A 19F NMR Study on the Interaction of the Hexafluoroanions of Group IV Elements with Cations in Solutions

In view of previous studies of tetrafluoroborate solutions¹, it appeared interesting to continue further investigations on the interactions of fluorocomplexes with different cations, in general, and of the MF₆ ^2- fluoro complexes, in particular. In this communication, the high resolution ¹⁹F NMR data are given for the aqueous and water-acetone solutions of silicon, germanium, tin and titanium hexafluorocomplexes, containing paramagnetic (Co²⁺, Ni²⁺, Cu²⁺, Cr³⁺) and diamagnetic (Be²⁺, Mg²⁺, Zn²⁺, NH₄ ⁺) cations.     

一维核磁共振谱数据的小波变换压缩

本成功地将小波变换的多尺寸信号分解（ＭＲＳＤ）方法用于一维核磁共振（ＮＭＲ）信号的数据压缩。将一幅由３２７６８个数据点构成的ＮＭＲ谱图压缩至５１２个数据点,仍能在均方差很小（２．７７６９×１０＾－４）的情况下很好地重建原始谱图。     

A Review of NMR Studies in RCo3 Systems Presenting d-Moment Instability

For the past few years, intermetallic systems with the formula RCo₃, where R is a rare earth, have attracted the attention of the magnetism community. In these systems, the magnetism associated to the Co ions presents a magnetic instability which gives rise to metamagnetic phase transitions observed as a change on the Co magnetic moment for some critical values of the molecular field acting on this sublattice. A number of publications about these systems is concerned with basic magnetic measurements and ⁵⁹Co NMR in compounds such as Y_1–x R _x Co₃, where R = Gd, Nd, Er. The Co ions are distributed among three crystal sites with different symmetries, one of these sites being further split into two magnetic sites, a fact in itself that considerably complicates the NMR spectra. Besides, as we have observed, the linewidths and even the number of lines appearing on the NMR spectra are strongly dependent on some NMR features, such as the radiofrequency power applied to the sample. Adding to this fact, these magnetic peculiarities depend on the compounds stoichiometry; therefore it is no surprise to find conflicting results in the literature. In the present paper a review of the NMR published data will be made, including some new results of our own.     

蚕丝蛋白的NMR研究Ⅲ.天蚕茧层固态13C CP-MASNMR研究

本文分别测定了东北天蚕茧和龙蛓天蚕茧各内,中,外三层茧层的固态¹³C CP-MASNMR波谱,对其谱峰进行了归属,估算了谱峰区主要谱线在该区所占的比例,还计算了各个茧层丝蛋白中无定形状态所占的百分含量。谱图显示了东北天蚕茧层与龙(蛓)天蚕茧层丝蛋白结构的差异。     

Irbesartan: FTIR and Raman spectra. Density functional study on vibrational and NMR spectra

Arterial hypertension is a very common disease, which is treated with different medications such as Irbesartan. This compound is a nonpeptide antagonist of the receptor of the enzyme angiotensin II. The infrared and Raman spectra of this compound were recorded and discussed assisted with density functional theory using the 6‐31G** basis set and animated pictures. Irbesartan exists in two tautomeric forms which can be isolated in the solid state. The vibrational study has been recorded using a mixture of both forms. ¹³C, ¹⁵N and ¹H NMR theoretical studies have been performed and compared with previously reported experimental data. Theoretical calculations allowed the determination of the main features of the A and B tautomers of Irbesartan both in the vibrational studies and in the NMR spectroscopy. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies of Hindered Rotation and Magnetic Anisotropy by 1H, 13C and 19F NMR. The Diels-Alder Adduct of N- Pentafluorophenylmaleimide and Phencyclone: A Model for Drugs.

The potent Diels-Alder diene, phencyclone, 1, reacts with N-pentafluorophenylmaleimide, 2, to form an adduct, 3, characterized by ¹H, ¹³C, and ¹⁹F NMR at 300, 75 and 282 MHz, respectively. The one-dimensional (1D) and two-dimensional (2D) ¹H and ¹³C NMR spectra of 3 at ambient temperatures imply a slow exchange limit (SEL) regime with respect to rotation of the unsubstituted bridgehead phenyl groups about severely hindered C(sp²)-C(sp³) bonds. Major non-bonded interactions are expected between the ortho protons of the C₆H₅ groups and H-1, 8 of the phenanthrenoid moiety of 3. ¹⁹F 1D and 2D (COSY) NMR spectra show that the SEL regime also obtains for rotation about the N-C₆F₅ bond of 3, with five separate fluorine signals seen, consistent with a preferred conformation in which the C₆F₅ may lie roughly perpendicular to the plane of the pyrrolidinedione moiety, and may be in the mirror symmetry plane of 3. The results are considered relevant to hindered aryl rotations in numerous Pharmaceuticals. Selected spectral data for 2 and precursors are also presented.     

