Conformational Equilibria in Polypeptides. I. Determination of AccurateJHCCoupling Constants in Antamanide by 2D NMR Multiplet Simulation

High-precision heteronuclear three-bond coupling constants including³J(H^N, C′),³J(H^N, C^β),³J(H^α,C^γ), and³J(H^β, C′) are determined for the nonproline residues in uniformly¹³C-enrichedantamanide,cyclo-(-Val¹-Pro²-Pro³-Ala⁴-Phe⁵-Phe⁶-Pro⁷-Pro⁸-Phe⁹- Phe¹⁰-), using quantitative numerical 2D NMR spectrum evaluation based on the product-operator formalism. The experimental basis comprises two-dimensional¹H,¹³C-heteronuclear relayed E.COSY spectra [J. M. Schmidt, R. R. Ernst, S. Aimoto, and M. Kainosho,J. Biomol. NMR6,95 (1995)], the multiplet patterns of which are subjected to iterative least-squares 2D multiplet-simulation procedures. Accuracy and precision of the spectrum fit are assessed byFstatistics and analysis of variances (ANOVA) leading to confidence intervals for the optimized spin-system parameters. The long-range J coupling constants obtained and their standard deviations provide the experimental foundation for a later detailed analysis of φ and χ₁dihedral-angle equilibrium conformations contributing to the flexible peptide structure.     

Laurdan Spectrum Decomposition as a Tool for the Analysis of Surface Bilayer Structure and Polarity: a Study with DMPG,Peptides and Cholesterol

The highly hydrophobic fluorophore Laurdan (6-dodecanoyl-2-(dimethylaminonaphthalene)) has been widely used as a fluorescent probe to monitor lipid membranes. Actually, it monitors the structure and polarity of the bilayer surface, where its fluorescent moiety is supposed to reside. The present paper discusses the high sensitivity of Laurdan fluorescence through the decomposition of its emission spectrum into two Gaussian bands, which correspond to emissions from two different excited states, one more solvent relaxed than the other. It will be shown that the analysis of the area fraction of each band is more sensitive to bilayer structural changes than the largely used parameter called Generalized Polarization, possibly because the latter does not completely separate the fluorescence emission from the two different excited states of Laurdan. Moreover, it will be shown that this decomposition should be done with the spectrum as a function of energy, and not wavelength. Due to the presence of the two emission bands in Laurdan spectrum, fluorescence anisotropy should be measured around 480 nm, to be able to monitor the fluorescence emission from one excited state only, the solvent relaxed state. Laurdan will be used to monitor the complex structure of the anionic phospholipid DMPG (dimyristoyl phosphatidylglycerol) at different ionic strengths, and the alterations caused on gel and fluid membranes due to the interaction of cationic peptides and cholesterol. Analyzing both the emission spectrum decomposition and anisotropy it was possible to distinguish between effects on the packing and on the hydration of the lipid membrane surface. It could be clearly detected that a more potent analog of the melanotropic hormone α-MSH (Ac-Ser¹-Tyr²-Ser³-Met⁴-Glu⁵-His⁶-Phe⁷-Arg⁸-Trp⁹-Gly¹⁰-Lys¹¹-Pro¹²-Val¹³-NH₂) was more effective in rigidifying the bilayer surface of fluid membranes than the hormone, though the hormone significantly decreases the bilayer surface hydration.     

Dissociative ionization of molecules in intense laser fields

Accurate and efficient grid based techniques for the solution of the time-dependent Schrödinger equation for few-electron diatomic molecules irradiated by intense, ultrashort laser pulses are described. These are based on hybrid finite-difference, Lagrange mesh techniques. The methods are applied in three scenarios, namely H₂ ⁺ with fixed internuclear separation, H₂ ⁺ with vibrating nuclei and H₂ with fixed internuclear separation and illustrative results presented.Received: 19 November 2002, Published online: 24 April 2003PACS: 02.60.Cb Numerical simulation; solution of equations - 02.70.Bf Finite-difference methods - 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 33.80.-b Photon interactions with molecules     

High-accuracy finite-difference beam-propagation method for cylindrical geometry

A high-accuracy finite-difference beam-propagation method (HAFD-BPM) based on high-accuracy divided-difference formulas is presented. The truncation error in this HAFD-BPM is reduced to o(Δr)⁴in the transverse direction, whereas the error in a conventional FD-BPM is typically o(Δr)². Gaussian beam propagation in vacuum and nonlinear medium is simulated by this new method and conventional one. The comparison between them in computing time and accuracy reveals the advantage of this new method. As an example, this method is applied to the simulation of blow-up in self-focusing of a Gaussian beam. PACS 42.65.Hw; 42.25.Bs; 02.70.Bf     

Design and gamma sensitivity measurement of a novel dual-emitter vacuum Compton detector

