On the reaction mechanism of adduct formation in LOV domains of the plant blue-light receptor phototropin

The blue-light sensitive photoreceptor, phototropin, is a flavoprotein which regulates the phototropism response of higher plants. The photoinduced triplet state and the photoreactivity of the flavin-mononucleotide (FMN) cofactor in two LOV domains of Avena sativa, Adiantum capillus-veneris, and Chlamydomonas reinhardtii phototropin have been studied by time-resolved electron paramagnetic resonance (EPR) and UV-vis spectroscopy at low temperatures (T < or = 80 K). Differences in the electronic structure of the FMN as reflected by altered zero-field splitting parameters of the triplet state could be correlated with changes in the amino acid composition of the binding pocket in wild-type LOV1 and LOV2 as well as in mutant LOV domains. Even at cryogenic temperatures, time-resolved EPR experiments indicate photoreactivity of the wild-type LOV domains, which was further characterized by UV-vis spectroscopy. Wild-type LOV1 and LOV2 were found to form an adduct between the FMN cofactor and the functional cysteine with a yield of 22% and 68%, respectively. The absorption maximum of the low-temperature photoproduct of wild-type LOV2 is red-shifted by about 15 nm as compared with the FMN C(4a)-cysteinyl adduct formed at room temperature. In light of these observations, we discuss a radical-pair reaction mechanism for the primary photoreaction in LOV domains.     

WAVELENGTH DEPENDENCE OF QUANTUM YIELDS AND PRODUCT DISTRIBUTION IN THE ANAEROBIC PHOTOCHEMISTRY OF BILIRUBIN DIMETHYL ESTER

Abstract— ( Z,Z )-Bilirubin dimethyl ester exists in two or more forms in solution, and photorearranges to the ( E,Z )- and ( Z,E )-isomers. Deaerated solutions of bilirubin dimethyl ester in 2-methyltetrahydrofuran and chloroform/ethanol were irradiated with light of 10nm bandwidth in the range 380–470 nm at room temperature. Absorption difference spectroscopy showed that the solution forms of bilirubin dimethyl ester differ in their photoreactivity, and that the quantum yields of their disappearance and the distribution of the photorearrangement isomers are wavelength dependent.     

室温水解法制备介孔二氧化钛的表征及应用

以氯化十六烷基吡啶为模板剂,在室温下直接合成出介孔TiO2,探讨了合成条件的影响,分别用红外光谱(FT IR)、热分析(TG DTA),X射线粉末衍射(XRD)和N2吸附等温线技术对产物进行了表征.结果表明:样品经均三甲苯和磷酸处理后能有效提高比表面积和热稳定性,具有较高的光催化活性.     

Benzylbenzoin benzyl ethers as new photoinitiators

The title benzoins are prepared and their photochemistry has been investigated. Product analysis studies indicate that the benzoin undergoes Norrish Type I photocleavage to generate benzoyl and benzyloxybenzyl radical, followed by thermal fragmentation to produce deoxybenzoin thereby generating benzyl radical. All three transient species are actually detected and characterized by laser flash photolysis of the benzoin in solution at room temperature. The efficiency of the benzoins as photoinitiator has been also investigated. Effects of ring substituents and polycyclic aromatic rings on the photoreactivity have been revealed.     

Aqueous solution-processed NiOx anode buffer layers applicable for polymer solar cells

A green and facile method has been developed for the room temperature and aqueous solution preparation of NiO_x film as anode buffer layers for polymer solar cells (PSCs). The NiO_x buffer layer is prepared simply by spin-coating nickel acetylacetonate precursor-based aqueous solution onto ITO substrate at room temperature in air. UV-ozone post-treatment promotes the formation of dipolar NiOOH species on the film surface, resulting in the anode buffer layer with suitable work function. PSCs have been fabricated with the device structure of ITO/NiO_x/photoactive layer/PFN/Al. The power conversion efficiencies of the PSCs based on PTB7:PC₇₁BM blends (8.43%) and P3HT:PC₇₁BM blends (3.04%) with NiO_x anode buffer layer are comparable to those with the commonly used PEDOT:PSS anode buffer layer. In addition, the devices made with NiO_x buffer layer exhibit much better air stability than those with PEDOT:PSS. These results indicate that the water solution processed NiO_x film at room temperature in air is a promising anode buffer layer for efficient and stable PSCs. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 747–753     

