Vitamin B1 as a scavenger of reactive oxygen species photogenerated by vitamin B2

Kinetics and mechanism of photoprocesses generated by visible light-irradiation of the system riboflavin (Rf, vitamin B2) plus Thiamine (Th) and Thiamine pyrophosphate (ThDP), representing vitamin B1, was studied in pH 7 water. A weak dark complex vitamin B2-vitamin B1, with a mean value of 4 ± 0.4 M(-1) is formed. An intricate mechanism of competitive reactions operates upon photoirradiation, being the light only absorbed by Rf. Th and ThDP quench excited singlet and triplet states of Rf, with rate constants in the order of 10(9) and 10(6 ) M(-1 ) s(-1), respectively. With Vitamin B1 in a concentration similar to that of dissolved molecular oxygen in water, the quenching of triplet excited Rf by the latter is highly predominant, resulting in the generation of O(2)((1)Δ(g)). Superoxide radical anion was not detected under work conditions. A relatively slow O(2)((1)Δ(g))-mediated photodegradation of Th and ThDP was observed. Nevertheless, Th and especially ThDP behave as efficient physical deactivators of O(2)((1)Δ(g)). The thiazol structure in vitamin B1 appears as a good scavenger of this reactive oxygen species. This characteristic, that presents at vitamin B1 as a potential photoprotector of biological entities against O(2)((1)Δ(g)) attack, was been experimentally confirmed employing the protein lisozime as a photo-oxidizable target.     

Acid-base titrations of schiff bases in deuteriomethanol as studied by1H NMR

The Schiff bases of salicylaldehyde and pyridoxal 5-phosphate with amino compounds were studied by¹H NMR in CD₃OD by using a glass electrode for the control of acidity. This study makes a new contribution for the elucidation of the structures of pyridoxylidene Schiff bases and gives additional data on the¹H NMR of the compounds that have not been available from the related studies in aqueous solutions.     

Dynamic behavior of water in hydro-swollen crosslinked polymer gel as studied by PGSE 1H NMR and pulse 1H NMR

¹H NMR measurements on spin-lattice relaxation time (T₁) and spin-spin relaxation time (T₂) were carried out on hydro-swollen crosslinked poly(methacrylic acid) (PMAA) gel to elucidate molecular motion of water molecules contained in the gel as a function of the degree of crosslinking. From these experimental results, it was found that ¹H T₁ and T₂ decrease with an increase of the degree of crosslinking. This shows that molecular motion of water molecules is strongly restrained owing to crosslinking. Further, pulsed-field-gradient spin-echo ¹H NMR measurements were carried out to determine the self-diffusion coefficient of water molecules (D_H2O contained in the PMAA gel at 300 K as a function of the degree of crosslinking. From these experimental results, it was found that the D_H2O value decreases with an increase of the degree of crosslinking. This shows that translational molecular motion of water molecules is restrained by crosslinking.     

Molecular dynamics in paramagnetic materials as studied by magic-angle spinning 2H NMR spectra

A magic-angle spinning (MAS) 2H NMR experiment was applied to study the molecular motion in paramagnetic compounds. The temperature dependences of 2H MAS NMR spectra were measured for paramagnetic [M(H2O)6][SiF6] (M=Ni2+, Mn2+, Co2+) and diamagnetic [Zn(H2O)6][SiF6]. The paramagnetic compounds exhibited an asymmetric line shape in 2H MAS NMR spectra because of the electron-nuclear dipolar coupling. The drastic changes in the shape of spinning sideband patterns and in the line width of spinning sidebands due to the 180 degrees flip of water molecules and the reorientation of [M(H2O)6]2+ about its C3 axis were observed. In the paramagnetic compounds, paramagnetic spin-spin relaxation and anisotropic g-factor result in additional linebroadening of each of the spinning sidebands. The spectral simulation of MAS 2H NMR, including the effects of paramagnetic shift and anisotropic spin-spin relaxation due to electron-nuclear dipolar coupling and anisotropic g-factor, was performed for several molecular motions. Information about molecular motions in the dynamic range of 10(2) s(-1)相似文献   

