The time evolution of the sol-gel process:29Si NMR study of hydrolysis and condensation reactions of tetramethoxysilane

The time evolution of the structural intermediate formation obtained during hydrolysis and condensation reactions in tetramethoxysilane (TMOS), methanol, H₂O, HCl (molar ratio 1:5:2: 0.001) sol-gel reaction mixture was investigated by²⁹Si NMR spectroscopy at ?75°C. It is obvious that the substitution of the Si methoxy group (OCH₃) by a hydroxyl (OH) shifts the resonance lines downfield. The dimer peaks are located about 9–10 ppm upfield from the corresponding monomers, and the Si located in the middle of the trimers appeared at the chemical shift of 18–19 ppm upfield from the corresponding monomers. The peaks of trimers, cyclic tetramers and the other higher oligomers are relatively broad and weak, and exhibit a multiplet structure. The time dependence of the concentrations of the individual types of silicon in the reaction mixture were evaluated from the integral intensity of the corresponding Si atoms from the²⁹Si NMR spectra. The results obtained represent input data to the various kinetic models of the complex hydrolysis and condensation reactions.     

Study of molecular dynamics and cross relaxation in tetramethylammonium hexafluorophosphate (CH(3))(4)NPF(6) by (1)H and (19)F NMR

(CH(3))(4)NPF(6) is studied by NMR measurements to understand the internal motions and cross relaxation mechanism between the heterogeneous nuclei. The spin lattice relaxation times (T(1)) are measured for (1)H and (19)F nuclei, at three (11.4, 16.1 and 21.34 MHz) Larmor frequencies in the temperature range 350-50K and (1)H NMR second moment measurements at 7 MHz in the temperature range 300-100K employing home made pulsed and wide-line NMR spectrometers. (1)H NMR results are attributed to the simultaneous reorientations of both methyl and tetramethylammonium groups and motional parameters are evaluated. (19)F NMR results are attributed to cross relaxation between proton and fluorine and motional parameters for the PF(6) group reorientation are evaluated.     

四氢β-咔啉类化合物的13C NMR研究

测定了四对新合成的四氢β-咔啉化合物的¹³C NMR谱,通过APT、HETCOR和HETCOLOC谱指认了所有碳的归属.所确定的化学位移规律可以用来确定它们的构型.     

19F NMR的特点

¹⁹F的磁旋比和相对灵敏度接近质子;¹⁹F NMR化学位移范围可达 δ 1 000,谱图分辨率高;¹⁹F NMR对环境因素较氢谱远为敏感、复杂,可反映出化合物结构的细微差别. 由于正常生物体内含氟成分很少,干扰小,因此在生物医学研究中引入氟代物进行¹⁹F NMR研究有特殊意义. 对氟化物的¹⁹F NMR化学位移和偶合常数的范围也分类作了总结.     

Identification of fluorine sites at the surface of fluorinated gamma-alumina by two-dimensional MAS NMR

By means of 27Al triple quantum Magic-Angle Spinning Nuclear Magnetic Resonance (3QMAS NMR) and 27Al[19F] WISE MAS NMR, we were able to detect three different Al-F sites on the surface of fluorinated gamma-alumina. Three 19F resonances at 9, 20, and 33 ppm (from C6F6) correlated to 27Al resonances in the octahedral range. While the positions of the maxima in the 27Al dimension were ill-defined due to the inherently low efficiency of the 27Al[19F] CPMAS process, the center of gravity of the lines shifted significantly upfield in that dimension with increasing wt.% F. Tentatively, these three resonances were assigned to (VI)Al(O(6-n)Fn) (n = 1, 2, 3) environments on the F/gamma-Al2O3 surface. At F contents above levels corresponding to the full fluorination of the gamma-Al2O3 surface, neoformation of an AlF3 x 3H2O phase was also evidenced with an 19F resonance at -8 ppm and with an 27Al resonance at -17 ppm.     

2-(2,5-二羟苯基)四苯基卟啉及其金属配合物的合成与表征

对苯二酚与 2 硝基 5 ,10 ,15 ,2 0 四苯基卟啉 1及其铜 (Ⅱ ) 2、镍 (Ⅱ ) 3、锌 (Ⅱ ) 4等金属配合物直接加热反应 ,分别制得 2 (2 ,5 二羟苯基 )四苯基卟啉 1′(81% )及相应金属配合物 2′(71% ) ,3′(6 1% ) ,4′(40 % )。它们的结构由IR ,MS ,UV及1 HNMR ,2D NMR等确定。发现对苯二酚通过碳 碳键与卟啉的吡咯环直接相连 ,氢醌与卟啉环趋于共平面 ,其中一个羟基位于卟啉环的去屏蔽区 ,H原子的核磁位移向低场移动 (δ =7 5 2 ) ,另一个则处于中位苯环的屏蔽区 ,H原子的核磁位移为δ =4 18;氢醌环上的质子也表现出不同的核磁位移 ,其中 6位上H的位移值为δ =4 93,明显向高场位移。     

Definitive Carbon-13 Chemical Shift Assignments in 2-Substituted Adamantane Derivatives by Deuterium Isotope Effects

Deuterium isotope effects on carbon-13 chemical shifts in 5-[²H]-isotopomeres of ten 2-substituted adamantane derivatives were determined and used for complete assignment of their carbon-13 NMR spectra.

