Inclusion of menadione with cyclodextrins studied by calorimetry and spectroscopic methods

Complex formation of menadione with α‐, hydroxypropyl α‐, β‐, hydroxypropyl‐β‐, methyl‐β‐ and hydroxypropyl‐γ cyclodextrins in aqueous solution at 298.15 K was studied by using isothermal titration calorimetry, ¹H NMR, and UV–vis spectrophotometry. The experimental data indicated the partial insertion of menadione into macrocyclic cavity upon formation of two alternative types of 1:1 inclusion complexes, whose thermodynamic parameters (K, Δ_cG⁰, Δ_cH⁰, and Δ_cS⁰) were calculated. The influence of host size on the complex formation process was analyzed. β‐Cyclodextrin and its hydroxypropylated and methylated derivatives were found more effective binders towards menadione than α‐ and γ‐cyclodextrins. Copyright © 2007 John Wiley & Sons, Ltd.     

Photoinduced electron transfer between hen egg white lysozyme and anticancer drug menadione

The protein, hen egg white lysozyme, on photoexcitation undergoes electron transfer with menadione (2-methyl-1,4-naphthoquinone), a widely known anticancer drug. With the addition of menadione the fluorescence of lysozyme is quenched with the simultaneous formation of an excited state charge-transfer complex in the longer wavelength and a ground state complex. The former is further evident from laser flash photolysis studies, which indicate a tryptophan to menadione electron transfer. From fluorescence quenching studies the binding constant is found to be ∼1.7×10⁴ M⁻¹ with the corresponding changes in enthalpy (ΔH°) and entropy (ΔS°) as 12.24 kJ mol⁻¹ and 124.12 J mol⁻¹ K⁻¹, respectively, indicative of an entropy-driven process. The circular dichroism studies also show some structural changes with increase in α-helical content in the protein on interaction with menadione. Finally, docking studies give some insight into the role of Trp 108 of lysozyme in the interaction.     

Interaction of quinones with three pyrimidine bases: A laser flash photolysis study

The interaction between three different pyrimidine bases, uracil (U), cytosine (C) and thymine (T) and two quinones, 2-methyl-1,4-naphthoquinone or menadione (MQ) and 9,10-anthraquinone (AQ) have been studied using laser flash photolysis technique in organic homogeneous medium. The three pyrimidines have revealed a difference in their extent of reactivity towards the quinones, which has been attributed to their structural difference. Our works have revealed that the difference in structural dimension of the quinones is also responsible for affecting the reactivity of these pyrimidines in homogeneous medium.     

利用NMR技术测定两个新倍半萜醇酯化合物的结构s

报道了从苦皮藤叶中得到的两个新倍半萜醇酯化合物.利用NMR和2D NMR技术测得它们的化学结构分别为1β-苯乙烯酰氧基,9β-(2-羟基)-异丁酰氧基,2β,6α,8α,15-四乙酰氧基-4α-羟基-β-二氢沉香呋喃和1β-苯甲酰氧基,9β-(2-羟基)-异丁酰氧基,2β,6α,8α,     

红外杂化单光束谱的性质

同一样品不同厚度(b₁和b₂)的两单光束谱ø_b1和ø_b2经线性组合得到杂化单光束谱ø_α=αø_b1+(1-α)ø_b2=αø₀e-Kb₁+(1-α)ø₀e-Kb₂,α为杂化系数。通过改变杂化系数α,就可获得任意强度的杂化谱ø_α。系统研究了杂化光谱ø_α的性质。研究表明,只要控制合适的条件,则厚度为(b₂-αb₂+αb₁)的真实样品的单光束谱ø_b(b=b₂-αb₂+αb₁)与杂化谱ø_α高度相似,ø_α的失真程度可忽略不计。也就是说,厚度在b₁～b₂间任一厚度b的真实样品的单光束谱都可用杂化谱ø_α来表达,ø_α≈ø_b。因此,不需制备厚度为b的样品,通过改变杂化系数α就可获得研究者所希望强度的单光束谱ø_b。杂化谱方法有望在扣除背景干扰等方面得到广泛应用。     

Role of sugar in controlling reaction pathways: A study with thymine and thymidine

Magnetic field effect in conjunction with laser flash photolysis have been used for studying interactions of 9,10-anthraquinone and 2-methyl 1,4-naphthoquinone (menadione) with a DNA base, thymine (Thy) and its nucleoside, thymidine (dThd). Irrespective of medium Thy has been found to support both electron transfer (ET) and hydrogen abstraction with the quinones while dThd has exhibited a complete reluctance towards ET. This unique behavior of dThd has been attributed to a failure in attaining aromaticity by virtue of keto-enol tautomerism upon addition of a sugar moiety. Electron withdrawing effect of sugar unit is also considered responsible for reduction of ET from dThd. Again both Thy and dThd have exhibited hydrogen abstraction in homogeneous medium, which is normally unexpected. The above behaviors of the bases have been explained on the basis of their chemical structures.     

