be related to the large two‐phase separation in its active layer. If 1,8‐diiodooctane (DIO) was used as the solvent additive, the PCE of PADT‐DPP remained almost unchanged due to very limited morphology variation. However, the addition of DIO could remarkably elevate the PCE of PADT‐FDPP to 2.62% because of the greatly improved morphology. Our results suggest that the anthradithiophene as an electron‐donating polycyclic system is useful to construct new D–A alternating copolymers for efficient polymer solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1652–1661     

Bayesian variable selection with sparse and correlation priors for high-dimensional data analysis

The main challenge in working with gene expression microarrays is that the sample size is small compared to the large number of variables (genes). In many studies, the main focus is on finding a small subset of the genes, which are the most important ones for differentiating between different types of cancer, for simpler and cheaper diagnostic arrays. In this paper, a sparse Bayesian variable selection method in probit model is proposed for gene selection and classification. We assign a sparse prior for regression parameters and perform variable selection by indexing the covariates of the model with a binary vector. The correlation prior for the binary vector assigned in this paper is able to distinguish models with the same size. The performance of the proposed method is demonstrated with one simulated data and two well known real data sets, and the results show that our method is comparable with other existing methods in variable selection and classification.     

高聚物粘结NTO的研究

运用付里叶变换红外，Ｘ射线光电子能谱及常规分析手段，研究了ＮＴＯ（３－硝基－１，２，４－三唑－５－酮）混合炸药粘结界面分子间的相互作用，造型粉的表面性能。结果表明，ＮＴＯ中唑环上的活泼氢与不同的高聚物形成氢键，高聚物的结构不同，形成的氢键强弱不同。氢键越强，对金属的腐蚀越小。腐蚀所得产物说明对金属腐蚀起主要作用的是ＮＴＯ中唑环上的活泼氢。它们的氢键强弱次序为ＮＴＯ／ＰＵ＞ＮＴＯ／Ｆ２４６Ｇ＞ＮＴＯ／Ｆ２３１１＞ＮＴＯ／ＰＶＢ＞ＮＴＯ／ＡＳ＞ＮＴＯ／ＰＳ。通过运用ＮＴＯ的饱和水溶液作为水浆液的载体，克服了由于ＮＴＯ部分溶于水而难于运用水悬浮法生产造型粉的工艺难题。     

Hydrophilic Conjugated Polymers with Large Bandgaps and Deep‐Lying HOMO Levels as an Efficient Cathode Interlayer in Inverted Polymer Solar Cells

Two hydrophilic conjugated polymers, PmP‐NOH and PmP36F‐NOH, with polar diethanol­amine on the side chains and main chain structures of poly(meta‐phenylene) and poly(meta‐phenylene‐alt‐3,6‐fluorene), respectively, are successfully synthesized. The films of PmP‐NOH and PmP36F‐NOH show absorption edges at 340 and 343 nm, respectively. The calculated optical bandgaps of the two polymers are 3.65 and 3.62 eV, respectively, the largest ones so far reported for hydrophilic conjugated polymers. PmP‐NOH and PmP36F‐NOH also possess deep‐lying highest occupied molecular orbital levels of −6.19 and −6.15 eV, respectively. Inserting PmP‐NOH and PmP36F‐NOH as a cathode interlayer in inverted polymer solar cells with a PTB7/PC₇₁BM blend as the active layer, high power conversion efficiencies of 8.58% and 8.33%, respectively, are achieved, demonstrating that the two hydrophilic polymers are excellent interlayers for efficient inverted polymer solar cells.

     

豆芽中甲硝唑、多菌灵、赤霉素、6-苄基腺嘌呤、2,4-二氯苯氧乙酸的定量检测

本文建立了快速筛查豆芽中常见添加物甲硝唑、多菌灵、赤霉素、6-苄基腺嘌呤和2,4-二氯苯氧乙酸的液相色谱定量方法。回收率为79%～96.6%,定量限在20～200μg/kg。对市场随机抽查64份豆芽样品检测发现,高达32份样品中含有1种以上添加物,主要是多菌灵、6-苄基腺嘌呤和2,4-二氯苯氧乙酸。     

Bioinspired polymer functionalized with a diiron carbonyl model complex and its assembly onto the surface of a gold electrode via “click” chemistry

A complex pendant with two ethynyl groups, [Fe₂(μ‐SCH₂CCH)₂(CO)₆] ( 2 ), as a model of the diiron subunit of [FeFe]‐hydrogenase was polymerized and the {Fe₂(CO)₆} core was successfully incorporated into the polymer matrix. The polymer was characterized by a variety of spectroscopic techniques, TGA, FTIR, SEM, TEM, and NMR. The resultant polymer was immobilized via “click” chemistry using its terminal C?CH bond onto the surface of a gold electrode, which was premodified with azidothiol by self‐assembled monolayer (SAM). The assembled electrode showed electrochemical responses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2410–2417, 2010     

Genetically engineered materials: Proteins and beyond

Information-rich molecules provide opportunities for evolution.Genetically engineered materials are superior in that their properties are coded within genetic sequences and could be fine-tuned.In this review,we elaborate the concept of genetically engineered materials(GEMs)using examples ranging from engineered protein materials to engineered living materials.Proteinbased materials are the materials of choice by nature.Recent progress in protein engineering has led to opportunities to tune their sequences for optimal material performance.Proteins also play a central role in living materials where they act in concert with other biological components as well as nonbiological cofactors,giving rise to living features.While the existing GEMs are often limited to those constructed by building blocks of biological origin,being genetically engineerable does not preclude nonbiologic or synthetic materials,the latter of which have yet to be fully explored.     

Solvothermal synthesis of mesoporous slabstone‐like TiO2 and its photodegradation preference in a methyl orange‐rhodamine B mixture solution

Mesoporous slabstone‐like anatase TiO₂ micro‐nanometer composite structure has been successfully synthesized by a facile solvothermal method at 180 °C using polyethylene glycol (PEG) as a structure‐directing agent, followed by calcination at 400 °C for 2 h. The crystal structure and morphology of the product were characterized by XRD, SEM, TEM and HRTEM. Its BET specific surface area was obtained from N₂ adsorption‐desorption isotherm measurement. Rhodamine B (RB) aqueous solution was used to evaluate the photocatalytic activity of the as‐prepared TiO₂ under simulated sunlight irradiation and compared with that of commercial TiO₂ (P25). A RB and methyl orange (MO) coexisting solution was chosen to investigate the photodegradation preference of the slabstone‐like TiO₂ on these two dyes. The results show that the photocatalytic activity of the as‐prepared TiO₂ is much higher than that of P25, and MO is the preferential degradation species in the MO‐RB mixture solution.     

Topology: a unique dimension in protein engineering

Controlling protein topology has been a long standing challenge to go beyond their linear configuration defined by the translation mechanism of cellular machinery. In this mini-review, we focus on the topological diversity in proteins and review the major categories of protein topologies known to date, including branched/star proteins, circular proteins, lasso proteins, knotted proteins, and protein catenanes. The discovery of these topologically complex natural proteins and their synthetic pathways, the rational design and recombinant synthesis of artificial topological proteins and their biophysical studies, are summarized and discussed with regard to their general features and broad implications. The complexity of protein topology is recognized and the routes to diverse protein topologies are illustrated. We believe that topology engineering is an important way to modify protein properties without alternating their native sequences and shall bring in valuable dynamic features central to the creation of artificial protein machinery.