Effect of cross-linking on the molecular motion of water in polymer gel as studied by pulse 1H NMR and PGSE 1H NMR

¹H NMR measurements on the spin-spin relaxation time (T₂) and self-diffusion coefficient (D_H2O) of water in a poly(metacrylic acid) gel were carried out to clarify the molecular motion of water molecules as a function of the degree of cross-linking under a constant amount of water contained in the gel. From experimental results, it was found that ¹H T₂ and D_H2O decrease with an increase in the degree of cross-linking in the gel. It can therefore be said that an increase in cross-linking leads to a restraint of molecular motion of the water molecules in the gel.     

Aromatic imine stereochemistry as studied by 13C and 1H NMR of 15N-enriched materials

A series of thirteen ¹⁵N-enriched N-aryl imines derived from benzaldehydes and acetophenones have been prepared and examined by ¹³C and ¹H NMR. Preferred conformations of the C-arvl and N-aryl rings have been deduced from ¹³C chemical shifts and ¹³C-¹⁵N couplings. Evidence for steric inhibition of resonance in O-alkylated materials is presented. Relative signs of ¹J(CN) and ²J(CCN) have been determined in some compounds. An E: Z interconversion barrier of 21.6 kcal mol^?1 has been obtained from ¹H NMR coalescence data.     

Electron spin density distribution of a series of nitroxide radicals with five-member ring as studied by solid-state 1H, 2H and 13C NMR

Stable nitroxide radicals are useful to construct molecular magnetic systems. Particularly, radicals substituted by –COOH and –CONH₂ can be coordinated to magnetic metal ions and may be used as cladding reagents of gold nano-particles for modifying magnetism. Nitroxide molecules with unsaturated five-member ring have almost planner structure and electron spin delocalization may be expected. We determined the hyperfine coupling constants (hfcc) of ¹H, ²H and ¹³C of a series of nitroxide radicals with five-member ring. Experimental values of hfcc were compared with those deduced from calculations based on density functional theory. The electron spin density distribution at β position of ring was sensitive to the ring structure, although the electron spin density at β position is small compared with N–O site. Magnetic susceptibility and UV–Vis absorption spectra were also measured and discussed.     

Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by 1H pulsed field gradient NMR spectroscopy

Deep Eutectic Solvents (DESs) are a novel class of solvents with potential industrial applications in separation processes, chemical reactions, metal recovery and metal finishing processes such as electrodeposition and electropolishing. Macroscopic physical properties such as viscosity, conductivity, eutectic composition and surface tension are already available for several DESs, but the microscopic transport properties for this class of compounds are not well understood and the literature lacks experimental data that could give a better insight into the understanding of such properties. This paper presents the first pulsed field gradient nuclear magnetic resonance (PFG-NMR) study of DESs. Several choline chloride based DESs were chosen as experimental samples, each of them with a different associated hydrogen bond donor. The molecular equilibrium self-diffusion coefficient of both the choline cation and hydrogen bond donor was probed using a standard stimulated echo PFG-NMR pulse sequence. It is shown that the increasing temperature leads to a weaker interaction between the choline cation and the correspondent hydrogen bond donor. The self-diffusion coefficients of the samples obey an Arrhenius law temperature-dependence, with values of self-diffusivity in the range of [10(-10)-10(-13) m(2) s(-1)]. In addition, the results also highlight that the molecular structure of the hydrogen bond donor can greatly affect the mobility of the whole system. While for ethaline, glyceline and reline the choline cation diffuses slower than the associated hydrogen bond donor, reflecting the trend of molecular size and molecular weight, the opposite behaviour is observed for maline, in which the hydrogen bond donor, i.e. malonic acid, diffuses slower than the choline cation, with self-diffusion coefficients values of the order of 10(-13) m(2) s(-1) at room temperature, which are remarkably low values for a liquid. This is believed to be due to the formation of extensive dimer chains between malonic acid molecules, which restricts the mobility of the whole system at low temperature (<30 °C), with malonic acid and choline chloride having almost identical diffusivity values. Diffusion and viscosity data were combined together to gain insights into the diffusion mechanism, which was found to be the same as for ionic liquids with discrete anions.     

