Spin polarization in the relaxed excited state of the F center in case of saturated optical pumping

The dependence of the F center MCP on the polarization of pumping light is explained in terms of the spin polarization in the RES (relaxed excited state) which is derived by examining the spin-mixing processes; the spin-mixing parameter in the RES and that associated with the relaxation from the URES (unrelaxed excited state) to RES are evaluated. A new ESR method in the RES is proposed.     

Preparation of modified Jiuzao glutelin isolate with carboxymethyl chitosan by ultrasound-stirring assisted Maillard reaction and its protective effect of loading resveratrol/quercetin in nano-emulsion

Jiuzao glutelin isolate (JGI) was reported to possess interface and functional properties. To enhance the stability and properties of JGI, conjugation between JGI and carboxymethyl chitosan (CTS) through ultrasound-stirring assisted Maillard reaction (UTSA-MR) was investigated and optimized. The changes of molecular distribution, secondary structure, morphology, and amino acid composition of JGI were detected after conjugation with CTS. The solubility, foaming property and stability, viscosity, and thermal stability of four conjugates (CTS-JGI, with weight ratios of 0.5:1, 1:1, 2:1, and 4:1) were significantly increased compared to native JGI. Under the optimal glycation, the conjugate (CTS/JGI, 2:1, w/w; CTS-JGI-2) exhibited the best emulsifying ability and stability against NaCl solution, in vitro antioxidant activity, and cholesterol-lowering ability. CTS-JGI-2 stabilized oil-in-water nano-emulsion improved resveratrol (RES) and quercetin (QUE) encapsulation efficiency (80.96% for RES and 93.13% for QUE) and stability during the simulated digestion process (73.23% for RES and 77.94% for QUE) due to the connection through hydrogen bonds, pi-anion, pi-sigma, and donors between CTS-JGI and RES/QUE. Taken together, the modification of JGI by conjugating with CTS through UTSA-MR could be an excellent method to improve the functional properties of JGI. CTS-JGI-2 is a potential conjugate with functions that can be used to encapsulate functional substances in the stabilized nano-emulsion.     

Rotational energy surface and quasiclassical analysis of the rotational energy level cluster formation in the ground vibrational state of PH3

We report and substantiate a method for constructing the rotational energy surface (RES) of a molecule as a pure classical object. For an arbitrary molecule we start from the potential energy surface rather than from a conventional “effective Hamiltonian”. The method is used for constructing the RES of the PH₃ molecule in its ground vibrational state. We have used an ab initio potential energy surface [D. Wang, Q. Shi, Q.-S. Zhu, J. Chem. Phys. 112 (2000) 9624-9631; S.N. Yurchenko, M. Carvajal, P. Jensen, F. Herregodts, T.R. Huet, Chem. Phys. 290 (2003) 59-67.]. The shape of the RES is shown not to change for J from 0 to 120. The procedure of quasiclassical quantization of the RES was also undertaken, yielding a set of quasiclassical critical values of the angular momentum. The results explain the structure of quantum rotational energy levels obtained by variational calculations [S.N. Yurchenko, W. Thiel, S. Patchkovskii, P. Jensen, Phys. Chem. Chem. Phys. 7 (2005) 573-582].     

