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ABSTRACT: BACKGROUND: Pyrroloquinoline quinone (PQQ), a tricarboxylic acid, has attracted attention as a growthfactor, and its application to supplements and cosmetics is underway. The product used forthese purposes is a water-soluble salt of PQQ disodium. Although in the past, PQQdisodiumpentahydrates with a high water concentration were used, currently, low hydrationcrystals of PQQ disodiumpentahydrates are preferred. RESULTS: We prepared a crystal of PQQ disodium trihydrate in a solution of ethanol and water, studiedits structure, and analyzed its properties. In the prepared crystal, the sodium atom interactedwith the oxygen atom of two carboxylic acids as well as two quinones of the PQQ disodiumtrihydrate. In addition, the hydration water of the prepared crystal was less than that of theconventional PQQ disodium crystal. From the results of this study, it was found that the colorand the near-infrared (NIR) spectrum of the prepared crystal changed depending on the watercontent in the dried samples. CONCLUSIONS: The water content in the dried samples was restored to that in the trihydrate crystal by placingthe samples in a humid environment. In addition, the results of X-ray diffraction (XRD) andX-ray diffraction-differential calorimetry (XRD-DSC) analyses show that the phase of thetrihydrate crystal changed when the crystallization water was eliminated. The dried crystalhas two crystalline forms that are restored to the original trihydrate crystals in 20% relativehumidity (RH). This crystalline (PQQ disodium trihydrate) is stable under normalenvironment. 相似文献
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Petri Kanninen Virginia Ruiz Tanja Kallio I.V. Anoshkin Esko I. Kauppinen Kyösti Kontturi 《Electrochemistry communications》2010,12(9):1257-1260
Pyrroloquinoline quinone (PQQ) was immobilized on glassy-carbon electrodes (GCE) modified with single-walled carbon nanotubes (SWCNT), few-walled carbon nanotubes (FWCNT) and carbon black (Vulcan XC72R). Modified electrodes were prepared by drop-casting. Immobilization was achieved with an extremely simple dipping procedure and without any further modification to the electrodes. Electrochemical performance of the electrodes was studied by cyclic voltammetry and spectroelectrochemistry. FWCNT adsorbed 30 times more PQQ than the other carbon materials. Compared to more complicated immobilization methods, PQQ/FWCNT/GCE showed well-defined electrochemistry in a considerably wide pH area from 2 to 12. The dipping process is affected by pH and electrostatic forces. At dipping pH 9.5, where both FWCNTs and PQQ have strong negative charge, the adsorption was halved compared to dipping pH 2, where the charges are smaller. 相似文献
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Background
Vibrio carchariae chitinase A (EC3.2.1.14) is a family-18 glycosyl hydrolase and comprises three distinct structural domains: i) the amino terminal chitin binding domain (ChBD); ii) the (α/β)8 TIM barrel catalytic domain (CatD); and iii) the α + β insertion domain. The predicted tertiary structure of V. carchariae chitinase A has located the residues Ser33 & Trp70 at the end of ChBD and Trp231 & Tyr245 at the exterior of the catalytic cleft. These residues are surface-exposed and presumably play an important role in chitin hydrolysis.Results
Point mutations of the target residues of V. carchariae chitinase A were generated by site-directed mutagenesis. With respect to their binding activity towards crystalline α-chitin and colloidal chitin, chitin binding assays demonstrated a considerable decrease for mutants W70A and Y245W, and a notable increase for S33W and W231A. When the specific hydrolyzing activity was determined, mutant W231A displayed reduced hydrolytic activity, whilst Y245W showed enhanced activity. This suggested that an alteration in the hydrolytic activity was not correlated with a change in the ability of the enzyme to bind to chitin polymer. A mutation of Trp70 to Ala caused the most severe loss in both the binding and hydrolytic activities, which suggested that it is essential for crystalline chitin binding and hydrolysis. Mutations varied neither the specific hydrolyzing activity against pNP-[GlcNAc]2, nor the catalytic efficiency against chitohexaose, implying that the mutated residues are not important in oligosaccharide hydrolysis.Conclusion
Our data provide direct evidence that the binding as well as hydrolytic activities of V. carchariae chitinase A to insoluble chitin are greatly influenced by Trp70 and less influenced by Ser33. Though Trp231 and Tyr245 are involved in chitin hydrolysis, they do not play a major role in the binding process of crystalline chitin and the guidance of the chitin chain into the substrate binding cleft of the enzyme. 相似文献6.