A novel dual-emitter vacuum Compton detector (D-VCD) with higher gamma ray detecting efficiency is proposed. The emitters are made of Ta--Al clad metal. The gamma ray sensitivity is studied by Monte Carlo simulation using the MCNP code. A comparison between calculations and results measured by using the 1.25~MeV gamma ray of Co-60 is also performed. Experimental sensitivities for two sample D-VCDs with the same materials and structures are 1.92×10^ - 20 and 2.02×10^ - 20~C.cm²/MeV separately, which are consistent with the simulation result of 1.98×10^ - 20~C.cm²/MeV and are 4 times higher than that of VCD with a single Fe emitter. According to the simulation results, in a gamma energy range from 0.5 to 3~MeV, the maximum sensitivity variance for the D-VCD is less than 15%, and less than 5% in a range from 1 to 2~MeV in particular. The novel D-VCD is applicable to the detection of intense pulse gamma rays.     

Frequency stabilization of a laser diode to hyperfine structure of the 4D5/2 state of Rb atoms

We observed hyperfine structures of the 4D_5/2 state of ⁸⁵Rb atoms and applied them to the frequency stabilization of a laser diode by using the double resonance optical pumping (DROP). The hyperfine structures of the 4D_5/2 states of ⁸⁵Rb atoms were highly resolved in the Rb vapor cell. We compared the DROP with the optical-optical double resonance (OODR) in the 5S_1/2-5P_3/2-4D_5/2 ladder-type system of ⁸⁵Rb atoms. When we stabilized the frequency of a laser diode to the hyperfine structure of the 5P_3/2(F″ = 4)-4D_5/2(F″ = 3) transition by using the DROP spectrum, the frequency stability was approximately 2.3 × 10^− 12 after 100 s.     

Low-temperature high-resolution VUV spectroscopy of Ce doped LiYF4, LiLuF4 and LuF3 crystals

For LiYF₄:Ce³⁺, LiLuF₄:Ce³⁺ and LuF₃:Ce³⁺ crystals UV/visible emission and time-resolved VUV/UV excitation spectra were recorded at liquid helium temperature with spectral resolution of 0.1 nm for excitation spectra and better than 0.3 nm for emission spectra. Well resolved fine structures due to zero-phonon lines were clearly observed in both excitation and emission spectra for LiYF₄:Ce³⁺ and LiLuF₄:Ce³⁺. For LuF₃:Ce³⁺ crystal no fine structure was detected in the spectra even at the highest spectral resolution. Under the host excitation, the fine structure for high-energy emission band of Ce³⁺ (5d-²F_5/2) in LiLuF₄:Ce³⁺ becomes well pronounced because of weaker reabsorption effect, as compared to Ce³⁺ 4f-5d absorption, due to small penetration depth for exciting radiation. As a result the crystal-field splitting for ²F_7/2 and ²F_5/2 levels of Ce³⁺ in LiLuF₄ crystal was measured. First observation of zero-phonon lines at ∼81,550 and ∼82,900 cm⁻¹ as well as vibronic side bands due to interconfigurational 4f¹⁴-4f¹³5d transitions in Lu³⁺ is reported for excitation spectrum of LiLuF₄:Ce³⁺.     

Analysis of Ω<Subscript>c</Subscript><Superscript>*</Superscript>(css) and Ω<Subscript>b</Subscript><Superscript>*</Superscript>(bss) with QCD sum rules

In this article, we calculate the masses and residues of the heavy baryons Ω_c ^*(css) and Ω_b ^*(bss) with spin–parity with the QCD sum rules. The numerical values are compatible with the experimental data and other theoretical estimations. PACS 14.20.Lq, 14.20.Mr     

Kinetic Study of the Emission of the First Negative System in an Argon-Nitrogen Plasma at Atmospheric Pressure

Quantitative optical spectroscopy measurements of the emission spectra of the N(B²∑_u,)ν′→X²∑_gν″ transition (first negative system) in an Ar-N₂ microwave discharge at atmospheric pressure have allowed determination of the rate coefficient of the production of N molecules in the B² ∑_u, state with vibrational level ν′ = 0. The N(B²∑_u, ν′) molecules are produced by the reaction in a surface-wave-induced microwave discharge (2450 MHz) sustained in an open-ended dielectric tube. The rate coefficient K (T) has been obtained for ν′ν″ = 0 for different gas temperatures by varying the incident microwave power. The K₀₀(T) values are between 7.10^?10 and 4.10^?10 cm³ s^?1 for the temperature range 2500 to 3450K.     