荧光光谱法和分子对接模拟技术研究白藜芦醇与胃蛋白酶的相互作用

白藜芦醇（Resveratrol, RES）属于非黄酮类多酚化合物,存在于葡萄科、百合科等多种植物体内,是一种具有多种生物活性和药理作用的天然活性物质,被广泛应用于食品和药品领域。研究表明多酚在生物体消化吸收过程中,会与消化酶（如胃蛋白酶、胰蛋白酶等）相互作用,使多酚类物质和消化酶的生物活性发生改变,进而影响多酚物质和其他营养物质的消化吸收,而RES与胃蛋白酶(Pepsin, PEP)的分子间相互作用机制未见报道。采用荧光光谱、紫外-可见吸收光谱、红外光谱和分子对接模拟等技术研究不同温度下RES与PEP相互作用的结合特性,为阐明RES和PEP的作用机制提供重要信息,同时为RES在食品和药品领域的应用提供理论参考。荧光光谱实验结果表明,PEP的荧光强度随着RES浓度的增加呈现出有规律的降低,表明RES对PEP有荧光猝灭作用。加入RES前后,PEP的紫外吸收光谱发生明显变化,初步判断RES与PEP的相互作用属于静态荧光猝灭类型;根据Stern-Volmer方程计算得到不同温度下最小猝灭速率常数K_q值远大于猝灭剂对生物大分子的最大扩散碰撞常数2.0×1010 L·mol-1·s-1,且猝灭常数(K_SV)与温度呈负相关关系,进一步验证了RES与PEP静态荧光猝灭类型结论。化学计量结合的值数目大约等于1,表明一个RES分子只能结合一个PEP分子。根据Van’t Hoff 方程以及热力学方程计算得到结果显示,ΔG＜0,说明RES与PEP的结合过程可以自发进行;ΔH＜0和ΔS＜0,表明RES与PEP之间结合作用力类型主要是氢键和范德华力。RES与PEP相互作用的同步荧光光谱和三维荧光光谱图表明,在RES的作用下,PEP的构象和微环境发生变化,色氨酸或酪氨酸残基所处微环境极性增强,疏水性减弱,蛋白构象变得疏松。红外光谱显示RES能使PEP的二级结构中α螺旋含量降低,β折叠含量增加,β转角和无规则卷曲变化不明显,这可能会影响PEP的活性。分子对接模拟实验结果显示RES与PEP中的残基Asp-32,Gly-34,Ser-35,Asn-37,Tyr-75,Gly-76,Thr-77,Ile-128,Ala-130及Gly-217有范德华力作用,与残基Ile-128及Asp-215产生超共轭效应,与残基Ser-36,Asn-37,Ile-128及Thr-218形成氢键,各种作用力使RES与PEP形成较稳定的复合物。     

Luminescence and decay times of CsI:In+

Luminescence spectra of single crystals of CsI:In⁺ excited in the A(304 nm), B(288 nm), C(268 nm) and D(257 nm) absorption bands have been studied in the temperature range 4.2–300 K. Excitation in the A band at 4.2 K gives rise to the principal emission at 2.22 eV accompanied by a partly-overlapping weak band at 2.49 eV. An additional emission band at about 2.96 eV is observed on excitation in the B, C or D bands. Yet another emission band located at 2.67 eV is excited only in the D band. The relative intensities of the bands are very sensitive to excitation wavelength as well as to temperature. The origin of all these bands is assigned in terms of a model for the relaxed excited states (RES). All the luminescence spectra were resolved into an appropriate number of skew-Gaussian components. Moments analysis leads to a value of (1.35 ± 0.02) × 10¹³ rad s^-1 for the effective frequency (ω_eff) of lattice vibrations coupled to the RES. At the lowest temperature, the radiative decay times of each of the intracenter emission bands (2.22, 2.49 and 2.96 eV) show a slow decay ( ～ 10–100 μs) and a fast decay ( ～ 10–100 ns). The 2.96 eV band, which is assigned to an emission process which is the inverse of the D-band absorption, exhibits a single decay mode ( ～ 10 μs). The intrinsic radiative decay rates (k₁, k₂), the one-phonon transition rate (K) and the second-order spin-orbit splitting (D) for the RES responsible for the principal emission are: k₁ = (6.0±-0.3)×10³ s^-1, k₂ = (1.33±-0.06)×10⁵ s^-1, K = (2.4±-0.4)×10⁷ s^-1 and D = (13.8±-0.5) cm^-1.     

Optically detected magnetic resonance of a relaxed excited state of atomic hydrogen centres in KCl and RbCl doped with I-

The ESR spectrum of relaxed excited state (RES) of inerstitial hydrogen centres in the “mixed” configuration with 3 Cl^- and 1 I^- ions next could be measured via the magnetic circular dichroism of the UV absorption bands. The g factor and I superhyperfine interactions of the RES and the ground state are practically the same, whereas the proton hyperfine interaction in the RES is reduced by ～ $\text{1}\text{3}$. The RES is a spin quartet charge transfer state with a very large zero field splitting.     

