Basic Principles in the Design of Spider Silk Fibers

The prominence of spider silk as a hallmark in biomimetics relies not only on its unrivalled mechanical properties, but also on how these properties are the result of a set of original design principles. In this sense, the study of spider silk summarizes most of the main topics relevant to the field and, consequently, offers a nice example on how these topics could be considered in other biomimetic systems. This review is intended to present a selection of some of the essential design principles that underlie the singular microstructure of major ampullate gland silk, as well as to show how the interplay between them leads to the outstanding tensile behavior of spider silk. Following this rationale, the mechanical behavior of the material is analyzed in detail and connected with its main microstructural features, specifically with those derived from the semicrystalline organization of the fibers. Establishing the relationship between mechanical properties and microstructure in spider silk not only offers a vivid image of the paths explored by nature in the search for high performance materials, but is also a valuable guide for the development of new artificial fibers inspired in their natural counterparts.     

甲酸存在下 N-四氢苯并噻唑亚胺希夫碱的化学发光

新合成的N(2-四氢苯并噻唑)-2-羟基苯甲亚胺希夫碱与酸性高锰酸钾反应产生微弱的化学发光,甲酸的存在有显著的增敏作用。报道了其荧光光谱、化学发光光谱、紫外可见吸收光谱和化学发光动力学曲线,并建立了流动注射化学发光测定噻唑类希夫碱的方法。该法线性范围为1.0×10-7～8.0×10-5mol/L,检测限为5.0×10-8mol/L,对1.0×10-6mol/L噻唑类希夫碱11次平行测定的相对标准偏差为1.7％。     

Biofabrication of Cell‐Loaded 3D Spider Silk Constructs

Biofabrication is an emerging and rapidly expanding field of research in which additive manufacturing techniques in combination with cell printing are exploited to generate hierarchical tissue‐like structures. Materials that combine printability with cytocompatibility, so called bioinks, are currently the biggest bottleneck. Since recombinant spider silk proteins are non‐immunogenic, cytocompatible, and exhibit physical crosslinking, their potential as a new bioink system was evaluated. Cell‐loaded spider silk constructs can be printed by robotic dispensing without the need for crosslinking additives or thickeners for mechanical stabilization. Cells are able to adhere and proliferate with good viability over at least one week in such spider silk scaffolds. Introduction of a cell‐binding motif to the spider silk protein further enables fine‐tuned control over cell–material interactions. Spider silk hydrogels are thus a highly attractive novel bioink for biofabrication.     

Dicarboxylic Acid Monoesters in β- and δ-Lactam Synthesis

A N-(2-methoxy-2-oxoethyl)-N-(phenylsulfonyl)glycine monomethyl ester of the respective dicarboxylic acid was involved in a reaction with imines promoted by acetic anhydride at an elevated temperature. Instead of the initially expected δ-lactam products of the Castagnoli–Cushman-type reaction, medicinally important 3-amino-2-azetidinones were obtained as the result of cyclization, involving a methylene group adjacent to an acid moiety. In contrast, replacing alcohol residue with hexafluoroisopropyl in the same substrate made another methylene group (adjacent to the ester moiety) more reactive to furnishing the desired δ-lactam in the Castagnoli–Cushman fashion.     

Selected β2-, β3- and β2,3-Amino Acid Heterocyclic Derivatives and Their Biological Perspective

Heterocyclic moieties, especially five and six-membered rings containing nitrogen, oxygen or sulfur atoms, are broadly distributed in nature. Among them, synthetic and natural alike are pharmacologically active compounds and have always been at the forefront of attention due to their pharmacological properties. Heterocycles can be divided into different groups based on the presence of characteristic structural motifs. The presence of β-amino acid and heterocyclic core in one compound is very interesting; additionally, it very often plays a vital role in their biological activity. Usually, such compounds are not considered to be chemicals containing a β-amino acid motif; however, considering them as this class of compounds may open new routes of their preparation and application as new drug precursors or even drugs. The possibility of their application as nonproteinogenic amino acid residues in peptide or peptide derivatives synthesis to prepare a new class of compounds is also promising. This review highlights the actual state of knowledge about β-amino acid moiety-containing heterocycles presenting antiviral, anti-inflammatory, antibacterial compounds, anaplastic lymphoma kinase (ALK) inhibitors, as well as agonist and antagonists of the receptors.     

Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid

Recently, there has been a strong demand for technologies that use hydrogen as an energy carrier, instead of fossil fuels. Hence, new and effective hydrogen storage technologies are attracting increasing attention. Formic acid (FA) is considered an effective liquid chemical for hydrogen storage because it is easier to handle than solid or gaseous materials. This review presents recent advances in research into the development of homogeneous catalysts, primarily focusing on hydrogen generation by FA dehydrogenation. Notably, this review will aid in the development of useful catalysts, thereby accelerating the transition to a hydrogen-based society.     

腐植酸作用下γ-六氯环己烷在冰相中的光转化

研究了腐植酸(HA)存在下冰相体系中γ-六氯环己烷(γ-HCH)的光转化规律. 结果表明, HA浓度对γ-HCH的光转化率呈现低浓度促进而高浓度抑制的现象; 盐离子浓度、 N\begin{array}{c}{O}_2^{-}\end{array}及N\begin{array}{c}{O}_3^{-}\end{array}对γ-HCH的光转化率均有促进作用; 低浓度Fe³⁺对γ-HCH的光转化率有促进作用, 当Fe³⁺的浓度增大到50 μmol/L时, 呈现抑制效应; γ-HCH在不同pH值条件下光转化速率的大小顺序为碱性>中性>酸性. 冰相中HA通过产生单线态氧(¹O₂)、 羟基自由基(·OH)及三重激发态(HA^*)加速γ-HCH的光转化. HA存在下γ-HCH的光转化产物主要是五氯环己烯、 邻二氯苯和对二氯苯、 一氯苯, 光转化过程中¹O₂通过消耗中间产物间接加速了γ-HCH的光转化过程.     

核壳结构C@WC载体的制备及Pd/C@WC催化剂对甲酸的电催化氧化

以活性碳为碳源,在碳表面原位生成碳化钨包覆的核壳结构的碳基材料(C@WC)。 TEM结果表明,制备的C@WC是具有核壳结构的碳材料,且WC中也有少量单质W。 BET比表面测量结果表明,C@WC较活性碳比表面小,但具有更多的介孔结构。 以C@WC为载体制备的Pd/C@WC催化剂电极的电化学比表积较大,为65.47 m2/g。 Pd/C@WC对甲酸的电催化氧化活性较高,氧化峰电流密度为0.222 A/cm2,比Pd/C电极上的氧化峰电流密度增加了0.128 A/cm2。 多周期循环伏安曲线的结果也表明,Pd/C@WC催化剂电极比Pd/C具有更高的活性和稳定性。     

Functional Dynamics of Deuterated β2‐Adrenergic Receptor in Lipid Bilayers Revealed by NMR Spectroscopy

G‐protein‐coupled receptors (GPCRs) exist in conformational equilibrium between active and inactive states, and the former population determines the efficacy of signaling. However, the conformational equilibrium of GPCRs in lipid bilayers is unknown owing to the low sensitivities of their NMR signals. To increase the signal intensities, a deuteration method was developed for GPCRs expressed in an insect cell/baculovirus expression system. The NMR sensitivities of the methionine methyl resonances from the β₂‐adrenergic receptor (β₂AR) in lipid bilayers of reconstituted high‐density lipoprotein (rHDL) increased by approximately 5‐fold upon deuteration. NMR analyses revealed that the exchange rates for the conformational equilibrium of β₂AR in rHDLs were remarkably different from those measured in detergents. The timescales of GPCR signaling, calculated from the exchange rates, are faster than those of receptor tyrosine kinases and thus enable rapid neurotransmission and sensory perception.     