Semi-coherent interfaces without length misfit accommodation in a lamellar Al–Al2Cu eutectic

Abstract

The interfacial structure of a lamellar Al(α)-Al₂Cu(θ) eutectic obtained by directional solidification is investigated using conventional transmission electron microscopy (TEM) and high-resolution TEM. The average lamellar habit plane is close to (2 3 3)α and lie 10° from the atomically densest planes (1 1 1)α//(2 –1 1)θ. Networks of linear contrasted features are observed along the interfaces, the lines being separated each other’s in a wide range of spacings, typically 6–500 nm. These features are identified as interfacial dislocations with 1/2<1 1 0>α Burgers vectors from image contrast analysis. According to previous works, they are associated with ledge-like defects, the heights of which can reach 3 nm. The high-resolution TEM images do not confirm the presence of atomic terraces parallel to the atomically dense plane (1 1 1)α or the habit plane (2 3 3)α. The interface ensures the quasi-continuity of atomically dense planes, which is a configuration corresponding to the plane-matching model. It is suggested that α/θ interfaces can be considered as semi-coherent but in a particular sense since, according to our analysis, the theoretical length misfits between the fcc and bct lattices are too large to explain the presence of some loose dislocation networks. Their general irregular geometry suggests that these dislocation networks behave like non-equilibrated low-angle grain boundaries superposed on the α–θ interfaces.     

利用NMR技术测定两个新倍半萜醇酯化合物的结构

报道了从苦皮藤叶中得到的两个新倍半萜醇酯化合物.利用NMR和2DNMR技术测得它们的化学结构分别为1β-苯乙烯酰氧基,9β-(2-羟基)-异丁酰氧基,2β,6α,8α,15-四乙酰氧基-4α-羟基-β-二氢沉香呋喃和1β-苯甲酰氧基,9β-(2-羟基)-异丁酰氧基,2β,6α,8α,15-四乙酰氧基-4α-羟基-β-二氢沉香呋喃.并对其¹H和¹³C NMR信号进行了全归属.     

Glycosylation patterns of human alpha2-macroglobulin: Analysis of lectin binding by electron microscopy

Human alpha2-macroglobulin (α2M) is a 720 kDa glycoprotein that presents two ultrastructural conformations: slow (S-α2M) and fast (F-α2M). α2M acts mainly as a proteinase scavenger, but an immunomodulatory role was also proposed. This work studies the effect of desialylation and deglycosylation on the structure patterns of α2M by ultrastructural analysis of lectin-induced aggregates, which represents a new approach that had never been previously used. Transmission electron microscopy (TEM) analysis showed the loss of S-α2M conformation after deglycosylation, indicating that glycosidic side-chains contribute to the molecular stability of S-α2M. TEM proved to be an important tool to analyze the effect of biochemical changes on α2M, yielding an objective qualitative control of its morphological state. Certain carbohydrate residues did not vary between the α2M conformations, since both bound similarly ConA and WGA lectins. However, the binding of PNA and BSI-B₄ was slightly lower in F-α2M than in S-α2M. Among the neuraminidases used to desialylate both conformations of α2M that from Arthrobacter ureafaciens was the most effective. Incubation with the lectins ConA or SNA, respectively specific for mannosyl and sialyl residues, led to dose-dependent patterns of aggregation of α2M molecules, mediated by lectin binding and clearly visualized by TEM.     

Parisaponin I 和Parisvietnaside A 的NMR数据分析

从滇重楼中分离得到2个甾体皂苷,利用¹H NMR、¹³C NMR、¹H-¹H COSY、HSQC、 HMBC、1D和2D TOCSY等多种核磁共振方法鉴定其结构分别为(25R)-26-O-β-D-吡喃葡萄糖基-3β, 22α, 26-三羟基-呋甾-5-烯- 3-O-α-L -吡喃鼠李糖基-(1→2)[α-L-呋喃阿拉伯糖基(1→4)]-β-D-吡喃葡萄糖苷（1, Parisaponin I）和(25R)-3β, 5α, 6β-三羟基-△7-螺甾烯-3-O-β-D-吡喃葡萄糖基-(1→3)[α-L-吡喃鼠李糖基-(1→2)]-β-D-吡喃葡萄糖苷（2, parisvietnaside A）. 对化合物1和2的¹H NMR和¹³C NMR信号分别进行了归属和详细分析,并纠正了文献中的核磁数据归属错误. 化合物2为首次从滇重楼中分离得到.      