Nature of acidic protons in metallosilicate molecular sieves as studied by variable temperature 1H MAS NMR

The dynamic properties of protons in H-[Ga]-ZSM-5, H-[B]-ZSM-5 and H-[Al-B]-ZSM-5 were compared with that of protons in H-[Al]-ZSM-5 by temperature dependence of ¹H MAS NMR in the range of 298 k and 473 K. The temperature dependence of the line width of ¹H MAS NMR reveals that protons in H-[Ga]-ZSM-5 were more mobile than those in H-[Al]-ZSM-5 at temperature as low as 373 K. The protons in H-[B]-ZSM-5 were not mobile at 473 K and fixed in the zeolite frame work as the bridging hydroxyl groups, ≡B-OH-Si≡. The thermal motion of protons in ≡Al-OH-Si≡ was suppressed by introducing B³⁺ cations into the framework of H-[Al]-ZSM-5.     

High resolution 1H NMR study of 2-vinyl pyridine methyl methacrylate copolymers

The compositions and the microstructures of the copolymers formed by radical-initiated copolymerization of 2-vinyl pyridine and methyl methacrylate have been quantitatively studied using 250 MHz ¹H NMR spectra. V-centered triad and M-centered triad distributions were quantitatively measured. These results confirmed that this copolymerization system belongs to the first order Markov chain model. Reactivity ratios for 2-vinyl pyridine and methyl methacrylate established are rv = 0.64 and rM = 0.31, respectively, agreeing very well with those calculated theoretically.     

Heterogeneity of polyelectrolyte diffusion in polyelectrolyte-protein coacervates: a 1H pulsed field gradient NMR study

Proton pulsed field gradient (PFG) NMR was used to study the diffusion of poly(diallyldimethylammonium chloride) (PDADMAC) in coacervates formed from this polycation and the protein bovine serum albumin (BSA). Application of high (up to 30 T/m) magnetic field gradients in PFG NMR measurements allowed probing the diffusion of PDADMAC on a length scale of displacements as small as 100 nm in coacervates formed at different pH's and ionic strengths, i.e., conditions of varying protein-polycation interaction energy. Studies were carried out for a broad range of diffusion times and corresponding values of the mean square displacements. Several ensembles of PDADMAC polycations with different diffusivities were observed in the measured range of diffusion times. The existence of these ensembles and the pattern of their changes with increasing diffusion time support the hypothesis about the microscopic heterogeneity of PDADMAC-BSA coacervates and also provide evidence for the dynamic disintegration and reformation of dense domains.     

2-乙烯基吡啶与甲基丙烯酸甲酯共聚物的高分辨^1HNMR研究

本文根据自由基引发聚合的2-乙烯基吡啶-甲基丙烯酸甲酯共聚物的~1H NMR谱,定量地研究了共聚物中的微结构单元及其组成.对分别以2-乙烯基吡啶和甲基丙烯酸甲酯为中心的三元组分分布,都做了定量测定.确定了该共聚体系属于一级Markov链模型和单体竞聚率γ_v=O.64,γ_m=O.31.与理论上的计算结果吻合良好.     

Dynamic and molecular association in premicellar aqueous solutions of dicarboxylate amino acid-based surfactant as studied by 1H NMR

We examined a series of amino acid-based surfactants with two carboxylic groups separated by a spacer of one, two, or three carbon atoms with sodium and calcium counterions in the premicellar concentration region near the CMC. ¹H nuclear magnetic resonance (NMR) spectroscopy and NMR diffusometry techniques were used to study the local environment, association, and translational dynamics of the surfactant's molecules. We measured the self-diffusion coefficients of the micelles, calculated the effective hydrodynamic radii, and determined the temperature region in which the premicelles exist. With an increase in temperature from 295 to 335 K, the premicellar state of the surfactant is replaced by the monomeric state.     

