Low-barrier hydrogen bond between phosphate and the amide group in phosphopeptide

As the conversion between the monoionic (1) and diionic (2) form of the phosphate occurs, the phosphorylated peptides or proteins can not only cause the formation of a hydrogen bond between the phosphate group and the amide group but also change the strength of the hydrogen bond to form low-barrier hydrogen bonds (LBHBs). This reversible protonation of the phosphate group, which changes both the electrostatic properties of the phosphate group and the strength of the hydrogen bond, provides a possible mechanism in regulating protein function.     

Synthetic studies on terpenic compounds—XI : Stereospecific total synthesis of portulal,

A stereospecific total synthesis of portulal 1 has been accomplished starting from the Diels-Alder adduct 2 from chloromethylmaleic anhydride and 1-vinylcyclohexene. Firstly 2 was converted by an efficient sequence of reactions to perhydroazulenoid lactone 5, which possesses the correct relative configuration with respect to three chiral centers out of the four present in 1. The fourth chiral center at C-6 was introduced stereospecifically together with the one-carbon substituent at C-4 by the ring formation between C-4 and C-6, and its cleavage to give an exomethylene lactone 35. At this stage the stereochemical validity of the crucial intermediate 35 was confirmed by chemical correlation with the hydroxy lactone 37 which was derived from natural 1 through a systematic degradation. Then 35 was transformed to 37 and the synthesis continued further by using 37 as a relay compound to afford 1.     

Quartz resonator signatures under Newtonian liquid loading for initial instrument check

The quartz crystal microbalance (QCM) has been increasingly utilized in the monitoring of the deposition of thin macromolecular films. Studies in the deposition of polymers, biomaterials, and interfacial reactions under electrochemical environment are some of the conditions for the study of these material and deposition properties at a lipid interface. Numerous studies have shown the difficulties in configuring an experimental setup for the QCM such that the recorded data reflect only the behavior of the quartz crystal and its load, and not some artifact. Such artifacts for use in liquids include mounting stress, surface properties such as hydrophobicity, surface roughness coupling to loading liquids, influence of compressional waves, and even problems with the electronic circuitry including the neglect of the quartz capacitance and the hysteretic effects of electronic components. It is thought useful to obtain a simple test by which the user could make a quick initial assessment of the instrument's performance. When a smooth quartz crystal resonator is immersed from air into a Newtonian liquid, the resonance and loss characteristics of the QCM are changed. A minimum of two experimental parameters is needed to characterize these changes. One of the changes is that of the resonant frequency. The second is characterized by either a change in the equivalent circuit resistance (DeltaR) or a change in the resonance dissipation (DeltaD). Two combinations of these observables, in terms of either Deltaf and DeltaR or Deltaf and DeltaD, which we define as Newtonian signatures of S(1) and S(2), are calculated to have fixed values and to be independent of the harmonic and of the physical values of the Newtonian liquid. We have experimentally determined the values of S(1) and S(2) using three different QCM systems. These are the standard oscillator, the network analyzer, and the QCM dissipation instrument. To test the sensitivity of these signatures to surface roughness, which is potential experimental artifact, we determined the values of S(1) and S(2) for roughened crystals and found that these signatures do reflect that experimental condition. Moreover, these results were qualitatively in accord with the roughness scaling factor described by Martin.     

High-energy, high-contrast, multiterawatt laser pulses by optical parametric chirped-pulse amplification

We describe a compact, reliable, high-power, and high-contrast noncollinear optical parametric chirped-pulse amplifier system. With a broadband Ti:sapphire oscillator and grating-based stretching and compression, the chirped pulses are amplified from 0.1 nJ to 122 mJ in type I beta-barium borate optical parametric chirped-pulse amplifiers with a total gain of over 10(9) at 10 Hz repetition rate. Pulse compression down to 19-fs duration achieved after amplification indicates a peak power of 3.2 TW at an average power of 0.62 W. The prepulse contrast is measured to be less than 10(-8) on picosecond time scales.     