《中国化学快报》2022,33(12):5218-5222
Treatment of antibiotics contaminated water remains a global environmental challenge. In this study, tetracycline (TC) was found to effectively sensitize pure TiO2 for visible light photocatalytic degradation via a ligand-to-metal charge transfer mechanism. The sensitization was attributed to the formation of TC-TiO2 complex and the overlap of the molecular orbitals of TC and the conduction band of TiO2. The intermediate degradation products of TC, however, did not sensitize TiO2, which was the reason for the low mineralization rate. Nevertheless, our results showed that the intermediate degradation products of TC had significantly reduced bactericidal effects and less induction of antibiotic-resistance genes (ARGs). This study showcases an effective treatment of antibiotics-containing wastewater using the most common photocatalyst TiO2 with reduced risk in the spread of ARGs. 相似文献
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Pan J Benkö G Xu Y Pascher T Sun L Sundström V Polívka T 《Journal of the American Chemical Society》2002,124(46):13949-13957
The dynamics of photoinduced electron injection and recombination between all-trans-8'-apo-beta-caroten-8'-oic acid (ACOA) and a TiO(2) colloidal nanoparticle have been studied by means of transient absorption spectroscopy. We observed an ultrafast ( approximately 360 fs) electron injection from the initially excited S(2) state of ACOA into the TiO(2) conduction band with a quantum yield of approximately 40%. As a result, the ACOA(*)(+) radical cation was formed, as demonstrated by its intense absorption band centered at 840 nm. Because of the competing S(2)-S(1) internal conversion, approximately 60% of the S(2)-state population relaxes to the S(1) state. Although the S(1) state is thermodynamically favorable to donate electrons to the TiO(2), no evidence was found for electron injection from the ACOA S(1) state, most likely as a result of a complicated electronic nature of the S(1) state, which decays with a approximately 18 ps time constant to the ground state. The charge recombination between the injected electrons and the ACOA(*)(+) was found to be a highly nonexponential process extending from picoseconds to microseconds. Besides the usual pathway of charge recombination forming the ACOA ground state, about half of the ACOA(*)(+) recombines via the ACOA triplet state, which was monitored by its absorption band at 530 nm. This second channel of recombination proceeds on the nanosecond time scale, and the formed triplet state decays to the ground state with a lifetime of approximately 7.3 micros. By examination of the process of photoinduced electron transfer in a carotenoid-semiconductor system, the results provide an insight into the photophysical properties of carotenoids, as well as evidence that the interfacial electron injection occurs from the initially populated excited state prior to electronic and nuclear relaxation of the carotenoid molecule. 相似文献
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《Bioelectrochemistry and bioenergetics (Lausanne, Switzerland)》1990,23(3):227-238
The voltammetric and spectroscopic properties of pyrroloquinoline quinone (PQQ) have been investigated in the pH range from 5 to 13.5. PQQ gives a reversible cyclic voltammogram at the mercury electrode, which is ascribed to a two-step one-electron redox reaction of the o-quinone moiety. Digital simulation analysis of the reversible voltammogram made it possible to evaluate the standard redox potentials of the PQQ/pyrroloquinoline semiquinone (PQQsem) and PQQsem/pyyroloquinoline quinol (PQQred) couples. From the redox potential vs. pH relationships, the acid dissociation constants of PQQ, PQQsem, and PQQred have also been determined. The absorption and electron spin resonance spectroscopic properties are explained by the acid-base and redox equilibria proposed here. 相似文献
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《Bioelectrochemistry and bioenergetics (Lausanne, Switzerland)》1998,44(2):209-214
A pyrroloquinoline quinone (PQQ) monolayer-functionalized-Au-electrode and a microperoxidase-11 (MP-11)-modified Au-electrode are used as catalytic anode and cathode in a biofuel cell element, respectively. The cathodic oxidizer is H2O2 whereas the anodic fuel-substrate is 1,4-dihydronicotinamide adenine dinucleotide, NADH. The PQQ-monolayer electrode catalyzes the oxidation of NADH in the presence of Ca2+ ions. The MP-11-functionalized electrode catalyzes the reduction of H2O2. The biofuel cell generates an open-circuit voltage, Voc, of ca. 320 mV and a short-circuit current density, Isc, of ca. 30 μA·cm−2. The maximum electrical power, Wmax, extracted from the cell is 8 μW at an external load of 3 kΩ. The fill factor of the biofuel cell, f=Wmax·Isc−1·Voc−1, is ca. 25%. 相似文献
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Yu S Ahmadi S Sun C Adibi PT Chow W Pietzsch A Göthelid M 《The Journal of chemical physics》2012,136(15):154703