Conformations of banana-shaped molecules studied by 2H NMR spectroscopy in liquid crystalline solvents

ClPbis11BB and Pbis11BB, two banana-shaped mesogens differing by a chlorine substituent on the central phenyl ring, show a nematic and a B2 phase, respectively. To obtain information on the structural features responsible for their different mesomorphic behavior, a study of the preferred conformations of these mesogens has been performed by NMR spectroscopy in two nematic media (Phase IV and ZLI1167), which should mimic the environment of the molecules in their own mesophases, avoiding problems of sample alignment by a magnetic field. To this aim, 2H NMR experiments have been performed on selectively deuterated isotopomers of ClPbis11BB and Pbis11BB and of two parent molecules, ClPbisB and PbisB, assumed as models in previous theoretical and experimental conformational studies. We found that only a limited number of conformations is compatible with experimental data, often very different from those inferred from theoretical calculations in vacuo, indicating a strong influence of the liquid crystalline environment on molecular conformation. No significant differences between chlorinated and non-chlorinated molecules were found, this suggesting that chlorine does not change the molecular conformational equilibrium, as previously proposed.     

Molecular motion of the main chain for a series of Poly(alkyl l-glutamate)s as studied by 2H NMR

²H NMR measurements were carried out for a series of poly(alkyl l-glutamate)s (PALG) in which the ¹H of the amide group in the main chain is replaced by ²H in order to investigate the mobility and motional mode of the main chain. At low temperature, the ²H spectra were typical powder patterns, which have three principal values. The temperature dependencies for the ²H NMR spectra varied with the side chain length. For PALG with a short side chain length, Δv₁, Δv₂, and Δv₃ are almost constant in all temperature ranges. As the side chain length increases, the difference between the peaks and shoulders decreased with temperature. For PG-12-N-D, the peaks and shoulders are fused at high temperature in a liquid crystalline state. The mobility and molecular motion of the main chain is discussed based on the obtained ²H NMR spectra.     

Structure of docosahexaenoic acid-containing phospholipid bilayers as studied by (2)H NMR and molecular dynamics simulations.

Polyunsaturated phospholipids are known to be important with regard to the biological functions of essential fatty acids, for example, involving neural tissues such as the brain and retina. Here we have employed two complementary structural methods for the study of polyunsaturated bilayer lipids, viz. deuterium ((2)H) NMR spectroscopy and molecular dynamics (MD) computer simulations. Our research constitutes one of the first applications of all-atom MD simulations to polyunsaturated lipids containing docosahexaenoic acid (DHA; 22:6 cis-Delta(4,7,10,13,16,19)). Structural features of the highly unsaturated, mixed-chain phospholipid, 1-palmitoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine (PDPC), have been studied in the liquid-crystalline (L(alpha)) state and compared to the less unsaturated homolog, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). The (2)H NMR spectra of polyunsaturated bilayers are dramatically different from those of less unsaturated phospholipid bilayers. We show how use of MD simulations can aid in interpreting the complex (2)H NMR spectra of polyunsaturated bilayers, in conjunction with electron density profiles determined from small-angle X-ray diffraction studies. This work clearly demonstrates preferred helical and angle-iron conformations of the polyunsaturated chains in liquid-crystalline bilayers, which favor chain extension while maintaining bilayer flexibility. The presence of relatively long, extended fatty acyl chains may be important for solvating the hydrophobic surfaces of integral membrane proteins, such as rhodopsin. In addition, the polyallylic DHA chains have a tendency to adopt back-bended (hairpin-like) structures, which increase the interfacial area per lipid. Finally, the material properties have been analyzed in terms of the response of the bilayer to mechanical stress. Simulated bilayers of phospholipids containing docosahexaenoic acid were less sensitive to the applied surface tension than were saturated phospholipids, possibly implying a decrease in membrane elasticity (area elastic modulus, bending rigidity). The above features distinguish DHA-containing lipids from saturated or monounsaturated lipids and may be important for their biological modes of action.     