Chiral analysis of biogenic D,L-amino acids derivatized by N-fluorenylmethoxycarbonyl-L-alanyl N-carboxyanhydride using high-performance liquid chromatography

Nineteen biogenic D,L-amino acids are derivatized with highly reactive N-fluorenylmethoxycarbonyl-L-alanyl N-carboxyanhydride. Using a 0.5M borate buffer at pH 7.5 and acetone, the derivatization of amino acids is completed in 5 min at room temperature. Some of the resulting diastereomeric N-protected dipeptides are successfully separated on an octylsilica stationary phase using 100mM acetate buffer (pH 4.4) and acetonitrile as the eluent.     

PHOTOCHEMICAL INTERACTIONS BETWEEN NITROXIDE FREE RADICALS AND PHENOTHIAZINES IN SOLUTION

Abstract— Ultraviolet irradiation of photosensitive molecules like phenothiazine derivatives leads to the formation of short lived free radicals which are able to reduce stable nitroxide free radicals generally used as spin labels. The measurement of the electron spin resonance signal decay of nitroxides offers a tool for studying the photochemical reaction of phenothiazine derivatives in solution at room temperature, in a 10^-5 to 10^-2 M concentration range. Analysis of the reaction mechanism shows that the paramagnetic nitroxide is an efficient quencher of the phenothiazine triplet state; this reaction was used to demonstrate the influence of the solvent, quenching by oxygen and the role of the chemical structure of six phenothiazine derivatives on their photoreactivity in solution.     

Kinetics of the OH initiated oxidation of nitrogen monoxide

The kinetics of the recombination reaction, OH+NO+(M) --> Products have been investigated by the Pulsed Laser Photolysis-Laser Induced Fluorescence (PLP-LIF) technique in nitrogen and helium buffer gases at room temperature and as a function of pressure (30-900 Torr). Our values for the absolute rate coefficient in nitrogen at room temperature are in excellent agreement with the JPL 2003 and with the current IUPAC 2003 recommendations. With the exception of a very old study by Overend, our rate constants in helium are the only ones to cover the range of pressures between 30 and 900 Torr.     

Synthesis and Cytotoxic Activity of 5-Benzoylhexahydropyrimidine Derivatives

Russian Journal of Organic Chemistry - The reaction of ethyl benzoylacetate with formaldehyde and natural amino acid ester hydrochlorides in acetate buffer (AcONa/AcOH, pH 4.0) at room temperature...     

Photo-degradation behaviour of roseoflavin in some aqueous solutions

An absorption and emission spectroscopic characterization of roseoflavin (8-dimethylamino-8-demethyl-riboflavin, RoF) in aqueous solutions was carried out. The studies were concentrated on roseoflavin in pH 8 phosphate buffer. Absorption cross-section spectra, fluorescence excitation spectra, fluorescence quantum distributions, fluorescence quantum yields and fluorescence lifetimes were determined. The fluorescence of RoF is quenched by photo-induced intra-molecular charge-transfer at room temperature. The photo-degradation of RoF in un-buffered water, in Tris–HCl buffer, and in phosphate buffer was studied. Phosphate buffer and to a smaller extent Tris buffer catalyse the RoF photo-degradation. Photo-excitation of the primary photoproduct, 8-methylamino-riboflavin (8-MNH-RF), enhanced the RoF degradation by triplet 8-MNH-RF – singlet RoF excitation transfer with subsequent triplet-state RoF degradation.     

