Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

计算机辅助设计三聚氰胺分子印迹聚合物

借助密度泛函理论(DFT)长程校正方法,以三聚氰胺(MAM)为印迹分子,甲基丙烯酸(MAA)为功能单体,分别以二甲基丙烯酸乙二醇酯(EGDMA)、三羟甲基丙烷三甲基丙烯酸酯(TRIM)及二乙烯苯(DVB)为交联剂,以乙腈(ACN)、甲醇(MT)、乙醇(EA)、甲苯(TL)、四氢呋喃(THF)及二甲基亚砜(DMSO)为溶剂,模拟了MAM与MAA单体分子印迹聚合物(MIPs)自组装体系的构型,讨论了MAM与MAA的成键作用位点,及其稳定复合物的印迹反应比例及印迹作用机理,依据结合能(△E)优化了交联剂和溶剂,并借助分子中原子理论(AIM)揭示了MAM与MAA印迹作用的本质.计算结果表明,MAM印迹分子三嗪环上的N与胺基上H均通过氢键与MAA单体进行印迹聚合反应,且在印迹反应比例为1∶6,以TL为溶剂时形成的MAM-MAA有序复合物结合能最低,构型最稳定;与TRIM及EGDMA交联剂相比,DVB与MAM结合能最低,更适宜作为MAM-MAA印迹聚合物的交联剂.本研究为MAM-MIPs合成时印迹比例、交联剂及溶剂的选择提供了理论依据.     

Immobilization of Distinctly Capped CdTe Quantum Dots onto Porous Aminated Solid Supports

Immobilization of quantum dots (QDs) onto solid supports could improve their applicability in the development of sensing platforms and solid‐phase reactors by allowing the implementation of reusable surfaces and the execution of repetitive procedures. As the reactivity of QDs relies mostly on their surface chemistry, immobilization could also limit the disruption of solution stability that could prevent stable measurements. Herein, distinct strategies to immobilize QDs onto porous aminated supports, such as physical adsorption and the establishment of chemical linking, were evaluated. This work explores the influence of QD capping and size, concentration, pH, and contact time between the support and the QDs. Maximum QD retention was obtained for physical adsorption assays. Freundlich and Langmuir isotherms were used to analyze the equilibrium data. Gibbs free energy, enthalpy, and entropy were calculated and the stability of immobilized QDs was confirmed.     

An Approach to NMR Assignment of Intrinsically Disordered Proteins

An efficient approach to NMR assignments in intrinsically disordered proteins is presented, making use of the good dispersion of cross peaks observed in [¹⁵N,¹³C′]‐ and [¹³C′,¹H^N]‐correlation spectra. The method involves the simultaneous collection of {3D (H)NCO(CAN)H and 3D (HACA)CON(CA)HA} spectra for backbone assignments via sequential H^N and H^α correlations and {3D (H)NCO(CACS)HS and 3D (HS)CS(CA)CO(N)H} spectra for side‐chain ¹H and ¹³C assignments, employing sequential ¹H data acquisitions with direct detection of both the amide and aliphatic protons. The efficacy of the approach for obtaining resonance assignments with complete backbone and side‐chain chemical shifts is demonstrated experimentally for the 61‐residue [¹³C,¹⁵N]‐labelled peptide of a voltage‐gated potassium channel protein of the Kv1.4 channel subunit. The general applicability of the approach for the characterisation of moderately sized globular proteins is also demonstrated.     

Sequential paired covariance for improved visualization of mass spectrometry imaging datasets

Untargeted analyses in mass spectrometry imaging produce hundreds of ion images representing spatial distributions of biomolecules in biological tissues. Due to the large diversity of ions detected in untargeted analyses, normalization standards are often difficult to implement to account for pixel-to-pixel variability in imaging studies. Many normalization strategies exist to account for this variability, but they largely do not improve image quality. In this study, we present a new approach for improving image quality and visualization of tissue features by application of sequential paired covariance (SPC). This approach was demonstrated using previously published tissue datasets such as rat brain and human prostate with different biomolecules like metabolites and N-linked glycans. Data transformation by SPC improved ion images resulting in increased smoothing of biological features compared with commonly used normalization approaches.     