The d-orbital contribution from the transition metal centers of phthalocyanine brings difficulties to understand the role of the organic ligands and their molecular frontier orbitals when it adsorbs on oxide surfaces. Here we use zinc phthalocyanine (ZnPc)/TiO(2)(110) as a model system where the zinc d-orbitals are located deep below the organic orbitals leaving room for a detailed study of the interaction between the organic ligand and the substrate. A charge depletion from the highest occupied molecular orbital is observed, and a consequent shift of N1s and C1s to higher binding energy in photoelectron spectroscopy (PES). A detailed comparison of peak shifts in PES and near-edge X-ray absorption fine structure spectroscopy illustrates a slightly uneven charge distribution within the molecular plane and an inhomogeneous charge transfer screening between the center and periphery of the organic ligand: faster in the periphery and slower at the center, which is different from other metal phthalocyanine, e.g., FePc/TiO(2). Our results indicate that the metal center can substantially influence the electronic properties of the organic ligand at the interface by introducing an additional charge transfer channel to the inner molecular part. 相似文献
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Hao Chenchun Zhang Ru Wang Wenzhong Liang Yujie Fu Junli Zou Bin Shi Honglong 《Journal of Solid State Electrochemistry》2019,23(8):2343-2353
Journal of Solid State Electrochemistry - Efficient charge transfer and separation play a significant role in determining the photoelectrochemical (PEC) water-splitting performance of... 相似文献
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Assembly and charge transfer in hybrid TiO(2) architectures using biotin-avidin as a connector 总被引:1,自引:0,他引:1
Dimitrijevic NM Saponjic ZV Rabatic BM Rajh T 《Journal of the American Chemical Society》2005,127(5):1344-1345
Exploiting the presence of undercoordinated surface Ti atoms at the tips of TiO2 nanorods and the dopamine selectivity for these Ti surface states, biotin was conjugated to TiO2 nanocrystallites using dopamine as a bridging linker. Using abiotin-avidin complex as a connector the "tip-to-tip" assembly of 400 nm elongated TiO2 rods was obtained. The photoexcitation of avidin-TiO2 hybrids resulted in the transfer of holes from nanocrystallites to protein and consequent oxidation of avidin, most probably at tyrosine 33. 相似文献
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Parallel syntheses of 2-hydro-, 2-methyl-, and 2-methoxycarbonylimidazo-7,9-dimethoxycarbonyl analogues of the oxidation-reduction cofactor pyrroloquinoline quinone [4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-f]quinoline-2,7,9-tricarboxylic acid] have been developed. The properties of the imidazolo analogues in relation to the corresponding pyrrole analogues will be important in assessing the origins of catalysis and biological activity in the cofactor, which has recently been shown to be a vitamin. 相似文献
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The charge exchange process in the intervalence (mixed-valence) system is interpreted in terms of the nonstationary state mechanism which is a well-known approach for rationalizing the molecular tautomerism process. The two kinds of processes are viewed in a close analogy in the sense that both involve a pair of near-degenerate levels in a double-well potential. However, a comparison is made between the two cases to demonstrate that an electron moves not only faster but also farther in distance than a nucleus does. 相似文献
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《化学研究》2017,(4)
染料敏化太阳能电池以其低成本高效率引起了人们广泛的关注,其中的光诱导电荷转移过程对太阳能电池的光电转化效率起着重要作用.本工作中我们以两种香豆素类染料分子7-羟基香豆素-4-乙酸(HCA)和7-N,N-二甲胺基香豆素-4-乙酸(DMACA)为例,从理论上研究了它们的几何结构和电子吸收光谱;并将其吸附在TiO_2表面上,计算了它们与TiO_2表面之间电荷转移的重组能、耦合强度和驱动力,进而计算了电荷转移速率.结果表明,DMACA分子中二甲胺基在第一激发态的旋转能垒约为0.08 eV,因此DMACA分子在第一激发态时很容易发生扭转.通过对HCA-TiO_2/DMACA-TiO_2体系中电子转移过程的研究,发现尽管两者重组能相似,但前者耦合强度和驱动力比后者小,使前者的电子转移速率略小于后者.当DMACA-TiO_2体系中二甲胺基在激发态发生扭转后,耦合强度略微减小,但由于驱动力减小,重组能增大,电子注入速率明显降低.因此,本工作不仅合理地解释了实验现象,而且也提供了一种理论预测染料分子-半导体界面上电子转移的可行性方法. 相似文献
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《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1986,42(2-3):209-214
A stable charge-transfer complex was formed between 5,10,15,20-tetraphenyl-21H,23H-porphine and a quinone in a neutral or acidic chloroform solution on irradiation with blue light. The existence of this photo-generated complex was confirmed by the change of visible absorption spectra, fluorescence spectra and NMR spectra. It had a high power of photo-induced charge separation even when irradiated with red light, as was proven from the intensity dependence of chemically induced dynamic nuclear polarization on the wavelength of excited light and on the irradiation time. 相似文献