Influences of thermal annealing, the electrolyte pH, and current density on the interface state density distribution of anodic MOS structures

2 /p-Si MOS structures were prepared in 0.1 M K₂SO₄ electrolyte with a pH of 7 (the 0.1 M KOH solution was buffered with H₂SO₄) at current densities of 3, 5, and 7 mA/cm² and with four different pH values of the electrolyte at 3 mA/cm². It is found that thermal annealing at a relatively low temperature can be used to improve the anodic MOS characteristics. Moreover, of the pH and current density it followed that the pH has a dominant role in the interface electrical properties. The lowest interface state densities at the maximum and the midgap positions are 7.1×10¹¹ and 2.7×10¹⁰ eV^-1cm^-2 for a sample made with pH=7, J=3 mA/cm². The characteristics of this sample seem satisfactory for device applications of anodized p-Si. Received: 8 July 1996/Accepted: 22 January 1997     

Boundary Dissipation in a Driven Hard Disk System

We perform a simulation with the aim of checking the existence of a well defined stationary state for a two dimensional system of driven hard disks when energy dissipation takes place at the system boundaries and no bulk impurities are present. PACS: 02.70.Ns, 05.60.-k, 47.27.ek     

Primary kinetic hydrogen isotope effects in deprotonations of a nitroalkane by intramolecular phenolate groups

Rate constants and kinetic isotope effects have been determined for the formation of nitronate anions from the ethers 1‐(2‐methoxyphenyl)‐2‐nitropropane, 7 (X = H, L = H and D) and 1‐(2‐methoxy‐5‐nitrophenyl)‐2‐nitropropane, 7 (X = NO₂, L = H and D), and from the corresponding phenols, 1‐(2‐hydroxyphenyl)‐2‐nitropropane, 3 (X = H, L = H and D), and 1‐(2‐hydroxy‐5‐nitrophenyl)‐2‐nitropropane, 3 (X = NO₂, L = H and D), in aqueous basic medium. For the ethers 7 , rates of deprotonation by hydroxide are comparable with those found for deprotonations of 2‐nitropropane, with k^H/k^D (25 °C) = 7.7 and 7.8, respectively. In both the cases, the isotope effects are conventionally temperature dependent. For the corresponding phenols 3 , conditions have been established under which the deprotonations of the nitroalkane are dominated by intramolecular deprotonation by the kinetically first‐formed phenolate anion, with an estimated effective molarity EM ～ 250. For 3 (X = H, L = H or D), k^H/k^D (25 °C) = 7.8, with E ? E = 6.9 kJ mol^?1 and A^H/A^D = 0.5. For 3 (X = NO₂, L = H or D), rates of intramolecular deprotonation are reduced 30‐fold, and an elevated kinetic isotope effect is found (k^H/k^D (25 °C) = 10.7). Activation parameters (E ? E = 17.8 kJ mol^?1 and A^H/A^D = 0.008) are compatible with an enhanced tunnelling contribution to reactivity in the H‐isotopomer. Copyright © 2009 John Wiley & Sons, Ltd.     

Use of PM6 quantum-chemical calculations in studying the properties of antioxidants in the biological environment

The energies of formation, enthalpies, and entropies of the conformers of 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionic acid and sodium and potassium 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionates are calculated by quantum-chemical methods in the PM6 approximation. A doubling of signals in the ¹H NMR spectrum of the first conformer is observed, which merge into singlets when the compound is heated. Changes in the structure of the conformers and donor-acceptor complexes (solvates) occur with the preservation of the metal-ligand coordination bond. Calculations of the characteristics of 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionic acid and sodium and potassium 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionates in the PM6 approximation make it possible to predict the structure and properties of the solvated structures. The energies of homolysis of the H-O bond D _(OH) are calculated, and a linear dependence of the antioxidant activity on D _(OH) for the structures of the studied compounds is demonstrated. The results make it possible to predict the properties of antioxidants in the biological environment.     

原子的解析波函数——Ⅱ.第二周期元素的正常态原子与离子的解析波函数与能量积分的计算

我们在文献[1]中设计了一套五个参数的变分波函数用来计算了周期表中前面十个原子的能量,所得结果比过去一些作者用四参数波函数所算得的结果为好。我们在过去计算经验的基础上,另外找到了一套特别简单的解析波函数,其形式为1s电子:ψ₁(r)=N₁e^-μar,2s电子:ψ₂(r)=N₂[(μr)e^-μr-Ne^-μar],2p电子:ψ₃(r)=N₃(μr)cosθe^-μr,ψ₄(r)=N₄(μr)sinθe^iφ-μr,ψ₅(r)=N₅(μr)sinθe^-iφ-μr,式中的α与μ为变分参数;N₁,N₂,N₃,N₄,N₅为归一化因子;N为正交化系数。μ可用解析法来决定,因而只有一个参数α要由数值法来决定。我们用这样的波函数算出了第二周期元素的正常态原子和离子(共有八十几个原子态)的各电子的各种能量积分值及总能量值,并确定了波函数的最佳参数值。其结果与五参数波函数的计算结果相比,一般相差在万分之一至千分之一的范围内,并比最近有些作者用一种三参数波函数所算的结果还好。根据这些结果,我们还讨论了Slater近似计算法的可靠程度和适用范围。     