The carbon-13 NMR spectra of ten 2-substituted adamantane derivatives have been assignated by consideration of deuterium isotope effects. Some four- and five-bond downfield deuterium effects on certain chemical shifts have been measured and attributed to remote hyperconjugative interactions.     

丙酮肟1H核磁共振溶剂效应的研究

测定了丙酮肟在四氯化碳、氯仿、二氯甲烷、苯和甲苯溶剂中随丙酮肟摩尔浓度变化的¹H NMR谱,观察到在氯代甲烷溶剂中,丙酮肟分子中两个甲基和氯代甲烷的质子共振峰随丙同肟摩尔浓度增加而逐渐移向高场,而羟基共振峰却逐渐移向低场。其两个甲基表现为单峰。在芳烃溶剂中,丙酮肟分子中两个甲基和芳烃质子共振峰随丙酮肟摩尔浓度增加逐渐移向低场,且两个甲基表现为双峰,得到了所有化学位移与丙酮肟摩尔浓度呈线性关系。     

A Spectroscopic Study of the Interaction of the Fluorescent β-Carboline-3-carboxylic Acid N-methylamide with DNA Constituents: Nucleobases, Nucleosides and Nucleotides

Interaction between beta-carboline-3-carboxylic acid N-methylamide, betaCMAM, and nucleobases, nucleosides and nucleotides is studied in the ground state with UV-visible, (1)H NMR and (31)P NMR spectroscopies and in the first excited state, with steady-state and time-resolved fluorescence spectroscopy. Job plots show a predominant 1:1 interaction in both electronic states. Association constants are estimated from changes in the absorption spectra, and show that the strongest interaction is produced with the nucleosides: 2'-deoxyadenosine (dAdo) and thymidine (Thd), and with the mononucleotides: 2'-deoxycytidine 5'- monophosphate (5'-dCMP) and uridine 5'- monophosphate (5'-UMP). These results are corroborated by the upfield shifts of two (1)H NMR resonances of the betaCMAM indole group. The (31)P NMR resonance of nucleotides is shifted downfield, suggesting the presence of electrostatic or hydrogen bond interaction with betaCMAM. In the first electronic singlet excited state, static and dynamic quenching of betaCMAM emission is achieved upon addition of nucleobases, nucleosides and nucleotides. This has been analysed using Stern-Volmer kinetics.     

A 1H/19F minicoil NMR probe for solid-state NMR: application to 5-fluoroindoles

We show that it is feasible to use a minicoil for solid-state 19F 1H NMR experiments that has short pulse widths, good RF homogeneity, and excellent signal-to-noise for small samples while using low power amplifiers typical to liquid-state NMR. The closely spaced resonant frequencies of 1H and 19F and the ubiquitous use of fluorine in modern plastics and electronic components present two major challenges in the design of a high-sensitivity, high-field 1H/19F probe. Through the selection of specific components, circuit design, and pulse sequence, we were able to build a probe that has low 19F background and excellent separation of 1H and 19F signals. We determine the principle components of the chemical shift anisotropy tensor of 5-fluoroindole-3-acetic acid (5FIAA) and 5-fluorotryptophan. We also solve the crystal structure of 5FIAA, determine the orientation dependence of the chemical shift of a single crystal of 5FIAA, and predict the 19F chemical shift based on the orientation of the fluorine in the crystal. The results show that this 1H/19F probe is suitable for solid-state NMR experiments with low amounts of biological molecules that have been labeled with 19F.     

2,2-二(甲硫基)乙烯基苯基酮1H NMR溶剂效应的研究

在四氯化碳介质中考察了苯对标题化合物的核磁共振谱的溶剂效应.观察到标题化合物分子中的两个甲硫基和混合溶剂中的苯的共振吸收峰随着苯的摩尔分数增加而逐渐移向高场,而且两个甲硫基向高场移动程度不同,ASIS值也随苯的摩尔分数增加而增加,得到了所有化学位移值和ASIS值与苯的摩尔分数呈线性关系,尝试用溶剂化作用解释了标题化合物的ASIS效应.     