苯甲酸及其甲基取代物的激光光解研究

研究了苯甲酸及其甲基取代物在248 nm激光作用下的光电离及光激发行为,测定了光电离量子产额和激发三线态寿命及其自猝灭速率常数。实验结果显示甲基在苯环不同位置的取代对苯甲酸化合物激发三线态的影响不明显。利用分步双激光技术对苯甲酸激发态进行共振激发,对可能生成的瞬态产物进行了初步探讨。     

Physicochemical Studies of Some Mercury Pyrimidine Complexes

Mercury(II) complexes of some pyrimidine derivatives were prepared and characterized by elemental analysis and spectral measurements. The ¹H n.m.r and i.r. spectra show the ligands to be in the keto form. Thermal analysis and electrical conductivity measurements of the complexes were investigated in the temperature range 30–250°C. The results indicate slight semiconducting behaviour. The disparity in the activation energy values, ΔE as calculated from the slopes of the linear parts of the electrical conductivity curves is due to the difference in the concentration of the imperfections contained in the different types of the complexes.     

Natural Abundance 17O NMR Studies on Methyl N-Arylcarbamates: Torsion Angle and Electronic Effects

Natural abundance ¹⁷O NMR data for 14 substituted methyl N-arylcarbamates obtained in acetonitrile solution at 75°C are reported. The ¹⁷O NMR chemical shifts of hindered ortho N-arylcarbamates are shielded relative to unhindered ones; a quantitative relationship is observed between the carbonyl ¹⁷O NMR chemical shifts and molecular mechanics (MM2) predicted torsion angles. The carbonyl ¹⁷O NMR chemical shifts of meta and para substituted N-arylcarbamates are correlated with Hammett sigma constants.     

Electronic Spectra of N-Methyl 8-Hydroxy Quinoline Methyl Sulphate Adsorbed on Sepiolite

Adsorption of the drug N-methyl 8-hydroxy quinoline methyl sulphate, used to prevent sunburning and to avoid the dangerous effect of erythematogenic radiations, on untreated and HCl-treated sepiolite has been studied. The adsorption complex formed extends the absorption properties of the drug in the visible and ultraviolet range. The behaviour shown by these samples is fairly similar in all cases with respect to light absorption. However, adsorption complexes prepared via a dry method, by mechanically mixing the drug and sepiolite, lead to samples with different light absorbent properties, due to the modification of the surface acid/base properties of the sepiolite and hence of the way the drug is adsorbed.     

Anisotropy of the Hyperfine Field on 57Fe in Pure and Substituted Yttrium Iron Garnet

Using NMR, anisotropy of the hyperfine field on ⁵⁷Fe nuclei was measured in Y₃Fe₅O₁₂ with nonmagnetic, trivalent substitutions on d (Ga³⁺) and a (Y³⁺ - yttrium antisite defect) sites which are occupied by ferric ions in a pure, stoichiometric system. The measurements were performed by the spin-echo method at liquid helium temperature. Thorough analysis of the hyperfine field anisotropy on the ⁵⁷Fe nuclei in an ideal environment and in an environment where one of Fe³⁺ nearest cation neighbours is replaced by the nonmagnetic impurity is given. When the Fe³⁺ on which the NMR is measured is on the a site and the impurity is Ga³⁺(d), the results may be interpreted in terms of the superposition model. On the other hand, the results for Fe³⁺ on the d site and Y³⁺(a) are in clear disagreement with the predictions of this model. This revised version was published online in July 2006 with corrections to the Cover Date.     

N.M.R. Spectral Studies of Some Quinolone Derivatives. Part II.1 Further Studies of the Effect of Substitution on the Degree of Hydrogen Bonding

The chemical shift of the NH proton for a series of 4-quinolone derivatives has been studied. It is proposed that the inhibition of π-hydrogen bonding is a dominant factor which contributes to the observed NH chemical shift. Details of the ¹H n.m.r. spectra of some 2- and 4- quinolone derivatives are presented.     

四种姜黄素类似物核磁共振谱的理论研究

在B3LYP/6-31G(d, p)水平下优化了四种姜黄素类似物的几何构型,并通过振动分析验证了其构型稳定性。在B3LYP/6-311G(d, p)水平下计算了该类化合物的核磁共振谱,研究结果表明：四种化合物主体结构共平面性较好,为一较大共轭体系。由于羟基及甲氧基的引入,使Compound-B/C/D中C₃,C₄以及Compound-A/D中C₅均具有较大δ值,Compound-A中C₄和C₆的δ值相对较小,C₃的δ值相对较大。而在羰基与碳碳双键所形成的共轭羰基化合物中,羰基C₁₃的δ值(183 ppm)相对于乙醛中的δ值(201ppm)有所减小,C_{11, 15}(α碳)的δ值(122 ppm)相对减小,而C_{9, 17}(β碳)的δ值(145 ppm)相对增大。最后,通过线性回归方法,利用相关系数值r研究了1H NMR δ值的实验和理论计算值的相关性,结果表明相关性较好,实验值和理论值基本吻合。     