Self-assembly of focal point oligo-catechol ethylene glycol dendrons on titanium oxide surfaces: adsorption kinetics, surface characterization, and nonfouling properties

This work covers the synthesis of second-generation, ethylene glycol dendrons covalently linked to a surface anchor that contains two, three, or four catechol groups, the molecular assembly in aqueous buffer on titanium oxide surfaces, and the evaluation of the resistance of the monomolecular adlayers against nonspecific protein adsorption in contact with full blood serum. The results were compared to those of a linear poly(ethylene glycol) (PEG) analogue with the same molecular weight. The adsorption kinetics as well as resulting surface coverages were monitored by ex situ spectroscopic ellipsometry (VASE), in situ optical waveguide lightmode spectroscopy (OWLS), and quartz crystal microbalance with dissipation (QCM-D) investigations. The expected compositions of the macromolecular films were verified by X-ray photoelectron spectroscopy (XPS). The results of the adsorption study, performed in a high ionic strength ("cloud-point") buffer at room temperature, demonstrate that the adsorption kinetics increase with increasing number of catechol binding moieties and exceed the values found for the linear PEG analogue. This is attributed to the comparatively smaller and more confined molecular volume of the dendritic macromolecules in solution, the improved presentation of the catechol anchor, and/or their much lower cloud-point in the chosen buffer (close to room temperature). Interestingly, in terms of mechanistic aspects of "nonfouling" surface properties, the dendron films were found to be much stiffer and considerably less hydrated in comparison to the linear PEG brush surface, closer in their physicochemical properties to oligo(ethylene glycol) alkanethiol self-assembled monolayers than to conventional brush surfaces. Despite these differences, both types of polymer architectures at saturation coverage proved to be highly resistant toward protein adsorption. Although associated with higher synthesis costs, dendritic macromolecules are considered to be an attractive alternative to linear polymers for surface (bio)functionalization in view of their spontaneous formation of ultrathin, confluent, and nonfouling monolayers at room temperature and their outstanding ability to present functional ligands (coupled to the termini of the dendritic structure) at high surface densities.     

氮氧自由基的研究(Ⅳ)——氮氧自由基对半胱氨酸的氧化反应

氮氧自由基是目前最广泛采用的自旋标记物^[1-2]。2,2,6,6-四甲基哌啶氮氧自由基虽然在许多情况下是很稳定的,但是仍然可以发生歧化、单电子氧化还原等反应^[3-4]。     

Spectrophotometric Study on the Interaction between Arsenazo M and Proteins

Dye binding protein assays are commonly used in biochemical and clinical laboratories, and the reaction mechanism is still under investigation1-2. In this paper, the interaction of Arsenazo M with serum proteins was studied. Procedure In most experiments, 1.20 mL of Arsenazo M (5.0010-4 mol/L), 2.0 mL of C-L buffer solution, 3.0 mL alcohol and certain amount of protein standard solutions or samples were added to 10 mL volumetric flasks, then diluted to mark with water, and mixed thor…     