Solvent effects on oxygen-17 chemical shifts in methyl formate: linear solvation shift relationships

A multiple linear regression analysis has been carried out using the Kamlet-Abboud-Taft solvatochromic parameters in order to quantify the solvent effects on the (17)O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than for N-methylformamide (NMF). The influence (in parts per million) of the solvent polarity-polarizability reduces from -21.9pi* in amides to -9.6pi* in MF. The influence of the solvent hydrogen-bond-donor acidities reduces from -42.0alpha in formamides to -16.9alpha in MF. The solvent effects upon the dicoordinated oxygen chemical shifts of MF are smaller in magnitude and opposite in direction, i.e., 4.8pi* and 2.6alpha, than those for the carbonyl oxygen. (17)O hydration shifts have been calculated for the NMF + (H(2)O)(6) and MF + (H(2)O)(5) complexes by the ab initio GIAO method at the 6-311 + G** level. The hydration shifts calculated for the carbonyl oxygens of NMF and MF and for the dicoordinated oxygen of MF, -102.4, -64.7, and 17.6 ppm, respectively, show the same trend as the corresponding empirical hydration shifts, -101.7, -42.0, and 14.2 ppm.     

A computational NICS and 13C NMR characterization of the substitution patterns of C70−2x(BN)x fullerenes (x=1–25)

A density functional study has been performed to investigate the electronic and magnetic properties of BN substituted fullerenes C_70?2x(BN)_x (x=1, 2, 3, 6, 9, 12, 15, 17, 19, 21, 23 and 25) based on the NMR parameters and NICS index. The calculated ¹³C chemical shielding (CS) tensors are found to be perturbed at the first and second neighbors of the doped atoms while the other distant carbon atoms not to be influenced significantly. ¹³C Chemical shifts (δ_iso) of the second neighbors of nitrogen and boron are significantly shifted to upfield and downfield (the second neighboring effects), respectively. Besides, chemical shifts are also affected by the curvature of the corresponding sites; for example, the perturbed sites at the caps yield smaller absolute values of chemical shifts than those located at the equator. Nucleus independent chemical shifts (NICS) at the cage centers of heterofullerenes (from ?25.29 to ?8.80) demonstrate that all the substituted species are aromatic, but less than C₇₀ (?27.29). The predicted NICS values may be useful for identification of the heterofullerenes through their endohedral ³He NMR chemical shifts.     

Cross-correlated (19)F relaxation measurements for the study of fluorinated ligand-receptor interactions.

Fluorine is often used in drug-design efforts to enhance the pharmacokinetic properties of biologically active compounds. Additionally fluorine nuclei ((19)F) have properties that are well suited to current pharmaceutical NMR screening programs. Together, these considerations have motivated our interest in the utility of fluorine relaxation parameters to study ligand-receptor interactions. Here, we investigate the potential for cross-correlated relaxation effects between the (19)F anisotropic chemical-shift and (19)F-(1)H dipole-dipole relaxation mechanisms to help pinpoint and quantify exchange processes. Methods are proposed and demonstrated in which the magnitude ratio of the transverse cross-correlation rate constant eta(xy) and the fluorine transverse relaxation rate constant, R(2), help estimate the exchange rate constant for ligand-binding equilibria. These exchange rate constants provide estimates of the ligand dissociation rate constants k(off) and can thus provide a means for rank-ordering the binding affinities of ligands identified in pharmaceutical screens.     

Carbon-13 and fluorine-19 NMR spectroscopy of the supramolecular solid p-tert-butylcalix(4)arene.alpha,alpha,alpha-trifluorotoluene

The supramolecular 1:1 host-guest inclusion compound, p-tert-butylcalix[4]arene x alpha,alpha,alpha-trifluorotoluene, 1, is characterized by 19F and 13C solid-state NMR spectroscopy. Whereas the 13C NMR spectra are easily interpreted in the context of earlier work on similar host-guest compounds, the 15F NMR spectra of solid 1 are, initially, more difficult to understand. The 19F[1H] NMR spectrum obtained under cross-polarization and magic-angle spinning conditions shows a single isotropic resonance with a significant spinning sideband manifold. The static 19F[1H] CP NMR spectrum consists of a powder pattern dominated by the contributions of the anisotropic chemical shift and the homonuclear dipolar interactions. The 19F MREV-8 experiment, which minimizes the 19F-19F dipolar contribution, helps to identify the chemical shift contribution as an axial lineshape. The full static 19F[1H] CP NMR spectrum is analysed using subspectral analysis and subsequently simulated as a function of the 19F-19F internuclear distance (D(FF) = 2.25 +/- 0.01 A) of the rapidly rotating CF3 group without including contributions from additional libration motions and the anisotropy in the scalar tensor. The shielding span is found to be 56 ppm. The width of the centerband in the 19F[1H] sample-spinning CP NMR spectrum is very sensitive to the angle between the rotor and the magnetic field. Compound 1 is thus an attractive standard for setting the magic angle for NMR probes containing a fluorine channel with a proton-decoupling facility.     