The pi-pi stacked geometries and association thermodynamics of quinacridone derivatives studied by 1H NMR

The pi-pi stacked associations of three N,N'-di(n-butyl) quinacridone derivatives, widely used dopants in organic light-emitting diodes, with different sizes of substituents were investigated in solution at various temperatures by (1)H NMR spectroscopy. The pi-pi stacked geometries were estimated by both the magnitudes of peak shifts with concentration and the directions of peak shifts induced by polar solvents. Two patterns of geometries with different pi-pi interaction strengths were found to coexist in solution for all the three samples. In both of the patterns, the preferential orientation of the stacking is the approach of the carbonyl groups on one molecule to the nitrogen atoms on the stacked partner, which makes the pi-deficient aromatic atoms interact with both pi-rich and pi-deficient aromatic atoms of the stacked partner to maximize the electrostatic complementarity. Differently, whereas the molecules in one pattern are face-to-face stacked in a parallel fashion and slip two rings relative to one another along with the long axis of the conjugated ring systems, the molecules in the other are either face-to-face stacked in an antiparallel fashion with slight slipping between layers or stacked in a turning fashion. Both association constants obtained by fitting the dilution curves and thermodynamic parameters obtained from van't Hoff analyses revealed unexpectedly three thermodynamic processes of aggregations for all the three samples in the temperature region of 298-213 K. The size of substituents on the outer aromatic rings significantly influences the pi-pi stacked structures and association thermodynamics.     

Hydrocarbon chain packing in the micellar core of surfactants studied by 1H NMR relaxation

 ¹H NMR spin–lattice and spin–spin relaxation of different types (cationic cetyltrimethyl ammonium bromide, anionic sodium dodecyl sulfonate and nonionic Triton X-100) of surfactants in water solution were studied. Simulation of the decay curves of proton relaxation shows that the spin lattice relaxation of all the samples exhibits exponentially, while the spin–spin relaxation for several protons on the hydrophobic chains forming the micellar core is bi-exponential. The fast relaxing component is attributed to the part of the segments of the hydrophobic chain, situated near or on the surface of the micellar core, while the slower relaxing component is attributed to the rest part staying in the interior. The latter exchanges with the former in equilibrium. Thus, a part of each certain segment of the hydrophobic chain has an opportunity to stay in the surface layer of the micellar core and spend some time on the interface experiencing hydrophilic environment. Generally, the protons on the methylene carbon of the hydrophobic chain nearest to the polar head have more chance to spend time in the hydrophilic environment. However, it seems to be dependent on the chemical structure of the surfactant molecule. Large size of the polar group of CTAB shows steric hindrance on the packing of the hydrophobic chain. Quantitative results are given. The fact, that the fraction of slow relaxing protons on the hydrophilic ethylene oxide long chain of Triton X-100 dominates over that of fast relaxing protons, and that their T ₂ values are larger than those of the protons on the hydrocarbon chain in the interior of the micellar core, suggests that the ethylene oxide chain does not participate in the formation of the micellar core. Received: 10 March 1998 Accepted: 19 June 1998     

Cyanocuprates as Homo-dimer in Etheral Solution:1H,6Li and 1H,1H Distances Information by NMR

Despite of the wide application of organocuprates in many areas of organic synthesis, little is known about their detailed structures in solution. Recently we found by NMR that organocuprates in etheral solution exist as an equilibrium between solvent separated ion pairs (SSIPs) and contact ion pairs (CIPs) with the preference of the equilibrium mainly dependent of the solvent properties, and the CIPs as the reactive species. We focus here on ¹H, ⁶Li and ¹H, ¹H distances investigation by NMR spectroscopy of Me₂CuLi(l) and Me₂CuLi*LiCN (1*LiCN) in Et₂O as models for the structure of salt-free and salt-containing CIPs in solution.