DNA-directed formation of peptide bond: a model study toward DNA-programmed peptide ligation

A model study of DNA-directed peptide ligation has been developed by transferring fluorescent reporting group from small molecule thioester to a DNA strand (template DNA) in the presence of a thiol-functionalized DNA strand (auxiliary DNA), mimicking the Native Chemical Ligation (NCL) reaction. This DNA-directed transfer shows dependence on the sequence complementarity of the two DNA strands, with in situ generated 4-thiolphenylmethyl functionalized oligonucleotide as the auxiliary DNA strand, under mild basic condition (pH=8.5), and with tris(2-carboxyethyl) phosphine hydrochloride (TCEP) as a reducing agent. Reactions with different amino acid α-thioesters resulted in varied transfer efficiencies from glycine to α-substituted amino acids. This study has provided the basic foundation to use DNA-programmed chemistry toward the chemical synthesis or unnatural modification of protein molecules.     

Deep-Eutectic-Solvent-Based Self-Healing Polymer Electrolyte for Safe and Long-Life Lithium-Metal Batteries

The deployment of high-energy-density lithium-metal batteries has been greatly impeded by Li dendrite growth and safety concerns originating from flammable liquid electrolytes. Herein, we report a stable quasi-solid-state Li metal battery with a deep eutectic solvent (DES)-based self-healing polymer (DSP) electrolyte. This electrolyte was fabricated in a facile manner by in situ copolymerization of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA) and pentaerythritol tetraacrylate (PETEA) monomers in a DES-based electrolyte containing fluoroethylene carbonate (FEC) as an additive. The well-designed DSP electrolyte simultaneously possesses non-flammability, high ionic conductivity and electrochemical stability, and dendrite-free Li plating. When applied in Li metal batteries with a LiMn₂O₄ cathode, the DSP electrolyte effectively suppressed manganese dissolution from the cathode and enabled high-capacity and a long lifespan at room and elevated temperatures.     

弹性非保守压杆的大幅度动力分析

本文讨论弹性非保守压杆的大幅度动力问题。导出了在一般非保守力作用下杆的非线性运动微分方程,并给出与此相应的拟Hamilton变分表达式,具体地分析了悬臂杆在大挠度下的动力特性,当挠度很小其高次项可以略去时,本文所得结论都能近似地退化为线性理论的结果。     

半平面多边缘裂纹反平面问题的奇异积分方程

利用复变函数和奇异积分方程方法,求解弹性范围内半平面多边缘裂纹的反平面问题．提出了满足半平面边界自由的由分布位错密度表示的单边缘裂纹的基本解,此基本解由主要部分和辅助部分组成．将半平面多边缘裂纹问题看作是许多单边缘裂纹问题的叠加,建立了一组Cauchy型奇异积分方程．然后,利用半开型积分法则求解该奇异积分方程,得到了裂纹端处的应力强度因子．最后,给出了几个数值算例．     

Allyl-Palladium-Catalyzed Ketone Dehydrogenation Enables Telescoping with Enone α,β-Vicinal Difunctionalization

The telescoping of allyl-palladium catalyzed ketone dehydrogenation with organocuprate conjugate addition chemistry allows for the introduction of aryl, heteroaryl, vinyl, acyl, methyl, and other functionalized alkyl groups chemoselectively to a wide variety of unactivated ketone compounds via their enone counterparts. The compatibility of the dehydrogenation conditions additionally allows for efficient trapping of the intermediate enolate with various electrophiles. The utility of this approach is demonstrated by comparison to several previously reported multistep sequences.     

求弹性半平面问题基本解的一个新方法

本文所提到的弹性半平面问题的基本解是一个满足特殊条件的弹性半平面的应力位移解答。这些条件为:(1)半平面内一点处作用有集中力X,Y或集中力偶M;(2)半平面边界为自由或固定边。利用平面弹性的复变函数方法,文中把弹性半平面基本解的问题归结为下列问题,使一个特定解析函数和另一个解析函数的共轭值在半平面边界上相等。对上述转化后的问题,只要利用复变函数的性质,不难从基本解的第一部分推导出基本解的第二部分。其中,基本解的第一部分是弹性全平面的本基解。从而,半平面问题基本解可以方便地得到。此外,文中还首次给出了:(1)集中力偶作用于半平面内一点时的基本解;(2)当半平面边界固定情况下的基本解。     

Biosynthesis, total syntheses, and antitumor activity of tanshinones and their analogs as potential therapeutic agents

Tanshinones are a series of abietane diterpenes, isolated exclusively from Salvia miltiorrhiza and related species. More than 40 tanshinones and their analogs have been isolated since the 1930s. Their biosynthetic pathway correlates with the MEP/DOXP pathway, and many key enzymes, such as mCPS, are responsible for establishing their molecular scaffolds and stereospeci?city. Because of their unique structural characteristics and promising biological activities, total syntheses of various tanshinones have attracted the interest of many synthetic chemists, including R. H. Thomson, H. Kakisawa, R. L. Danheiser, Y. Inouye and J. K. Snyder. Tanshinones and their analogs exhibit interesting and broad antitumor activity in various cell and animal models. Most recently, the tanshinone analog neo-tanshinlactone has shown potent and selective activity against breast cancer. This review will discuss the biosynthesis, total syntheses, and antitumor activities of tanshinones,especially neo-tanshinlactone and its analogs.     

Adsorption of heavy metal ions by immobilized phytic acid

Applied Biochemistry and Biotechnology - Phytic acid (myoinositol hexaphosphate) or its calcium salt, phytate, is an important plant constituent. It accounts for up to 85% of total phosphorus in...     

Lactic acid fermentation and adsorption on PVP

Applied Biochemistry and Biotechnology - Lactic acid was produced by immobilizedLactobacillus delbreückii cells in a fixedbed reactor and then separated by a column packed with...     

Direct measurement of dipole-dipole/CSA cross-correlated relaxation by a constant-time experiment

Relaxation rates in NMR are usually measured by intensity modulation as a function of a relaxation delay during which the relaxation mechanism of interest is effective. Other mechanisms are often suppressed during the relaxation delay by pulse sequences which eliminate their effects, or cancel their effects when two data sets with appropriate combinations of relaxation rate effects are added. Cross-correlated relaxation (CCR) involving dipole-dipole and CSA interactions differ from auto-correlated relaxation (ACR) in that the signs of contributions can be changed by inverting the state of one spin involved in the dipole-dipole interaction. This property has been exploited previously using CPMG sequences to refocus CCR while ACR evolves. Here we report a new pulse scheme that instead eliminates intensity modulation by ACR and thus allows direct measurement of CCR. The sequence uses a constant time relaxation period for which the contribution of ACR does not change. An inversion pulse is applied at various points in the sequence to effect a decay that depends on CCR only. A 2-D experiment is also described in which chemical shift evolution in the indirect dimension can share the same constant period. This improves sensitivity by avoiding the addition of a separate indirect dimension acquisition time. We illustrate the measurement of residue specific CCR rates on the non-myristoylated yeast ARF1 protein and compare the results to those obtained following the conventional method of measuring the decay rates of the slow and fast-relaxing (15)N doublets. The performances of the two methods are also quantitatively evaluated by simulation. The analysis shows that the shared constant-time CCR (SCT-CCR) method significantly improves sensitivity.