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Pyrroloquinoline quinone (PQQ) was immobilized on the silica gel surface modified with zirconium oxide, designated as Si:Zr, by the carboxylic groups of the PQQ molecule and the zirconium oxide on the silica surface. The electrochemistry of PQQ immobilized on the Si:Zr matrix, incorporated in a carbon paste electrode, was evaluated using the cyclic voltammetry technique. The Si:Zr:PQQ-modified electrode showed a redox couple at E(m)=(E(pa1)+E(pc))/2=-0.150 V vs SCE at pH 7, close to that observed in aqueous solution, and another oxidation peak, E(pa2)=-0.100 V vs SCE. Studies in different pH solutions in the range of 3-7 showed that the first oxidation peak, E(pa1), is highly dependent on the solution pH shifting from to -0.175 to 0.100 V vs SCE, while E(pa2) remains practically constant at 0.100 V as the pH decreases from 7 to 3. The immobilized PQQ electrode presented the property to electrocatalyze the NADH at 150 mV vs SCE. The effect of addition of Ca(2+) ions on the electrode electroactivity for the NADH oxidation was also verified. Different from that observed for the PQQ immobilized on other electrode materials, the Ca(2+) ions did not influence the electrocatalytical response; however, the electrode stability was considerably improved in the presence of Ca(2+) ions, indicating that the matrix surface has a great influence on the electrochemical behavior of PQQ. 相似文献
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Liu L Cai X Li Y Richards O'Grady E Farrar JM 《The Journal of chemical physics》2004,121(8):3495-3506
The charge transfer and deuterium ion transfer reactions between D(2)O(+) and C(2)H(4) have been studied using the crossed beam technique at relative collision energies below one electron volt and by density functional theory (DFT) calculations. Both direct and rearrangement charge transfer processes are observed, forming C(2)H(4) (+) and C(2)H(3)D(+), respectively. Independent of collision energy, deuterium ion transfer accounts for approximately 20% of the reactive collisions. Between 22 and 36 % of charge transfer collisions occur with rearrangement. In both charge transfer processes, comparison of the internal energy distributions of products with the photoelectron spectrum of C(2)H(4) shows that Franck-Condon factors determine energy disposal in these channels. DFT calculations provide evidence for transient intermediates that undergo H/D migration with rearrangement, but with minimal modification of the product energy distributions determined by long range electron transfer. The cross section for charge transfer with rearrangement is approximately 10(3) larger than predicted from the Rice-Ramsperger-Kassel-Marcus isomerization rate in transient complexes, suggesting a nonstatistical mechanism for H/D exchange. DFT calculations suggest that reactive trajectories for deuterium ion transfer follow a pathway in which a deuterium atom from D(2)O(+) approaches the pi-cloud of ethylene along the perpendicular bisector of the C-C bond. The product kinetic energy distributions exhibit structure consistent with vibrational motion of the D-atom in the bridged C(2)H(4)D(+) product perpendicular to the C-C bond. The reaction quantitatively transforms the reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the deuterium ion is transferred in a configuration in which both the breaking and the forming bonds are extended. 相似文献
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Berger T Sterrer M Diwald O Knözinger E Panayotov D Thompson TL Yates JT 《The journal of physical chemistry. B》2005,109(13):6061-6068
Ultraviolet light-induced electron-hole pair excitations in anatase TiO(2) powders were studied by a combination of electron paramagnetic resonance and infrared spectroscopy measurements. During continuous UV irradiation in the mW.cm(-2) range, photogenerated electrons are either trapped at localized sites, giving paramagnetic Ti(3+) centers, or remain in the conduction band as EPR silent species which may be observed by their IR absorption. Using low temperatures (90 K) to reduce the rate of the electron-hole recombination processes, trapped electrons and conduction band electrons exhibit lifetimes of hours. The EPR-detected holes produced by photoexcitation are O(-) species, produced from lattice O(2-) ions. It is found that under high vacuum conditions, the major fraction of photoexcited electrons remains in the conduction band. At 298 K, all stable hole and electron states are lost from TiO(2). Defect sites produced by oxygen removal during annealing of anatase TiO(2) are found to produce a Ti(3+) EPR spectrum identical to that of trapped electrons, which originate from photoexcitation of oxidized TiO(2). Efficient electron scavenging by adsorbed O(2) at 140 K is found to produce two long-lived O(2)(-) surface species associated with different cation surface sites. Reduced TiO(2), produced by annealing in vacuum, has been shown to be less efficient in hole trapping than oxidized TiO(2). 相似文献