蛋氨酸改性TiO2空心纳米盒高效可见光催化RhB分解和NO氧化

由高能面 TiO2纳米片 (TiO2-NSs) 组装成的 TiO2空心纳米盒 (TiO2-HNBs)显示出比单独 TiO2-NSs 更强的光催化性能, 但是 TiO2-HNBs 依然属于紫外光催化剂, 无法充分利用太阳能. 因此, 开发具有可见光响应的由高能面 TiO2-NSs 组装而成的 TiO2-HNBs 具有重要意义. 本文将立方体 TiOF2与含有 N 和 S 元素的生物分子蛋氨酸混合, 通过一步焙烧制备了具有可见光响应活性的 N 和 S 元素共掺杂的 TiO2-HNBs(掺杂催化剂标记为 TMx, 未掺杂催化剂标记为 Tx, x 代表焙烧温度).由立方体 TiOF2到锐钛矿相 TiO2空心纳米盒的转变是一个自模板转化过程. 氟离子的存在降低了 TiO2高能面(001)面的表面能, 从而使得高能面 TiO2纳米片的形成变得可能. 因此, 热处理立方体 TiOF2可得到由高能面 TiO2纳米片组装的 TiO2空心纳米盒.本文系统研究了焙烧温度 (300-500 ℃) 对所制 TiO2-HNBs 结构与光催化性能的影响. 结果发现, 在 350 ℃下焙烧, TiOF2完全转化成锐钛矿相 TiO2-HNBs. 但是焙烧蛋氨酸与 TiOF2的混合物, 需 400 ℃才能完全实现 TiOF2到锐钛矿相TiO2-HNBs 的转变. 这说明蛋氨酸的加入阻碍了 TiOF2向锐钛矿相 TiO2-HNBs 的转变. XPS 结果显示, 经过 400 ℃焙烧的蛋氨酸改性样品 (TM400), N 和 S 元素成功掺入了 TiO2-HNBs 晶格, 使其产生可见光催化活性.相对于 400 ℃焙烧 TiOF2所得样品 T400, 蛋氨酸改性的 TM400 催化剂可见光降解罗丹明 B 染料 (RhB) 和 NO 氧化的性能分别提升了 1.55 倍和 2.0 倍, 这与其更强的可见光吸收性能和光生载流子分离效率有关. 400 ℃焙烧的蛋氨酸改性的 TM400 可见光催化活性稳定, 连续 5 次可见光催化 RhB 降解后, 其活性没有明显改变, 显示了潜在的应用前景.     

Highly efficient photochemical generation of a triple bond: synthesis, properties, and photodecarbonylation of cyclopropenones

UV irradiation of alkyl-, aryl-, and heteroatom-substituted cyclopropenones results in the loss of carbon monoxide and the formation of quantitative yields of corresponding alkynes. The quantum yield of the photochemical decarbonylation reaction ranges from 20% to 30% for alkyl-substituted cyclopropenones to above 70% for the diphenyl- and dinaphthylcyclorpopenones. Rapid formation (<5 ns) and then a somewhat slower decay (ca. 40 ns) of an intermediate in this reaction was observed by using laser flash photolysis. The DFT calculations allowed us to identify this intermediate as a zwitterionic species formed by a cleavage of one of the carbon-carbon bonds of the cyclopropenone ring. The latter then rapidly loses carbon monoxide to produce the ultimate acetylenic product. Despite their high photoreactivity, cyclopropenones were found to be thermally stable compounds with the exception of hydroxy- and methoxy-substituted cyclopropenones. The latter undergo rapid solvolysis in hydroxylic solvents even at room temperature. The application of this reaction to the in situ generation of the enediyne structure was illustrated by the photochemical preparation of benzannulated enediyne 12.     

Room temperature operation of all-solid-state battery using a closo-type complex hydride solid electrolyte and a LiCoO_2 cathode by interfacial modification

We report on an all-solid-state battery that employs a closo-type complex hydride solid electrolyte and a LiCoO2 cathode.Interfacial modification between the solid electrolyte and cathode with a LiNbO_3 buffer layer enables reversible charge-discharge cycling with a cell voltage of 3.9V (vs.Li+/Li) at room temperature.Electrochemical analyses clarify that the given modification effectively suppresses side reactions at the cathode/solid electrolyte interface.The interfacial resistance is lowered by ca.10 times with a 5 nm thick LiNbO_3 buffer layer compared to that without a buffer layer,so that a discharge capacity of 109 mAh g~(-1) is achieved.These results suggest that interfacial modification can be a viable approach to the development of high-voltage all-solid-state batteries using closo-type complex hydride solid electrolytes and oxide cathodes.     