光氧化还原催化自由基偶联合成β-氟代-α-氨基酸衍生物

通过可见光驱动光氧化还原催化, 发展了一种新颖、便利的β-氟代-α-氨基酸衍生物的合成方法. 以非金属的二氰基吡嗪衍生物(DPZ)为光催化剂, 以易于制备的N-芳基甘氨酸酯和芳基乙酸氧化还原酯为原料, 通过单电子氧化还原分别生成酯基取代α-氨烷基自由基及α-氟代苄基自由基. 经过高反应活性自由基的交叉偶联, 高产率地得到目标产物. 该方法由于氧化还原中性反应途径而无需额外的氧化剂或还原剂, 且属于绿色、可持续的有机催化合成策略.     

Molecular Regulation of Betulinic Acid on α3β4 Nicotinic Acetylcholine Receptors

Betulinic acid (BA) is a major constituent of Zizyphus seeds that have been long used as therapeutic agents for sleep-related issues in Asia. BA is a pentacyclic triterpenoid. It also possesses various anti-cancer and anti-inflammatory effects. Current commercially available sleep aids typically use GABAergic regulation, for which many studies are being actively conducted. However, few studies have focused on acetylcholine receptors that regulate wakefulness. In this study, we utilized BA as an antagonist of α3β4 nicotinic acetylcholine receptors (α3β4 nAChRs) known to regulate rapid-eye-movement (REM) sleep and wakefulness. Effects of BA on α3β4 nAChRs were concentration-dependent, reversible, voltage-independent, and non-competitive. Site-directed mutagenesis and molecular-docking studies confirmed the binding of BA at the molecular level and showed that the α3 subunit L257 and the β4 subunit I263 residues affected BA binding. These data demonstrate that BA can bind to a binding site different from the site for the receptor’s ligand, acetylcholine (ACh). This suggests that BA may be an effective antagonist that is unaffected by large amounts of ACh released during wakefulness and REM sleep. Based on the above experimental results, BA is likely to be a therapeutically useful sleep aid and sedative.     

Unprecedentedly High Formic Acid Dehydrogenation Activity on an Iridium Complex with an N,N′‐Diimine Ligand in Water

Hydrogen production from the dehydrogenation of formic acid (FA) is promising. Most of the current catalysts for FA dehydrogenation are effective only in the presence of bases or additives. We report here newly developed iridium complexes containing conjugated N,N′‐diimine ligands for FA dehydrogenation in water without the addition of bases or additives. A turnover frequency (TOF) of 487 500 h^?1 with [Cp*Ir( L1 )Cl]Cl ( L1 =2,2′‐bi‐2‐imidazoline) at 90 °C and a turnover number (TON) of 2 400 000 with in situ prepared catalyst from [IrCp*Cl₂]₂ and 2,2′‐bi‐1,4,5,6‐tetrahydropyrimidine ( L2 ) at 80 °C were obtained, the highest values reported for FA dehydrogenation to date. A mechanistic study reveals that the formation of [Ir‐H] intermediate species is the rate‐determining step in the catalytic cycle.     

The Amyloid Fibril-Forming β-Sheet Regions of Amyloid β and α-Synuclein Preferentially Interact with the Molecular Chaperone 14-3-3ζ

14-3-3 proteins are abundant, intramolecular proteins that play a pivotal role in cellular signal transduction by interacting with phosphorylated ligands. In addition, they are molecular chaperones that prevent protein unfolding and aggregation under cellular stress conditions in a similar manner to the unrelated small heat-shock proteins. In vivo, amyloid β (Aβ) and α-synuclein (α-syn) form amyloid fibrils in Alzheimer’s and Parkinson’s diseases, respectively, a process that is intimately linked to the diseases’ progression. The 14-3-3ζ isoform potently inhibited in vitro fibril formation of the 40-amino acid form of Aβ (Aβ₄₀) but had little effect on α-syn aggregation. Solution-phase NMR spectroscopy of ¹⁵N-labeled Aβ₄₀ and A53T α-syn determined that unlabeled 14-3-3ζ interacted preferentially with hydrophobic regions of Aβ₄₀ (L11-H21 and G29-V40) and α-syn (V3-K10 and V40-K60). In both proteins, these regions adopt β-strands within the core of the amyloid fibrils prepared in vitro as well as those isolated from the inclusions of diseased individuals. The interaction with 14-3-3ζ is transient and occurs at the early stages of the fibrillar aggregation pathway to maintain the native, monomeric, and unfolded structure of Aβ₄₀ and α-syn. The N-terminal regions of α-syn interacting with 14-3-3ζ correspond with those that interact with other molecular chaperones as monitored by in-cell NMR spectroscopy.     