Ground and Excited States of Bipolarons in Two and Three Dimensions

The properties of large bipolarons in two and three dimensions are investigated by averaging over the relative wavefunction of the two electrons and using the Lee-Low-Pines-Huybrechts variational method. The ground-state (GS) and excited-state energies of the Fröhlich bipolaron for the whole range of electron-phonon coupling constants can be obtained. The energies of the first relaxed excited state (RES) and Franck-Condon (FC) excited state of the bipolaron are also calculated. It is found that the first RES energy is lower than the FC state energy. The comparison of our GS and RES energies with those in literature is also given.     

Fine-tuning parameters to describe the total charged-current neutrino-nucleon cross section

The total charged-current (CC) (anti)neutrino-nucleon cross section is usually estimated by the sum of contributions from quasielastic scattering (QES), single-pion production through baryon resonances (RES), and deep-inelastic scattering (DIS) with an appropriate scratching of the phase space of the RES and DIS contributions. However, the resulting total cross section is very sensitive to the value of the cutoff in invariant mass of the final hadron system produced in RES and DIS. We examine available experimental data on the QES and total CC cross sections in order to extract the best-fit value for this cutoff. By using the same data set, we attempt to adjust the poorly known values of the axial mass for QES and RES. The text was submitted by the authors in English.     

On theg-factor shift of the relaxed excited state ofF-centres in alkali halides

An interpretation of the large shifts of the electronicg-factors of the relaxed excited state (RES) ofF-centres relative to theg-factor of the free electron is given. Theseg-shifts are quantitatively explained by admixture of higher excited states to the RES through the magnetic interaction. This interpretation avoids the serious difficulties and contradictions which arise when one tries to explain theg-factor shifts exclusively within the framework of the vibronic model. As a byproduct new values for the mean radius of the RES wavefunctions are given.     

The effect of surface treatment of carbon fiber on the flexural property of thermoplastic polyimide composite

Rare earth solution (RES) surface modification and air-oxidation methods were used to improve the interfacial adhesion of the carbon fiber reinforced polyimide (CF/PI) composite. The flexural property of the PI composites reinforced by the carbon fibers treated with different surface modification methods was comparatively investigated. Results showed that the flexural strength of CF/PI composite was improved after RES treatment. The improvement of impact and flexural property of the CF/PI composite was mainly due to the improvement in interfacial adhesion after RES treatment. X-ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that the oxygen concentration was obviously increased after RES treatment. The increase in the amount of organic functional groups increased the interfacial adhesion between CF and PI matrix.     

Electron spin resonance and the spatial extension of the relaxed excited state ofF- andF A -centres

By means of an ESR detection method based on the optical pumping technique theg-factors and ESR-linewidths of the relaxed excited state (RES) of a number ofF- andF _A -centres have been measured. From the linewidths information on the spatial distribution of the RES is obtained: The data are interpreted in terms of a very diffuse wavefunction which is essentially the same for all crystals when scaled with the lattice constant. A numerical value for the parameter describing the spatial extension is given.     