呋喃阿洛糖衍生物水解产物的结构确定

1,2;5,6-双-O-异丙叉基-3-C-硝甲基-α-D-呋喃阿洛糖（化合物1）在酸性条件下选择性脱除5,6-异丙叉基得到C-3位构型保持的水解产物1,2-O-异丙叉基-3-C-硝甲基-α-D-呋喃阿洛糖（化合物2）;化合物1先经过Moffatt脱水生成C-3硝基烯产物1,2;5,6-双-O-异丙叉基-3-脱氧-亚甲基硝基-α-D-呋喃木糖（化合物3）,然后在酸性条件下选择性脱除5,6-异丙叉基过程中协同发生氧杂-Michael加成反应得到C-3位构型反转的水解产物1,2-O-异丙叉基-3-C-硝甲基-α-D-呋喃葡萄糖（化合物2′）,两种产物化合物2和2′互为C-3差向异构体.通过¹H NMR、¹³C NMR、DEPT-135、¹H-¹H COSY、gHSQC和gHMBC等核磁共振（NMR）技术,对化合物2′的¹H和¹³C NMR数据进行了全归属．     

Effects of cooling rate on the microstructure and solute partitioning in near eutectoid Ti–Cu alloys

The effect of cooling rate on eutectoid decomposition in a near eutectoid (Ti-5.5 at.% Cu) alloy has been investigated in a systematic manner by coupling scanning electron microscopy, transmission electron microscopy and atom probe tomography studies. Thus, the competition between nucleation and growth of proeutectoid α plates from pre-existing β grain boundaries, and eutectoid decomposition (α?+?Ti₂Cu) via a pearlitic mechanism has been studied as a function of cooling rate, using a Jominy-end quenched sample that was cooled from the high-temperature single β phase. When the alloy was subjected to very fast cooling (160?K/s), proeutectoid α plates, supersaturated in Cu, are formed along with a highly refined lamellar eutectoid product between these α plates. In contrast, intermediate (9?K/s) and slow (2?K/s) cooling results in considerably coarser proeutectoid α plates as well as lamellar eutectoid products. With the decrease in the cooling rate, there was a substantial increase in the volume fraction of the lamellar eutectoid product and the composition of all decomposition products approached their equilibrium values. Also, the slowest cooled sample (2?K/s) exhibited substantially rougher and irregular interfaces between the proeutectoid α and the lamellar eutectoid product, which seems to promote the cooperative growth of lamellar α?+?Ti₂Cu. Irrespective of the cooling rate, nucleation of the lamellar eutectoid (α?+?Ti₂Cu) product appears to only occur at the interface between the proeutectoid α plates and the β matrix.     

Total cross sections for some (α, n) and (α, p) reactions in medium-weight nuclei

Total cross sections have been measured for the ⁴⁵Sc(α, n), ⁴⁶Ti(α, n), ⁵⁰Cr(α, n), ⁵¹V(α, n), ⁵⁴Fe(α, n) and ⁵⁸Ni(α, p) reactions, and stellar reaction rates have been calculated from them. These have been compared to recent theoretical calculations which used compound nuclear theory. The calculated values are generally higher than the experimental values by factors ranging from 2 to 10.     

苦皮藤中两个新的 β-二氢沉香呋喃型化合物的 NMR 数据解析

从南蛇藤属植物苦皮藤中分离出两个新的β-二氢沉香呋喃型化合物：1β,2β,15-三乙酰氧基-8α-(α-甲基)-丁酰氧基-9β-苯甲酰氧基-4α,6α-二羟基-β-二氢沉香呋喃（化合物I）和1β,15-二乙酰氧基-8α-(α-甲基)-丙酰氧基-2β,9β-二苯甲酰氧基-4α,6α-二羟基-β-二氢沉香呋喃（化合物II）．通过核磁共振（NMR，包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、NOESY、HSQC、HMBC）技术对化合物所有的¹H和¹³C NMR信号进行了全归属和详细解析.     

1,2-环己二酮基态光解离反应的理论研究

通过密度泛函理论计算研究了1, 2-环己二酮(α-CHD)基态光解离反应的势能面. 通过IRC方法确定了5个主要的反应通道, 相应的产物分别为P₁(c-C₅H₈O+CO), P₂(2C₂H₄+2CO), P₃(CH₂CHCH₂CH₂CHO+CO), P₄(2CH₂CO+C₂H₄)和P₅(CH₃CHCO+CH₂CHCHO). 获得了反应过程中反应物、产物、中间体和过渡态的结构参数. 详细阐述了这些通道的反应过程, 分析了其反应机理, 总结出最优的反应路径为α-CHD→c-C₅H₈O+CO. 理论分析与实验结果相符. 获得的结果为进一步进行与1, 2-环己二酮相关的研究提供有价值的信息.     