易解石族矿物的Raman光谱和光致发光谱研究

测定并讨论了中国白云鄂博矿区变生及退火晶态易解石族矿物Ｒａｍａｎ光谱和光致发光谱,与退火晶质矿物相比,变生态易解石的Ｒａｍａｎ光谱和光致发光谱的强度降低,谱线宽化弥散,说明在变生过程中,矿物的结构发生畸变,元素分布趋于无序。分析表明,易解石族矿物在５１４．５ｎｍ激光激发下的所有光致发光谱峰均出自Ｎｄ＾３＋的辐射跃迁。     

光谱法研究普利沙星与小牛胸腺DNA的结合作用

利用紫外光谱,荧光光谱及流体动力学方法,研究了普利沙星与小牛胸腺DNA的作用机理。讨论了不同浓度普利沙星与DNA作用的紫外光谱,荧光光谱,磷酸盐效应以及离子强度对两者相互作用的影响,测量了DNA的热变性温度和粘度。从紫外光谱图上看出DNA发生了明显的减色效应, 说明普利沙星可能与DNA发生作用。普利沙星的荧光光谱发生了有规律的猝灭,最大发射峰发生红移, 猝灭常数为3.1×104 L·mol-1, 为静态猝灭,表明普利沙星与DNA结合生成了二元复合物。磷酸盐效应表明普利沙星与DNA的磷酸基团不发生静电作用。普利沙星引起了DNA的热变性温度略微升高(≤7℃)和DNA粘度略微下降, 表明普利沙星与DNA之间不存在插入作用, 只是在DNA的外部发生沟槽作用。     

Spectral and Computational Studies on Benzil Mono-(2-Pyridyl)Hydrazone

In the present study, structural properties of Mono-(2-Pyridyl) Hydrazone were studied extensively utilizing density functional theory (DFT) employing B3LYP exchange correlation. The Fourier transform infrared (solid phase) was recorded. The vibrational frequencies in the ground state were calculated by using density functional method (B3LYP) with 6-31G* and 6-311G** as basis sets. The spectral studies revealed that the title compound exists in Keto form. Spectral techniques that we employed include ¹H and ¹³C NMR, electronic, thermal techniques. Correlation between experimental chemical shifts and GIAO/B3LYP/6-311G**-calculated isotropic shielding constants, δ_exp = a + bσ_calc, are reported. Good linear regressions between experimental and theoretical results for ¹H and ¹³C were obtained.     

菌紫质光致各向异性动力学的理论和实验

对菌紫质(Bacteriorhodopsin,BR)薄膜的光致各向异性特性进行了理论模拟.由随机取向的极性BR分子构成的聚合物薄膜在宏观上是各向同性的,但在线偏振光的作用下,BR分子对激发光的选择性吸收,导致不同异构体分子取向的不均匀分布,从而使BR薄膜在宏观上呈现出各向异性.利用BR光循环的二能级模型,得到了B态分子取向分布随时间的变化关系,推导出了BR薄膜光致各向异性动力学的数学表达式,模拟了不同激发光强下BR薄膜的光致各向异性动力学曲线,得到了和实验结果一致的计算结果.     

3-取代苯基-5-(3'-吲哚基)-异(噁)唑啉衍生物的谱学研究

现代红外光谱技术以其分析速度快、重现性好、成本低、且不消耗样品等特点正得到越来越广泛的应用,文章利用傅里叶红外技术,研究了9种含有吲哚基和苯基的3-取代苯基-5-(3'-吲哚基)-异(噁)唑啉衍生物的红外光谱的特征吸收规律,指出了这类化合物不同取代基对红外吸收谱带的影响;同时,利用核磁共振技术,对3-取代苯基-5-(3'-吲哚基)-异(噁)唑啉衍生物的1H NMR的共振谱带做了全面的归属,其化学位移的变化规律与红外光谱一致,为这类化合物的结构与谱学研究提供了一条很好的途径.     

N.M.R. Spectral Studies of Some Quinolone Derivatives. Effect of Substitution on the Degree of Hydrogen Bonding

The chemical shift of the NH protons for a series of monomethyl-, dimethyl- and trimethyl- substituted 2- and 4- quinolones has been studied. Compounds with an 8-methyl substituent exhibit a characteristic upfield shift which is considered to be due to a reduction in hydrogen bonding as a result of steric effects. The application of this effect to the identification of alkyl substituted quinolones and some natural products is discussed.     

稳态荧光及各向异性方法研究环糊精纳米管的生成

本文运用稳态荧光和稳态荧光各向异性方法,研究了双喹啉(BQ)和1,1’-(甲撑双-1,4-苯基)二顺丁烯二酰亚胺(MDP-BMI)分子分别与α-,β-,和γ-环糊精(CD)的作用。实验结果表明,这两个客体分子与不同环糊精的作用不同。它们均可以和γ-CD生成纳米管状聚集物,在MDP-BMI-β-CD体系中也有纳米管存在,而在其它情况下,只有简单的环糊精包合物生成。