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91.
We have investigated the photoinduced decomposition of formaldehyde (CH2O) on a rutile TiO2(100)-(1×1) surface at 355 nm using temperature-programmed desorption. Products, formate (HCOO-), methyl radical (CH3·), ethylene (C2H4), and methanol (CH3OH) have been detected. The initial step in the decomposition of CH2O on the rutile TiO2(100)-(1×1) surface is the formation of a dioxymethylene intermediate in which the carbonyl O atom of CH2O is bound to a Ti atom at the five-fold-coordinated Ti4+ (Ti5c) site and its carbonyl C atom bound to a nearby bridge-bonded oxygen (Ob) atom, respectively. During 355 nm irradiation, the dioxymethylene intermediate can transfer an H atom to the Ob atom, thus forming HCOO- directly, which is considered as the main reaction channel. In addition, the dioxymethylene intermediate can also transfer methylene to the Ob row and break the C-O bond, thus leaving the original carbonyl O atom at the Ti5c site. After the transfer of methylene, several pathways to products are available. Thus, we have found that Ob atoms are intimately involved in the photoinduced decomposition of CH2O on the rutile TiO2(100)-(1×1) surface. 相似文献
92.
Graphene quantum dots(GQDs) have both the properties of graphene and semiconductor quantum dots,and exhibit stronger quantum confinement effect and boundary effect than graphene.In addition,the band gap of GQDs will transform to non-zero from 0 eV of graphene by surface functionalization,which can be dispersed in common solvents and compounded with solid materials.In this work,the SnO2 nanosheets were prepared by hydrothermal method.As the sensitizer,nitrogen-doped graphene quantum do... 相似文献
93.
《Tetrahedron letters》2019,60(24):1620-1623
5-Aryloxazolidines react with active methylene compounds in the presence of catalytic magnesium ethoxide to give methylene-linked 1,3-dicarbonyl compounds, while the similar reaction with 2-oxindoles results in 3-methyl derivatives. 相似文献
94.
Christopher J. Butch Jing Wang Jiande Gu Rebeca Vindas Jacob Crowe Pamela Pollet Leslie Gelbaum Jerzy Leszczynski Ramanarayanan Krishnamurthy Charles L. Liotta 《Journal of Physical Organic Chemistry》2016,29(7):352-360
The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative 13C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
95.
Christina Katranushkova Bonka Tzvetkova Lila Losseva 《Applied biochemistry and biotechnology》1997,66(1):31-37
The effects of formaldehyde on the growth of two strains of fodder yeastsCandida diddensii 74-10 andCandida tropicalis R-70 were investigated using the method of continuous cultivation under conditions of carbon limitation and at dilution rates
of 0.1/h and 0.25/h. The results indicate that formaldehyde induces a decrease in the yield of biomass, but stimulates the
synthesis of protein and RNA. The authors studied the activities of the following enzymes: NADPH-linked glutamate dehydrogenase,
NADH-linked glutamate dehydrogenase, alanine dehydrogenase, glutamine synthetase, and glutamate synthase, which are utilized
in nitrogen metabolism. The data obtained showed an increase in the activity of the glutamate dehydrogenase pathway of ammonium
assimilation. It was also established that formaldehyde caused considerable changes in the micro-organisms at the higher dilution
rate. 相似文献
96.
Simple high‐performance liquid chromatography method for formaldehyde determination in human tissue through derivatization with 2,4‐dinitrophenylhydrazine
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Bilal Yilmaz Ali Asci Kaan Kucukoglu Mevlut Albayrak 《Journal of separation science》2016,39(15):2963-2969
A simple high‐performance liquid chromatography method has been developed for the determination of formaldehyde in human tissue. FA Formaldehyde was derivatized with 2,4‐dinitrophenylhydrazine. It was extracted from human tissue with ethyl acetate by liquid–liquid extraction and analyzed by high‐performance liquid chromatography. The calibration curve was linear in the concentration range of 5.0–200 μg/mL. Intra‐ and interday precision values for formaldehyde in tissue were <6.9%, and accuracy (relative error) was better than 6.5%. The extraction recoveries of formaldehyde from human tissue were between 88 and 98%. The limits of detection and quantification of formaldehyde were 1.5 and 5.0 μg/mL, respectively. Also, this assay was applied to liver samples taken from a biopsy material. 相似文献
97.