松材线虫危害下马尾松光谱特征与估测模型研究

松材线虫病又叫松树枯萎病,是由于松材线虫寄生在松树上引起的毁灭性死亡病害,其发病速度快、传播迅速、防治难度大。如何识别松材线虫害并对其程度进行估测,对我国森林资源及生态环境保护具有重要意义。研究表明,马尾松叶绿素、水含量会随着虫害程度的加深逐渐减少,不同虫害程度的马尾松光谱反射率呈现较大差异,因此光谱分析技术在虫害程度估测方面具有独特优势。针对不同虫害程度的马尾松样本,研究了其光谱特征参数的变化规律,以实测光谱特征参数为自变量,样本虫害程度量化值为因变量,利用线性回归方程构建了虫害程度估测模型。该研究在光谱特征指标选择和估测模型方法上作了有价值的探索,对评估松材线虫病害有一定的指导意义,可为相关研究及当地精准农业提供科学支持和应用参考。首先针对不同虫害程度的马尾松样本,研究其在绿光、红光及近红外波段内的光谱反射率变化规律,构建指示样本虫害程度的六个光谱特征参数：绿峰反射率(RGP)、绿峰位置(GPP)、红谷反射率(FRB)、红谷位置(RBP)、红边斜率(RES)、红边位置(REP),分析光谱特征参数与虫害程度的相关性。然后构建虫害程度估测模型,其步骤可描述为：(1)计算健康、轻度、中度、重度四种不同虫害程度下的样本光谱特征参数RGP,FRB和RES;(2)量化健康、轻度、中度、重度四种样本虫害程度值;(3)以实测光谱特征参数为自变量,样本虫害程度量化值为因变量,利用线性回归方程构建虫害程度估测模型。实验中选取重庆市涪陵区永胜林场、冒合寨工区的马尾松林为研究对象,随机选取健康、染病、完全枯死的马尾松植株进行监测。数据采集过程中使用ASD野外光谱分析仪FieldSepc4,采集波段范围为从可见光400 nm到近红外波段1 100 nm处,分辨率为1 nm。共采集了70条马尾松植株的有效光谱数据,根据不同虫害程度,将其划分为健康、轻度、中度、重度和枯死五种类型,并利用Matlab软件进行处理分析,得到其光谱反射率曲线。选择涵盖绿光区(510～580 nm)、红光区(620～680 nm)和近红外区(680～780 nm)三个波段,计算各个波段的光谱特征参数,构建虫害程度估测模型。实验结果表明：(1)针对枯死样本,其“绿峰”和“红谷”特征消失,红边陡峭上升趋势被拉平。其他几种类型样本光谱特征参数RGP,FRB和RES与虫害程度呈负相关,虫害程度越深,其光谱特征参数值越小,即健康(RGP)>轻度(RGP)>中度(RGP)>重度(RGP),健康(FRB)>轻度(FRB)>中度(FRB)＞重度(FRB),健康(RES)>轻度(RES)>中度(RES)>重度(RES)。(2)随着虫害程度加深,光谱特征参数GPP向长波方向移动,即存在“红移”现象,而光谱特征参数RBP和REP向短波方向移动,即存在“蓝移”现象。(3)与一元线性估测模型相比,二元线性估测模型具有较大的相关系数R2,较小的估计误差E以及残差。实验中对两棵马尾松样本虫害程度进行估测,二元线性估测模型的结果为PD=2.990 7和PD=3.679,与实际情况相符。在后续研究中将对1 100~2 500 nm波段特征进行相关性分析。     

Ground and Excited States of Bipolarons in Two and Three Dimensions

The properties of large bipolarons in two and three dimensions are investigated by averaging over the relative wavefunction of the two electrons and using the Lee-Low-Pines-Huybrechts variational method. The groundstate (GS) and excited-state energies of the Fr(o)hlich bipolaron for the whole range of electron-phonon coupling constants can be obtained. The energies of the first relaxed excited state (RES) and Franck-Condon (FC) excited state of the bipolaron are also calculated. It is found that the first RES energy is lower than the FC state energy. The comparison of our GS and RES energies with those in literature is also given.     

双通道回声抵消系统中改进算法的定点化实现

本文研究了双通道回声抵消系统的三个核心模块:频域多延时自适应滤波器算法(MDF),双端说话检测算法(DTD),以及残留回声抑制算法(RES)。针对频域算法的特点提出了改进的双端说话检测算法和基于维纳滤波与谱减法的残留回声抑制算法,然后以上述三种算法为核心模块实现双通道回声抵消系统,并对系统定点化以便在定点DSP处理器上实时实现,分析并解决了定点化的精度问题所带来的影响。     

Peptide‐Targeted Gold Nanoparticles for Photodynamic Therapy of Brain Cancer

Targeted drug delivery using epidermal growth factor peptide‐targeted gold nanoparticles (EGF_pep‐Au NPs) is investigated as a novel approach for delivery of photodynamic therapy (PDT) agents, specifically Pc 4, to cancer. In vitro studies of PDT show that EGF_pep‐Au NP‐Pc 4 is twofold better at killing tumor cells than free Pc 4 after increasing localization in early endosomes. In vivo studies show that targeting with EGF_pep‐Au NP‐Pc 4 improves accumulation of fluorescence of Pc 4 in subcutaneous tumors by greater than threefold compared with untargeted Au NPs. Targeted drug delivery and treatment success can be imaged via the intrinsic fluorescence of the PDT drug Pc 4. Using Pc 4 fluorescence, it is demonstrated in vivo that EGF_pep‐Au NP‐Pc 4 impacts biodistribution of the NPs by decreasing the initial uptake by the reticuloendothelial system (RES) and by increasing the amount of Au NPs circulating in the blood 4 h after IV injection. Interestingly, in vivo PDT with EGF_pep‐Au NP‐Pc 4 results in interrupted tumor growth when compared with EGF_pep‐Au NP control mice when selectively activated with light. These data demonstrate that EGF_pep‐Au NP‐Pc 4 utilizes cancer‐specific biomarkers to improve drug delivery and therapeutic efficacy over untargeted drug delivery.     