TEMPERATURE DEPENDENCE OF THE PHOSPHORESCENCE LIFETIMES OF HETEROGENEOUS TRYPTOPHAN RESIDUES IN GLOBULAR PROTEINS BETWEEN 293 AND 77 K

Abstract— The phosphorescence of five globular proteins containing tryptophan residues was observed in deoxygenated neutral ethylene glycol-phosphate buffer (1:1 by volume) at 293 and 77 K. Their spectral features at 293 K are closely identical to those at 77 K apart from a lack of tyrosine phosphorescence at 293 K. and are independent of the excitation wavelength between 250 and 310 nm. From the present results. it can be concluded that the buried tryptophan residues are the only phosphorescing centers at room temperature. Their phosphorescence lifetimes were measured as a function of temperature in the range from 77 to 293 K. At room temperature, their phosphorescence lifetimes are between about 1 and 500 ms. On the basis of their temperature dependence, the heterogeneous tryptophan environments are discussed in terms of a temperature-activated nonradiative rate. We suggest that the observation of the phosphorescence characteristics of globular proteins containing tryptophan residues buried in the interior of the protein molecule at room temperature is likely to prove useful in probing the protein structure in solution.     

Effective interaction energy of water dimer at room temperature: an experimental and theoretical study

Buffer-gas pressure broadening for the nu(1)+nu(3) band of H(2)O at 1.34-1.44 mum for a variety of buffer gases was investigated at room temperature using continuous-wave cavity ring-down spectroscopy. The effective interaction energy of water dimer under room temperature conditions was evaluated from the pressure broadening coefficients for rare gases using Permenter-Seaver's relation. Monte Carlo simulations were performed using ab initio molecular orbital calculations to evaluate the interaction energies for the water dimer at 300 K. In this theoretical calculation, the orientations of the two water molecules were statistically treated.     

Bamboo (<Emphasis Type="Italic">Phyllostachys pubescens</Emphasis>) as a Natural Support for Neutral Protease Immobilization

Lignin polymers in bamboo (Phyllostachys pubescens) were decomposed into polyphenols at high temperatures and oxidized for the introduction of quinone groups from peroxidase extracted from bamboo shoots and catalysis of UV. According to the results of FT-IR spectra analysis, neutral proteases (NPs) can be immobilized on the oxidized lignin by covalent bonding formed by amine group and quinone group. The optimum condition for the immobilization of NPs on the bamboo bar was obtained at pH 7.0, 40 °C, and duration of 4 h; the amount of immobilized enzyme was up to 5 mg g^?1 bamboo bar. The optimal pH for both free NP (FNP) and INP was approximately 7.0, and the maximum activity of INP was determined at 60 °C, whereas FNP presented maximum activity at 50 °C. The K_m values of INP and FNP were determined as 0.773 and 0.843 mg ml^?1, respectively; INP showed a lower K_m value and V_max, than FNP, which demonstrated that INP presented higher affinity to substrate. Compared to FNP, INP showed broader thermal and storage stability under the same trial condition. With respect to cost, INP presented considerable recycling efficiency for up to six consecutive cycles.     

自旋阀多层膜的电化学制备及其巨磁电阻效应

采用双槽控电位电沉积法在n-Si(111)基体上以NiFe 薄膜为缓冲层制备了[Ni80Fe20/Cu/Co/Cu]n自旋阀多层膜, 并确定了电沉积的工艺条件. 利用X射线衍射(XRD)表征了自旋阀多层膜的超晶格结构, 研究了NiFe缓冲层对自旋阀生长取向的影响. 采用四探针法研究了各子层厚度对自旋阀巨磁电阻效应的影响, 通过振动样品磁强计(VSM)测试了自旋阀的磁滞回线. 自旋阀的巨磁电阻(GMR)值最初随着铜层厚度的变化并发生周期性振荡, Cu 层厚度为3.6 nm时, GMR 达到最大值,随后逐渐减小. 随着Co层和NiFe 层厚度的增大, GMR 值的变化趋势均为先增大后减小. 当自旋阀的结构为NiFe(25 nm)/[Cu(3.6 nm)/Co(1.2 nm)/Cu(3.6 nm)/NiFe(2.8 nm)]30时, GMR 值可达5.4%, 对应的磁电阻灵敏度(SV)为0.2%·Oe-1, 饱和磁场仅为350 Oe.