原子的解析波函数

我们设计了一套变分波函数,用来计算了周期表中前面十个原子的能量。我们设计的单电子试探波函数具有下列形式:1s:ψ₁(r)=N₁e^-μαr[1+(μbr)²], 2s:ψ₂(r)=N₂[(μr)e^-μr-Ne^-μcr], 2p:ψ₃(r)=N₃(μdr)cosθe^-μdr, ψ₄(r)=N₄(μdr)sinθe^iφ-μdr, ψ₅(r)=N₅(μdr)sinθe^-iφ-μdr。式中的a,b,c,d及μ为五个变分参数。N₁,N₂,N₃,N₄与N₅为归一化因子;N由ψ₁与ψ₂的正交条件来决定。用这种波函数来计算原子的能量,所得的结果比莫尔斯等人(P.M.Morse,L.A.Young and E.S.Haurwitz)用他们设计的四参数波函数所算得的结果为好,更接近实验值,同时也接近于由自洽场所算出的结果。若我们的波函数中固定c等于1不变,这时就变为只有四个参数的波函数,结果仍比莫尔斯等人的好。     

Protonic conductivity of β″ and ion-rich β-alumina. II: Ammonium compounds

The conductivity and thermal stability of NH⁺₄, H⁺(H₂O)_nβ″ and ion-rich β-alumina single crystals have been measured by the complex impedance method in the 25–700°C temperature range. Both structures have similar properties, but ion-rich β-alumina shows a higher stability and a lower activation energy (β: 0.18 eV, β″ 0.24 eV below 400°C and 250°C respectively). The room temperature conductivity is about 3×10^-5ω^-1cm^-1. The conducting properties and mechanisms are discussed and compared to other protonic or ionic conductors.     

Spectra analysis of Tm in K2YF5

Emission and absorption spectra of Tm³⁺ in single crystal K₂YF₅ with different concentrations are reported and analyzed. The non-exponential feature of the fluorescence decay of ¹D₂ level for the high concentration sample indicates the existence of a cross-relaxation process. Energy level simulation has been carried out by using a phenomenological model with 16 parameters accounting simultaneously for the free ion and crystal field (CF) effects. A good fit was achieved with a root mean square deviation σ=18 cm⁻¹. The free ion and CF effects were then discussed by comparing the available data of K₂YF₅:Nd³⁺, LiYF₄:Tm³⁺ and LiYF₄:Nd³⁺.     

(Ca3N2)n(n=1—4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G^*基组水平上对(Ca₃N₂)_n(n=1—4)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了理论分析.结果表明,(Ca₃N₂)_n(n=1—4)团簇最稳定构型中N原子为3—5配位,Ca—N键长为0.231—0.251nm,Ca—Ca键长为0.295—0.358nm;N原子的自然电荷在-1.553e—-2.241e之间,Ca原子的自然电荷在1.035e—1.445e之间,Ca和N原子间相互作用呈现较强的离子性,Ca₃N₂和(Ca₃N₂)₃团簇有相对较高的动力学稳定性. 关键词： 3N₂)_n(n=1—4)团簇')" href="#">(Ca₃N₂)_n(n=1—4)团簇 密度泛函理论 结构与性质     

Crystalline-structure-dependent green and red upconversion emissions of Er-Yb-Li codoped TiO2

Crystalline structures and infrared-to-visible upconversion luminescence spectra have been investigated in 1 mol% Er³⁺, 10 mol% Yb³⁺ and 0-20 mol% Li⁺ codoped TiO₂ [1Er10Yb(0-20)Li:TiO₂] nanocrystals. The crystalline structures of 1Er10Yb(0-20)Li:TiO₂ were divided into three parts by the addition of Yb³⁺ and Li⁺. Both green and red upconversion emissions were observed from the ²H_11/2/⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ in Er³⁺-Yb³⁺-Li⁺ codoped TiO₂, respectively. The green and red upconversion emissions of 1Er:TiO₂ were enhanced significantly by Yb³⁺ and Li⁺ codoping, in which the intensities of green and red emissions and the intensity ratio of green to red emissions (I_green/I_red) were highly dependent on the crystalline structures. The significant enhanced upconversion emissions resulted from the energy migration between Er³⁺ and Yb³⁺ as well as the distortion of crystal field symmetry of Er³⁺ caused by the dissolving of Li⁺ at lower Li⁺ codoping concentration and the phase transformation at higher Li⁺ concentration. It is concluded that codoping with ions of smaller ionic radius like Li⁺ can efficiently improve the upconversion emissions of Er³⁺ or other rare-earth ions doped luminsecence materials.