Random matrix ensembles with random interactions: Results for EGUE(2)-SU(4)

We introduce in this paper embedded Gaussian unitary ensemble of random matrices, for m fermions in Ω number of single particle orbits, generated by random twobody interactions that are SU(4) scalar, called EGUE(2)-SU(4). Here the SU(4) algebra corresponds to Wigner’s supermultiplet SU(4) symmetry in nuclei. Formulation based on Wigner-Racah algebra of the embedding algebra U(4Ω) ? U(Ω) ? SU(4) allows for analytical treatment of this ensemble and using this analytical formulas are derived for the covariances in energy centroids and spectral variances. It is found that these covariances increase in magnitude as we go from EGUE(2) to EGUE(2)-s to EGUE(2)-SU(4) implying that symmetries may be responsible for chaos in finite interacting quantum systems.     

Hyperfeinstrukturuntersuchung der 4p und 5p 2 P 3/2-Terme im K I-Spektrum durch Resonanzstreuung von Licht zur Bestimmung der Kernquadrupolmomente von K39 und K41

In order to determine the nuclear quadrupol moments of the stable K-isotopes, the hyperfine structure of the 4p and5p ²P_3/2-states was investigated by resonance scattering of light. The scattered intensityR(H) from separated isotopes in a sealed off resonance cell, as function of an external magnetic fieldH was observed with different polarisations (σ- andπ-components perpendicular toH) both in exciting and scattered light. Because the hfs-splitting of the investigated states is comparable to the radiation widthГ, the measured change in intensityΔR(H)/ΔH is due to interference effects (Hanle-effect, level-crossing, anti-crossing) and decoupling of electronic and nuclear spin (Heydenburg-effect). The different effects are not distinguishable in contrary to an usual level-crossing experiment and therefore the measured signal-structure is compared with line shape calculations according to Breit's-formula. Assuming “white” excitation andg _J =4/3, the measured signal-structure can be explained with the following values:Γ/2π (4p)=5.7 (4) MHzΓ/2π (4p)=5.7 (4) MHz K³⁹:A(4p)=6.13(5) MHzB(4p)=2.72(12) MHzA(5p)=1.97(2) MHzB(5p)=0.85 (3) MHz K⁴¹:A(4p)=3.40(8) MHzB(4p)=3.34(24) MHzA(5p)=1.08(2) MHzB(5p)=1.06 (4) MHz. Without Sternheimer corrections one obtains from these values Q(K³⁹)=0.062 · 10^?24 cm² and Q(K⁴¹)=0.076 · 10^?24 cm² for the electrical nuclear quadrupolmoments of K³⁹ and K⁴¹.     

Photoelectron (He(I), He(II) and X-ray) spectroscopy of γ-pyrone and its related sulphur derivatives: valence and core ionization energies and shake-up satellites

The photoelectron He(I) and He(II) spectra of 4H-pyran-4-one (1), 4H-thiopyran-4-one (2), 4H-pyran-4-thione (3) and 4H-thiopyran-4-thione (4) are reported. The assignments are based on experimental evidence, taking into account the results of theoretical calculations. The outermost orbital sequences proposed (X = O, S) are n_X (σ), 3b₁ (π), 1a₂(π) for 1, 2 and 4; and 3b₁(π), n_X(σ) and 1a₂(π) for 3. The shifts of the core-ionization energy values for 1–4 are ascribed to a drift of π-charge from the intracyclic heteroatom towards the carbonyl or thiocarbonyl group. Low-energy shake-up satellites (up to 25% with respect to the main line) are observed in the various energy regions of the XPS spectra. They are qualitatively reproduced by CNDO/2 calculations. The most important satellites derive from the transition in the ion corresponding to the 3b₁ (π) → 4b₁(π*) transition in the UV-visible spectra of the neutral molecules. Charge rearrangements accompanying this transition lead to charge depletion of the core-ionized atom.     

