Isolation and Identification of Pentalenolactone Analogs from Streptomyces sp. NRRL S-4

Terpene synthases are widely distributed in Actinobacteria. Genome sequencing of Streptomyces sp. NRRL S-4 uncovered a biosynthetic gene cluster (BGC) that putatively synthesizes pentalenolactone type terpenes. Guided by genomic information, the S-4 strain was chemically investigated, resulting in the isolation of two new sesquiterpenoids, 1-deoxy-8α-hydroxypentalenic acid (1) and 1-deoxy-9β-hydroxy-11-oxopentalenic acid (2), as shunt metabolites of the pentalenolactone (3) biosynthesis pathway. Their structures and absolute configurations were elucidated by analyses of HRESIMS and NMR spectroscopic data as well as time-dependent density functional theory/electronic circular dichroism (TDDFT/ECD) calculations. Compounds 1 and 2 exhibited moderate antimicrobial activities against Gram-positive and Gram-negative bacteria. These results confirmed that the pentalenolactone pathway was functional in this organism and will facilitate efforts for exploring Actinobacteria using further genome mining strategies.     

CO2腐蚀环境下P110套管材料性能的实验研究

针对CO2腐蚀环境下P110套管材料性能动态变化的难题,基于腐蚀实验与拉伸实验,对含腐蚀损伤的P110套管进行了力学性能分析。根据现场资料对钻井液注入CO2配置腐蚀液,将腐蚀后试件与现场失效套管的腐蚀产物进行EDS能谱分析对比,确定了腐蚀液的适用性。设置固定井深,在100℃高温时不同的腐蚀实验周期内,将所得的含腐蚀损伤试件进行质量损失测试及拉伸实验,分析了材料力学性能的变化。由MTS液压式万能试验机得出应力-应变曲线,并拟合得到了等效屈服强度变化公式及等效抗拉强度变化公式。结果表明:套管试样腐蚀后的屈服强度和抗拉强度随着失重率增大而减小,当套管试样经腐蚀后失重率低于15%时,材料的力学性能,如等效屈服强度和等效抗拉强度随失重率的增加会以较大幅度降低;而当试样失重率大于15%时,随着失重率的增加,等效屈服强度急剧减小,等效抗拉强度则以较为平缓的趋势降低。     

A boronate affinity restricted-access material with external hydrophilic bottlebrush polymers for pretreatment of cis-diols in biological matrices

Restricted-access materials (RAMs) with an external hydrophilic bottlebrush polymer layer was prepared for sample pretreatment of bioanalysis.     

A comparative study of jet formation in nozzle‐ and nozzle‐less centrifugal spinning systems

Centrifugal spinning, a recently developed approach for ultra‐fine fiber production, has attracted much attention as compared with the electrospinning, due to its high yield, no solution polarity and high‐voltage electrostatic field requirements, etc. In this study, the jet formation process and spinning parameters on jet path are explored and compared in nozzle‐ and nozzle‐less centrifugal spinning systems. For nozzle‐less centrifugal spinning, fingers are formed at the front of thin liquid film due to the theory of Rayleigh–Taylor instability. We find that the lower solution concentration and higher rotational speed favor the formation of thinner and longer fingers. Then, the critical angular velocity and initial jet velocity for nozzle‐/nozzle‐less centrifugal spinning are obtained in accordance with the balance of centrifugal force, viscous force, and surface tension. When jet leaves the spinneret, it will undergo a series of motions including necking and whipping processes, and then, a steady spiral jet path is formed with its radius getting tighter. Finally, we experimentally study the effect of rotational speed and solution concentration on jet path, which shows that the higher rotational speed results in a larger radius of jet path while the solution concentration has little effect on it. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1547–1559     

1,8-位修饰杂芴类有机光电功能材料的合成与应用

以氧、硫、硅、氮、磷等杂原子取代芴中sp3杂化的碳原子所形成的杂芴,不仅可以通过杂原子和π共轭体系间的相互作用有效地调控材料的电子结构,而且可以影响芴不同位置的修饰,从而得到了广泛关注。本文详细分析了1,8-位修饰杂芴的分子结构特点和光电特性,根据不同的杂原子分类论述了相关材料的合成方法和原理,综述了1,8-位修饰杂芴类材料在磷光主体材料、电致发光材料、太阳能电池材料以及有机配体材料等方面的应用进展,展望了其在有机光电材料方面的应用前景和发展趋势。     

