The practical synthesis of a novel and highly potent analogue of bryostatin

Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer.     

铜电极表面的电致发光法现场测试

采用电致发光等方法, 初步探讨了铜电极在0.25 mol·L~(-1)Na_2S_2O_8+1.25 mol·L~(-1)NaOH溶液中的电致发光特性及其相关性能, 给出了电致发光法现场测试铜电极表面性质的初步结果。     

Ultrafast time-resolved study of photophysical processes involved in the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds

A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR(3)) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR(3) was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two emitting components were assigned to originate from the (1)pipi (S(3)) and (1)npi (S(1)) states, respectively. This was based on the lifetime, the spectral location, and how these varied with the type of solvent. By correlating the dynamics of the singlet decay with the triplet formation, a direct (1)npi --> (3)pipi ISC mechanism was found for these compounds with the ISC rate estimated to be approximately 5 x 10(11) s(-)(1) in both solvent systems. These photophysical processes were found to be little affected by the kind of leaving group indicating the common local pHP chromophore is largely responsible for the fluorescence and relevant deactivation processes. The triplet lifetime was found to be approximately 420 and 2130 ps for HPDP and HPA, respectively, in the mixed solvent compared to 150 and 137 ns, respectively, in neat MeCN. The solvent and leaving group dependent quenching of the triplet is believed to be associated with the pHP deprotection photochemistry and indicates that the triplet is the reactive precursor for pHP photorelease reactions for the compounds examined in this study.     

邻菲啰啉对固定尿酸酶催化反应动力学的影响

The activation energy of the enzyme-catalyzed reaction for uric acid decreases markedly in the presence of o-phenanthroline, which activates the bioelectrochemicla activity of the polypyrrole uricase electrode. The response current of the enzyme electrodeis independent of the concentration of o-phenanthroline. Based on the experimental results, the mechamsm of the enzyme-catalyzed reaction for uric acid in the presence of o-phenanthroline is presented as follows: E+A→EA, EA+S EAS, EAS→EA+P, where E, A, S and P are the enzyme, activator, substrate and product, respectively. The effects of pH value, potential and the uric acid concentration on the response currents of the uricase electrode have been studied in the presence of o-phenanthroline. In the presence of o-phenanthroline, the response current of the enzyme electrode increase linearly with increasing concentration of uric acid in the region of 0.07 to 0.67 mmol·L~(-1), therefore the polypyrrole uricase electrode which has once lost its activity can be activated and used again to determine the substrate concentration.     

Reliability bounds in DFRA class with known mean and variance

ＲＥＬＩＡＢＩＬＩＴＹＢＯＵＮＤＳＩＮＤＦＲＡＣＬＡＳＳＷＩＴＨＫＮＯＷＮＭＥＡＮ　ＡＮＤ　ＶＡＲＩＡＮＣＥＣＨＥＮＧＫＡＮ（程侃）（ＩｎｓｔｉｔｕｔｅｏｆＡｐｐｌｉｅｄＭａｔｈｅｍａｔｉｃｓ,ｔｈｅＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅ,Ｂ...     

Incombustible Polymer Electrolyte Boosting Safety of Solid-State Lithium Batteries: A Review

Lithium-ion batteries with their portability, high energy density, and reusability are frequently used in today's world. Under extreme conditions, lithium-ion batteries leak, burn, and even explode. Therefore, improving the safety of lithium-ion batteries has become a focus of attention. Researchers believe using a solid electrolyte instead of a liquid one can solve the lithium battery safety issue. Due to the low price, good processability and high safety of the solid polymer electrolytes, increasing attention have been paid to them. However, polymer electrolytes can also decompose and burn under extreme conditions. Moreover, lithium dendrites are formed continuously due to the uneven charge distribution on the surface of the lithium metal anode. A short circuit caused by a lithium dendrite can cause the battery to thermal runaway. As a result, the safety of polymer solid-state batteries remains a challenge. In this review, the thermal runaway mechanism of the batteries is summarized, and the batteries abuse test standard is introduced. In addition, the recent works on the high-safety polymer electrolytes and the solution strategies of lithium anode problems in polymer batteries are reviewed. Finally, the development direction of safe polymer solid lithium batteries is prospected.     

New Polymerized Small Molecular Acceptors with Non-Aromatic π-Conjugated Linkers for Efficient All-Polymer Solar Cells

Developing new polymerized small molecular acceptor (PSMA) is pivotal for improving the performance of all-polymer solar cells. On the basis of this newly developed CH-series small molecule acceptors, two PSMAs are reported herein (namely PZC16 and PZC17, respectively). To reduce the molecular torsion caused by the traditional aromatic π-bridges, non-aromatic conjugated units (ethynyl for PZC16 and vinylene for PZC17) are adopted as the linkers and their effect on the photo-physical properties as well as the device performance are systematically investigated. Both polymer acceptors exhibit co-planar molecular conformation, along with broad absorption ranges and suitable energy levels. In comparison with the PM6:PZC16 film, the PM6:PZC17 film exhibits more uniform phase separation in morphology with a distinct bi-continuous network and better crystallinity. The PM6:PZC17-binary-based devices exhibit a satisfactory PCE of 16.33%, significantly higher than 9.22% of the PZC16-based devices. Impressively, PM6:PZC17-based large area device (ca. 1 cm²) achieves an excellent PCE of 15.14%, which is among the top performance for reported all-polymer solar cells (all-PSCs).     

茶碱对聚苯胺尿酸酶电极的生物电化学活性的抑制

用聚苯胺尿酸酶电极研究了茶碱对固定酶的影响，结果表明，茶碱对固定尿酶酶有明显的抑制作用，但这种抑制作用是可逆的，在茶碱的存在下，ＰＨ对酶电极的响应电流影响与无茶碱存在时不同；在０．２－０．５Ｖ之间，酶电极的响应电流随电位加而迅速升高，当电位进一步升高时，其变化速度减慢，茶碱使尿酶酶催化反应的活化能从无抑制剂存在的时的２９．９ｋＪ．ｍｏｌ＾－１提高到４７．８ｋＪ．ｍｏｌ＾－１，即抑制剂改变了尿酸催化     

中国南海海绵Seletta tenuis Lindgren中24-亚甲基-27-甲基胆甾醇的结构鉴定

自七十年代以来,已从海绵中发现了许多结构独特的、具有强烈生理活性的新化合物,有些已发展成为特效的药物。我们在研究中国南海海绵生物活性成分的过程中,从南海海绵Seletta teuuis Lindgren中分离出24-亚甲基-27-甲基胆甾醇(1)。虽然这个化合物已由De Luca等于1972年从海绵(Aplysina aerophoba)中发现了它。次     

聚苯胺尿酸酶电极性能的研究

依据pH对聚苯胺尿酸酶电极最大响应电流的影响, logim～pH图表明尿酸酶电极的催化活性只与其电离基团的碱性形式有关. 扫描电镜的结果表明, 聚苯胺尿酸酶电极的稳定性与其制备方法有关. 电化学法固定的尿酸酶电极具有高的稳定性.