Synthesis of p-hydroxycinnamic acid derivatives and investigation of fluorescence binding with bovine serum albumin

Four novel p-hydroxycinnamic acid amides, (E)-4-(3-oxo-3-((4-(N-(pyrimidin-2-yl)sulfamoyl)phenyl)amino)prop-1-en-1-yl)phenyl-acetate (SPPA), (E)-3-(4-hydroxyphenyl)–N-(4-(N-(pyrimidin-2-yl)sulfamoyl)phenyl)acrylamide (SPAA), (E)-4-(3-((4-(N-(4,6-dimethylpyrimidin-2-yl)sulfamoyl)phenyl)amino)-3-oxoprop-1-en-1-yl)phenyl acetate (SPOA), and (E)-N-(4-(N-(4,6-dimethylpyrimidin-2-yl)sulfamoyl)phenyl)-3-(4-hydroxyphenyl)acrylamide (SPHA), were synthesized. The chemical structures of these compounds were confirmed using ¹H-NMR, ESI-MS, and elemental analyses. SPPA and SPOA were determined using single-crystal X-ray diffraction analysis. The interactions of these four compounds with bovine serum albumin (BSA) were investigated through fluorescence and UV–vis spectral studies. The thermodynamic parameters (i.e., ΔH, ΔG, and ΔS) and the quenching constants were calculated. The binding constants and the number of binding sites, n, were investigated. The distances between BSA and its derivatives were obtained based on fluorescence resonance energy transfer, and the conformational changes in BSA were observed from synchronous fluorescence spectra.     

三维荧光光谱结合二阶校正方法同时测定水中两种酚类

水是生命之源,人们日常生产生活离不开水。近年来水体污染日趋严重,已经危害到人类的健康。酚类化合物(Phenolic Compound)是一种广泛存在且很难降解的有机污染物,指的是芳香烃中苯环上的氢原子被羟基取代所生成的含羟基衍生物,毒性很强,对动植物及人类的生命活动有严重危害。实验研究对象选取间苯二酚(resorcinol,RES)和对苯二酚(hydroquinone,HYD)来配制待测样本,并且在其中3组预测样本中加入苯酚(phenol,PHE)作为干扰物,待测样本和空白溶剂分别用FS920稳态荧光光谱仪(edinburgh instruments,EI)扫描得到荧光光谱数据。对所得到的数据通过扣除空白溶剂法来消除拉曼散射的影响,得到的数据在消除干扰的同时最大程度保留下来原光谱所包含的重要信息。校正后光谱变得更加圆滑,荧光强度显著增强,因此,校正处理后的光谱信息更为准确。利用三维荧光光谱(EEM)结合平行因子分析(PARAFAC)和交替惩罚三线性分解(APTLD)两种二阶校正方法,分别完成在不含干扰物和含有干扰物、同时激发-发射光谱严重重叠时对间苯二酚、对苯二酚的快速、直接、准确测量,并给出定性、定量分析结果。PARAFAC算法对混合体系的组分数(即化学秩)较敏感,组分数选取过大易使其陷入计算"沼泽",迭代次数增多,计算耗时变长。故本文利用核一致诊断法(CORCONDIA)预估计出准确的组分数,保证PARAFAC算法更加快速准确。从定性分析结果知,当不含有干扰物时,PARAFAC能够准确分辨出间苯二酚和对苯二酚,二者荧光峰位置极为接近,很难用传统方法分辨,体现出将三维荧光光谱技术与化学计量学二阶校正方法相结合所具有的"二阶优势";定量分析结果给出,在有干扰物共存时,分别应用两种二阶校正法解析光谱数据结果显示:PARAFAC的浓度预测回收率为93.4%±0.5%~97.1%±1.0%,预测均方根误差小于0.190 mg·L^-1;APTLD的浓度预测回收率为95.9%±1.6%~97.2%±0.8%,预测均方根误差小于0.116 mg·L^-1,通过比较两种方法性能得:PARAFAC对待测物组分数敏感,对待分解的光谱数据严格线性要求高;而APTLD对混合物组分数不敏感,计算速度快,抗噪声能力较强,结果稳定,具有较明显的优势。