Poly(Ethylene Piperidinium)s for Anion Exchange Membranes

The lack of anion exchange membranes (AEMs) that possess both high hydroxide conductivity and stable mechanical and chemical properties poses a major challenge to the development of high-performance fuel cells. Improving one side of the balance between conductivity and stability usually means sacrificing the other. Herein, we used facile, high-yield chemical reactions to design and synthesize a piperidinium polymer with a polyethylene backbone for AEM fuel cell applications. To improve the performance, we introduced ionic crosslinking into high-cationic-ratio AEMs to suppress high water uptake and swelling while further improving the hydroxide conductivity. Remarkably, PEP80-20PS achieved a hydroxide conductivity of 354.3 mS cm⁻¹ at 80 °C while remaining mechanically stable. Compared with the base polymer PEP80, the water uptake of PEP80-20PS decreased by 69 % from 813 % to 350 %, and the swelling decreased substantially by 85 % from 350.0 % to 50.2 % at 80 °C. PEP80-20PS also showed excellent alkaline stability, 84.7 % remained after 35 days of treatment with an aqueous KOH solution. The chemical design in this study represents a significant advancement toward the development of simultaneously highly stable and conductive AEMs for fuel cell applications.     

The preparation of high-capacity boronate affinity adsorbents by surface initiated reversible addition fragmentation chain transfer polymerization for the enrichment of ribonucleosides in serum

Boronate affinity adsorption is uniquely selective for cis-diol-containing molecules. The preparation and application of boronate affinity materials has attracted much attention in recent years. In this work, a high-capacity boronate affinity adsorbent was prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization (SI-RAFT). Commercial aminated poly(glycidyl methacrylate) (PGMA) microspheres were modified with the chain transfer agent (CTA) S-1-dodecyl-S-(α,α-dimethyl-α-acetic acid)trithiocarbonate (DDATC). Boronate-affinity adsorbents were then prepared via SI-RAFT polymerization employing 3-acrylamidophenylboronic acid (AAPBA) as the monomer. The Fourier transform infrared spectroscopy (FT-IR), nitrogen adsorption and desorption measurements have proven the successful grafting of AAPBA on PGMA microspheres surface. The boronate affinity adsorbents thus prepared possess much higher adsorption capacity (99.2 µmol/g of adenosine) and both faster adsorption and desorption speed towards ribonucleosides, the adsorption and desorption could be completed in 2 min. The high selectivity of the adsorbents to ribonucleosides was verified in the presence of a large excess of deoxynucleosides. The boronate affinity adsorbents were then employed for sample pretreatment before HPLC analysis of ribonucleosides in serum. The ribonucleosides were effectively enriched by boronate affinity dispersive solid-phase extraction (BA-DSPE), with high mass recoveries and good precision. The simultaneous determination of uridine and guanosine in calf serum was achieved by utilizing the standard addition method, their contents were determined to be 170 ± 11.6 ng/mL and 39.6 ± 4.4 ng/mL respectively. The results proved that the prepared boronate affinity materials could be applied for sample pretreatment of cis-diol containing molecules in biological samples.     

A Smart Photosensitizer–Manganese Dioxide Nanosystem for Enhanced Photodynamic Therapy by Reducing Glutathione Levels in Cancer Cells

Photodynamic therapy (PDT) has been applied in cancer treatment by utilizing reactive oxygen species to kill cancer cells. However, a high concentration of glutathione (GSH) is present in cancer cells and can consume reactive oxygen species. To address this problem, we report the development of a photosensitizer–MnO₂ nanosystem for highly efficient PDT. In our design, MnO₂ nanosheets adsorb photosensitizer chlorin e6 (Ce6), protect it from self‐destruction upon light irradiation, and efficiently deliver it into cells. The nanosystem also inhibits extracellular singlet oxygen generation by Ce6, leading to fewer side effects. Once endocytosed, the MnO₂ nanosheets are reduced by intracellular GSH. As a result, the nanosystem is disintegrated, simultaneously releasing Ce6 and decreasing the level of GSH for highly efficient PDT. Moreover, fluorescence recovery, accompanied by the dissolution of MnO₂ nanosheets, can provide a fluorescence signal for monitoring the efficacy of delivery.