Aqueous chromatographic system for separation of biomolecules using thermoresponsive polymer modified stationary phase

We have investigated a new method for HPLC using packing materials modified with a functional polymer, such as thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm). PNIPAAm-modified silica exhibits temperature-controlled hydrophilic-hydrophobic surface property changes in aqueous systems. Temperature-responsive chromatography is performed with an aqueous mobile phase without using an organic solvent. We designed ternary copolymers of NIPAAm introduced 2-(dimethyl-amino) ethyl methacrylate (DMAEMA) as a cationic monomer and butyl methacrylate (BMA) as a hydrophobic monomer. A cationic thermoresponsive hydrogel grafted surface would produce an alterable stationary phase with both thermally regulated hydrophobicity and charge density for separation of bioactive compounds. In this study, we achieved successful separation of lysozyme without the loss of bioactivity by temperature-responsive chromatography. The electrostatic and hydrophobic interactions could be modulated simultaneously with the temperature in an aqueous mobile phase, thus the separation system would have potential applications in the separation of biomolecules.     

Photon‐Quantitative 6π‐Electrocyclization of a Diarylbenzo[b]thiophene in Polar Medium

The high reactivity of 6π‐electrocyclization in polar solvents has remained one of the important challenges for diarylethenes because of the emergence of a twisted intramolecular charge transfer (TICT) state at the excited state in such polar media, which usually quenches the photocyclization reaction. Herein we report on the preparation and highly efficient photocyclization of 2,3‐diarylbenzo[b]thiophenes with nonsymmetric side‐aryl units in a polar solvent. While the dithiazolylbenzo[b]thiophene showed a suppressed quantum yield of 6π‐electrocyclization of 54 % in methanol, the replacement of a thiazole unit with a thiophene ring led to a photon‐quantitative 6π‐cyclization reaction. The nonsymmetrical modification into the side‐aryl units was considered to enhance the CH/π interactions between side‐aryl units to support a photoreactive conformation in methanol. The stabilization of the photochromic reactive conformation is expected to suppress the formation of the TICT state at the excited state, leading to highly efficient photoreactivity.     

放射性束辐照生物学效应及相关生物物理机理

介绍了β缓发粒子衰变放射性束 9C辐照处于不同贯穿深度上人类唾液腺细胞的深度存活效应。 与稳定的 12C束流相比, 放射性 9C束流在其Bragg峰区附近展示了增强的生物学效应, 即细胞的致死效率明显增强。 探讨了放射性束 9C在其Bragg峰区展示增强生物学效应的生物物理机制, 并介绍了利用另一种放射性束 8B进行辐照生物学效应研究的新进展。 最后, 提出了一些利用放射性束可进行的辐照生物学效应前沿研究。 The depth survival effect of a β delayed particle decay 9C beam on human salivary gland (HSG) cells is presented in this paper. Compared with a stable 12C ion beam, the radioactive 9C ion beam showed an enhanced biological effect, i.e., remarkably enhanced efficiency in cell killing, at the penetration depths around its Bragg peak. The biophysical mechanisms underlying the enhanced biological effect are discussed herein, and the latest progress in biological effect induced by another radioactive 8B ion beam is introduced. In the end of this paper, several topics concerning the frontier of the radiation induced biological effects using radioactive ion beams are proposed.     

N‐Carboxy‐l‐phenyl­alanine anhydride

The mol­ecules of the title compound, 4‐benzyl‐1,3‐oxazolidene‐2,5‐dione, C₁₀H₉NO₃, are linked by intermolecular hydrogen bonds between the imino group of the five‐membered ring and an adjacent carbonyl O‐atom, along the c axis. The benzyl groups are stacked in a layer and the five‐membered rings are arranged in another layer sandwiched by the benzyl group layer. This sandwich structure should explain the high polymerizability of the title compound in the solid state.     

Synthesis of poly(O-phospho-L-serine) and its structure in aqueous solution

A novel polypeptide, poly(O-phospho-L -Ser), was synthesized through the following three steps: i) preparation of O-diphenylphospho-L -serine N-carboxyanhydride [Ser(PPh₂) NCA]; ii) polymerization of Ser(PPh₂) NCA; iii) removal of phenyl groups from poly[Ser(PPh₂)]. The overall yield in the three- step synthesis was 71%, and the phospho-Ser content in poly(O-phospho-L -Ser) was 98 ± 1%. Circular dichroism spectra suggest that the polypeptide has two different disordered structures in aqueous solution.