基于光子晶体带边效应的表面增强拉曼基底

将光子晶体的带边效应与金纳米粒子的拉曼散射增强作用相结合,制备了一种新型光子晶体表面增强拉曼散射基底(PC-AuNPs),利用罗丹明B(RhB)作为报告分子,对所得基底性能进行检测.PC-AuNPs基底的制备包括3个步骤:在SiO2微球表面修饰氨基,再通过垂直沉降自组装得到蛋白石结构光子晶体(PC), 最后, 在光子晶体表面负载金纳米粒子(AuNPs).结果表明,光子晶体的带隙范围及AuNPs的负载量直接影响了PC-AuNPs基底的检测效果;以所得的PC-AuNPs基底测定RhB分子,其拉曼散射特征峰强度与浓度对数值呈现良好的线性关系,线性方程为I=1711lg[RhB(mol/L)]+15244,线性相关系数R2=0.9994,检出限为1×10-8 mol/L,表明此PC-AuNPs基底可用于目标物的定性及定量检测.本方法提高了传统拉曼散射光谱检测灵敏度,操作简单,具有良好的重现性,可为其它新型检测基底的制备提供.     

On the Minimum Number of Spanning Trees in k‐Edge‐Connected Graphs

We show that a k‐edge‐connected graph on n vertices has at least spanning trees. This bound is tight if k is even and the extremal graph is the n‐cycle with edge multiplicities . For k odd, however, there is a lower bound , where . Specifically, and . Not surprisingly, c₃ is smaller than the corresponding number for 4‐edge‐connected graphs. Examples show that . However, we have no examples of 5‐edge‐connected graphs with fewer spanning trees than the n‐cycle with all edge multiplicities (except one) equal to 3, which is almost 6‐regular. We have no examples of 5‐regular 5‐edge‐connected graphs with fewer than spanning trees, which is more than the corresponding number for 6‐regular 6‐edge‐connected graphs. The analogous surprising phenomenon occurs for each higher odd edge connectivity and regularity.     

High‐Mass MALDI‐MS Analysis for the Investigation of Protein Encapsulation within an Engineered Capsid Forming Protein

Chemical cross‐linking combined with MALDI ‐MS was applied to structural analysis of a protein nanocontainer. Specifically, an engineered variant of lumazine synthase from Aquifex aeolicus (AaLS ‐13) was investigated that self‐assembles into a capsid‐like structure and is known to encapsulate other proteins by Coulombic attraction. Two complementary soft ionization techniques, MALDI ‐MS and native ESI ‐MS , were utilized to map the subunit stoichiometry of the high molecular weight capsid. In accordance with the previously reported cryo‐electron microscopy structure of this protein container, only pentameric subunits were detected. This study highlights the possibility to map subunit stoichiometry via chemical cross‐linking with glutaraldehyde followed by MALDI ‐MS . The same approach was used to study protein‐protein interactions during encapsulation of GFP (+36) by the AaLS ‐13 capsid. Heterocomplexes between GFP (+36) and AaLS ‐13 multimers were not observed when mixed at maximal loading capacity (AalS‐13 monomer:GFP (+36) 4:1). This is in agreement with the known fast encapsulation of GFP (+36) by the protein capsid, which essentially removes any free GFP (+36) from the solution. Exceeding the maximal loading capacity by addition of excess GFP (+36) results in aggregation.     

Formation of Stone–Wales edge: Multistep reconstruction and growth mechanisms of zigzag nanographene

Although the existence of Stone–Wales (5‐7) defect at graphene edge has been clarified experimentally, theoretical study on the formation mechanism is still imperfect. In particular, the regioselectivity of multistep reactions at edge (self‐reconstruction and growth with foreign carbon feedstock) is essential to understand the kinetic behavior of reactive boundaries but investigations are still lacking. Herein, by using finite‐sized models, multistep reconstructions and carbon dimer additions of a bared zigzag edge are introduced using density functional theory calculations. The zigzag to 5‐7 transformation is proved as a site‐selective process to generate alternating 5‐7 pairs sequentially and the first step with largest barrier is suggested as the rate‐determining step. Conversely, successive C₂ insertions on the active edge are calculated to elucidate the formation of 5‐7 edge during graphene growth. A metastable intermediate with a triple sequentially fused pentagon fragment is proved as the key structure for 5‐7 edge formation. © 2017 Wiley Periodicals, Inc.     

Morita–Baylis–Hillman (MBH) Reaction Derived Nitroallylic Alcohols,Acetates and Amines as Synthons in Organocatalysis and Heterocycle Synthesis

The Morita–Baylis–Hillman (MBH) reaction is one of the most useful and efficient protocols for constructing new carbon–carbon bonds between an activated olefin and electrophiles in the presence of a tertiary amine/phosphine. Herein, we present the use of MBH alcohols, which are obtained from the reaction of nitrostyrenes with aldehydes, as well as acetates and amines derived thereof in several organocatalytic transformations. Densely functionalised MBH adducts can also be used to synthesise substituted heteroaromatic compounds, such as furan, pyrrole, pyrazole and imidazole derivatives.