Nan Wu 《Analytica chimica acta》2009,653(1):103-967
A novel and highly selective optical sensor with molecularly imprinted polymer (MIP) film was fabricated and investigated. The optical sensor head employing a medium finesse molecularly imprinted polymer film has been fabricated and characterised. A blank polymer and formaldehyde imprinted polymer were using methacrylic acid as the functional monomer and the ethylene glycol dimethacrylate as a crosslinker. The transduction mechanism is discussed based on the changes of optical intensity of molecularly imprinted polymer film acting as an optical reflected sensor. Template molecules, which diffused into MIP, could cause film density, and refractive index change, and then induce measurable optical reflective intensity shifts. Based on the reflective intensity shifts, an optical reflection detection of formaldehyde was achieved by illuminating MIP with a laser beam. For the same MIP, the reflective intensity shift was proportional to the amount of template molecule. This optical sensor, based on an artificial recognition system, demonstrates long-time stability and resistance to harsh chemical environments. As the research moves forward gradually, we establish the possibilities of quantitative analysis primly, setting the groundwork to the synthesis of the molecular imprinted optical fiber sensor. The techniques show good reproducibility and sensitivity and will be of significant interest to the MIPcommunity. 相似文献
98.
Xiao-Qing Zhao 《Talanta》2009,80(1):242-385
A rapid and sensitive flow injection fluorometry has been developed for the determination of formaldehyde based on the microwave on-line accelerating its Hantzsch reaction with cyclohexane-1,3-dione. Under the optimized conditions, the fluorescent intensity is proportional to formaldehyde content in the range from 0.05 ng/mL to 2.000 μg/mL. The detection limit (S/N = 3) is 0.02 ng/mL and the analytical frequency is 28 injections per hour. The relative standard deviations are 2.2% and 3.1% for eleven injections of 0.100 and 0.001 μg/mL of formaldehyde, respectively. With the assistance of microwave irradiation, a best sensitive fluorometry was established for the determination of formaldehyde at a high analytical frequency. This method was successfully applied to food analysis without requiring any sample pretreatment, and the determination results were correlated well with those obtained by the standard method with a sample pretreatment of steam distillation. 相似文献
99.
Dr. Abhijeet Gaur Max Schumann Dr. Kristian Viegaard Raun Matthias Stehle Dr. Pablo Beato Prof. Anker Degn Jensen Prof. Jan-Dierk Grunwaldt Dr. Martin Høj 《ChemCatChem》2019,11(19):4871-4883
The structural changes of an iron molybdate/molybdenum oxide (Mo/Fe=2.0) catalyst for the selective oxidation of methanol to formaldehyde were studied using combined operando X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) as well as operando Raman spectroscopy. Under operating conditions, the Mo K-edge XANES spectra showed a transition from a mixture of α-MoO3 and Fe2(MoO4)3 towards only Fe2(MoO4)3. XRD and Raman spectroscopy also showed disappearance of the α-MoO3 phase with time on stream. The results evidenced that the α-MoO3 component evaporated completely, while the Fe2(MoO4)3 component remained stable. This was linked to a decrease in catalytic activity. Further studies unraveled that the rate of α-MoO3 evaporation increased with increasing MeOH concentration, decreasing O2 concentration and increasing temperature. The simultaneous measurements of catalytic activity and spectroscopy allowed to derive a structure-activity relationship showing that α-MoO3 evaporation needs to be prevented to optimize MoO3-based catalysts for selective oxidation of methanol. 相似文献
100.
氢有较高的能量密度,其能量转换过程可循环、零污染,是未来替代传统化石燃料的理想能源载体.甲醛相较于其它的氢载体,具有可规模制备、来源广泛、安全性高、易于输运、储存和转化的特点,已逐渐成为一种新的制氢原料.此外甲醛制氢技术还可以应用于其它对环境有一定毒性的有机化合物转变为清洁的氢的过程.我们较全面的总结了甲醛的工业化制备... 相似文献