Selective detection of the proton NMR spectra of molecules containing rare spins at natural abundance in liquid crystalline samples

It is shown that the proton NMR spectra of molecules containing rare spins at natural abundance dissolved in a liquid crystalline solvent can be obtained free from the strong lines from the spectrum of the abundant isotopomer by the 2D HSQC NMR experiment. The technique can also give the individual chemical shifts of the rare spins, and, for a molecule containing another abundant nucleus, such as fluorine, the rare spin--(19)F total anisotropic couplings are also obtained. The usefulness of the technique is demonstrated for molecules containing (13)C as the rare spins.     

Air- and N(2)-Broadening Parameters of Water Vapor: 604 to 2271 cm(-1)

High-resolution measurements of air- and N(2)-broadened widths and pressure-induced frequency shifts of water vapor were obtained covering the spectral region between 604 and 2271 cm(-1). Over 1300 vibration-rotation transitions were measured including the (000)-(000), (010)-(010), (010)-(000), (020)-(010), and (100)-(010) vibrational bands of H(2)(16)O. Also included were measurements of H(2)(18)O and H(2)(17)O from normal water vapor samples and H(2)(18)O + N(2) observations with oxygen-18-enriched gas samples. Collision-narrowing effects were observed in a few lines involving high J and low K(a) transitions with the lowest measured linewidth coefficient equal to 0.0057(4) cm(-1)/atm (air-broadening) for the completely overlapping transitions, 17 0 17 <-- 18 1 18 and 17 1 17 <-- 18 0 18, at 1235.204 cm(-1). The majority of the linewidth values were derived from the measurements using a Voigt line profile. A few lines with air- or N(2)-broadened half-width values of about 0.012 cm(-1) or less were found to exhibit collision-narrowing effects and were also analyzed with a profile proposed by Galatry. The results are compared to values given in previous studies. Copyright 2000 Academic Press.     

Uniform mixing of antiferromagnetism and high-temperature superconductivity in electron-doped layers of four-layered Ba(2)Ca(3)Cu(4)O(8)F(2): a new phenomenon in an electron underdoped regime

We report (63,65)Cu- and (19)F-NMR studies on a four-layered high-temperature superconductor Ba(2)Ca(3)Cu(4)O(8)F(2)((0234F(2.0)) with apical fluorine (F(-1)), an undoped 55 K superconductor with a nominal Cu(2+) valence on average. We reveal that this compound exhibits the antiferromagnetism (AFM) with a Néel temperature T(N)=100 K despite being a T(c)=55 K superconductor. Through a comparison with a related trilayered cuprate Ba(2)Ca(3)Cu(4)O(8)F(2)(0233F(2.0)), it is demonstrated that electrons are transferred from the inner plane (IP) to the outer plane (OP) in 0234F(2.0) and 0223F(2.0), confirming the self-doped high-temperature superconductivity (HTSC) having electron and hole doping in a single compound. Remarkably, uniform mixing of AFM and HTSC takes place in both the electron-doped OPs and the hole-doped IPs in 0234F(2.0).     

Natural abundance (17)O NMR spectroscopy of rat brain in vivo

Oxygen is an abundant element that is present in almost all biologically relevant molecules. NMR observation of oxygen has been relatively limited since the NMR-active isotope, oxygen-17, is only present at a 0.037% natural abundance. Furthermore, as a spin 5/2 nucleus oxygen-17 has a moderately strong quadrupole moment which leads to fairly broad resonances (T(2)=1-4 ms). However, the similarly short T(1) relaxation constants allow substantial signal averaging, whereas the large chemical shift range (>300 ppm) improves the spectral resolution of (17)O NMR. Here it is shown that high-quality, natural abundance (17)O NMR spectra can be obtained from rat brain in vivo at 11.74 T. The chemical shifts and line widths of more than 20 oxygen-containing metabolites are established and the sensitivity and potential for (17)O-enriched NMR studies are estimated.     

Fluorine NMR Chemical Shifts in Certain Ionic Fluorides

NMR chemical shifts are known for various nuclei in numerous solid compounds. Especially detailed data were obtained for NMR of ¹⁹F. The present work cites the measurement results for fluorine NMR chemical shifts in several d¹⁰-element fluorides previously not investigated. At the same time, the fluorine chemical shift values in alkali, alkali-earth and some other metal fluorides were measured anew. (This was necessitated by the discrepancies in the shift magnitudes, cited by various authors, as well as by the inaccuracy of the mutual chemical shifts of some standards commonly used.