High—Temperature Cutoff Approximation of the 3D kinetic Ising Model

A single-spin transition critical dynamics is used to investigate the three-dimensional kinetic Ising model on an anisotropic cubic lattice,We first derive the fundamental dynamical equations.and then linearize them by a cutoff approximation.We obtain the approximate solutions of the local magnetization and equal-time pair correlation function approximation.We obtain the approximate solutions of the local magnetization and equal-time pair correlation function in zero field.In which the axial-decoupling terms γ1γ2,γ2γ3and γ1γ3as higher infinitesimal quantity are ignored,where γα=tanh(2k0633)=tanh(2Jα/kβT）（α=1,2,3,)We think that it is reasonable as the temperature of the system is very high.The result of what we obtain in this paper can go back to the one-dimensional Glauber‘s theory as long as k2=k3=0.     

Synthesis of ZnAl2O4/α-Al2O3 complex substrates and growth of GaN films

With the solid phase reaction between pulsed-laser-deposited (PLD) ZnOfilm and α-Al2O3 substrate, ZnAl2O4/α-Al2O3 complex substrates were synthesized. X-ray diffraction (XRD) spectra show that as the reaction proceeds, ZnAl2O4 changes from the initial (111)-oriented single crystal to poly-crystal, and then to inadequate (111) orientation. Corresponding scanning electron microscope (SEM)images indicate that the surface morphology of ZnAl2O4 transforms from uniform islands to stick structures, and then to bulgy-line structures. In addition, XRDspectra present that ZnAl2O4 prepared at low temperature is unstable at the environment of higher temperature. On the as-obtained ZnAl2O4/α-Al2O3 substrates, GaN films were grown without any nitride buffer using light-radiation heating low-pressure MOCVD (LRH-LP-MOCVD). XRD spectra indicate that GaN film on this kind of complex substrate changes from c-axis single crystal to poly-crystal as ZnAl2O4 layer is thickened. For the single crystal GaN, its full width at half maximum (FWHM) of X-ray rocking curve is 0.4°. Results indicate that islands on thin ZnAl2O4 layer can promote nucleation at initial stage of GaN growth, which leadsto the (0001)-oriented GaN film.     

Superconductivity in the cuprates: Deduction of mechanism for d-wave pairing through analysis of ARPES

In the Eliashberg integral equations for d-wave superconductivity, two different functions (α²F)_n(ω, θ) and (α²F)_p,d(ω) determine, respectively, the “normal” self-energy and the “pairing” self-energy. ω is the frequency of fluctuations scattering the fermions whose momentum is near the Fermi-surface and makes an angle θ to a chosen axis. We present a quantitative analysis of the high-resolution laser based Angle Resolved Photoemission Spectroscopy (ARPES) data on a slightly under doped cuprate compound Bi2212 and use the Eliashberg equations to deduce the ω and θ dependence of (α²F)_n(ω, θ) for T just above T_c and below T_c. Besides its detailed ω dependence, we find the remarkable result that this function is nearly independent of θ between the (π; π)-direction and 25 degrees from it, except for the dependence of the cut-off energy on θ. Assuming that the same fluctuations determine both the normal and the pairing self-energy, we ask what theories give the function (α²F)_p,d(ω) required for the d-wave pairing instability at high temperatures as well as the deduced (α²F)_n(θ, ω). We show that the deduced (α²F)_n(θ, ω) can only be obtained from antiferromagnetic (AFM) fluctuations if their correlation length is smaller than a lattice constant. Using (α²F)_p,d(ω) consistent with such a correlation length and the symmetry of matrix-elements scattering fermions by AFM fluctuations, we calculate T_c and show that AFM fluctuations are excluded as the pairing mechanism for d-wave superconductivity in cuprates. We also consider the quantumcritical fluctuations derived microscopically as the fluctuations of the observed loop–current order discovered in the under-doped cuprates, and which lead to the marginal Fermi–liquid properties in the normal state. We show that their frequency dependence and the momentum dependence of their matrix-elements to scatter fermions are consistent with the θ and ω dependence of the deduced (α²F)_n(ω, θ). The pairing kernel (α²F)_p,d(ω) calculated using the experimental values in the Eliashberg equation gives d-wave instability at T_c comparable to the experiments.     

量子系统的Ergodlc定理

在Klein的一篇论文中,他指出了当量子系统的ergodic定理成立时,所有的运动积分R必须满足以下的条件:sumfrom r″to (α′γ″|R|β′γ″=常数δ_α′β′, (1) 式中α′,β′,…等代表我们所研究的系统的态,γ″,ρ″…等代表舆我们的系统共同平衡的外界的态。在这篇短文中,我们指出:Klein的讨论在一点是可以怀疑的,而用了另一个方法来讨论ergodic定理。这样,我们证明了(1)式只是在引入另一个假定——外界各态有同一个几率——后才是充分的,而在一般情形下,我们须要更强的条件,例如(α′ρ″|R|β′γ″)=常数δ_α′β′δ_ρ″γ″。(2)以上相当於没有运动积分的情形。有运动积分的情形也在本文中作了讨论。