Selective Hydrogen Generation from Formic Acid with Well‐Defined Complexes of Ruthenium and Phosphorus–Nitrogen PN3‐Pincer Ligand

An unsymmetrically protonated PN³‐pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved.     

钌催化二氧化碳加氢合成甲酸的研究

钌催化二氧化碳加氢合成甲酸的研究张俊忠，李忠，王辉，王常有（太原工业大学煤化所Ｃ１室，太原０３００２４）关键词ＣＯ_２催化加氢，甲酸合成，钌络合催化剂１．前言由于ＣＯ２对环境、气候和生态等方面带来愈加恶劣的影响以及碳资源的日益短缺，近年来对ＣＯ２开发?..     

Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H2 or CO

Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon‐neutral economy. We present an inexpensive system for the selective room‐temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible‐light irradiation (λ>420 nm, 1 sun), suspensions of ligand‐capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H₂ g_cat^?1 h^?1 with >99 % selectivity when combined with a cobalt co‐catalyst; the quantum yield at λ=460 nm was 21.2±2.7 %. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO g_cat^?1 h^?1 with >95 % selectivity and 19.7±2.7 % quantum yield. H₂ and CO production was sustained for more than one week with turnover numbers greater than 6×10⁵ and 3×10⁶, respectively.     

Facile Synthesis of Carbon‐Supported Ultrasmall Ag@Pd Core‐Shell Nanocrystals with Superior Electrocatalytic Activity for Direct Formic Acid Fuel Cell Application

To design electrocatalysts with excellent performance, morphology, composition and structure is a decisive influential factor. In this work, ultrasmall Ag@Pd core‐shell nanocrystals supported on Vulcan XC72R carbon with different Ag/Pd atomic ratios are synthesized via a facile successive reduction approach with formaldehyde and ethylene glycol as reducing agents, respectively. The Ag‐core/Pd‐shell nanostructures are revealed by high‐resolution transmission electron microscopy (HRTEM). Ag@Pd core‐shell nanocrystals possess a narrow size distribution with an average size of ca. 4.3 nm. In comparison to monometallic Pd/C and commercial Pd black catalysts, such Ag@Pd core‐shell nanocrystals display excellent electrocatalytic activities for formic acid oxidation, which may be due to high Pd utilization derived from the formation of Ag@Pd core‐shell nanostructure and the strong interaction between Ag and Pd.     

β‐Peptide Conjugates: Syntheses and CD and NMR Investigations of β/α‐Chimeric Peptides,of a DPA‐β‐Decapeptide,and of a PEGylated β‐Heptapeptide

β³‐Peptides consisting of six, seven, and ten homologated proteinogenic amino acid residues have been attached to an α‐heptapeptide (all d‐ amino acid residues; 4 ), to a hexaethylene glycol chain (PEGylation; 5c ), and to dipicolinic acid (DPA derivative 6 ), respectively. The conjugation of the β‐peptides with the second component was carried out through the N‐termini in all three cases. According to NMR analysis (CD₃OH solutions), the (M)‐3₁₄‐helical structure of the β‐peptidic segments was unscathed in all three chimeric compounds (Figs. 2, 4, and 5). The α‐peptidic section of the α/β‐peptide was unstructured, and so was the oligoethylene glycol chain in the PEGylated compound. Thus, neither does the appendage influence the β‐peptidic secondary structure, nor does the latter cause any order in the attached oligomers to be observed by this method of analysis. A similar conclusion may be drawn from CD spectra (Figs. 1, 3, and 5). These results bode well for the development of delivery systems involving β‐peptides.