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131.
Libertino S Giannazzo F Aiello V Scandurra A Sinatra F Renis M Fichera M 《Langmuir : the ACS journal of surfaces and colloids》2008,24(5):1965-1972
A process to immobilize the enzyme glucose oxidase on SiO2 surfaces for the realization of integrated microbiosensors was developed. The sample characterization was performed by monitoring, step by step, oxide activation, silanization, linker molecule (glutaraldehyde) deposition, and enzyme immobilization by means of XPS, AFM, and contact angle measurements. The control of the environment during the procedure, to prevent silane polymerization, and the use of oxide activation to obtain a uniform enzyme layer are issues of crucial importance. The correct protocol application gives a uniform layer of the linker molecule and the maximum sample surface coverage. This result is fundamental for maximizing the enzyme bonding sites on the sample surface and achieving the maximum surface coverage. Thin SiO2 layers thermally grown on a Si substrate were used. The XPS Si 2p signal of the substrate was monitored during immobilization. Such a signal is not completely shielded by the thin oxide layer and it is fully suppressed after the completion of the whole protocol. A power spectral density analysis on the AFM measurements showed the crucial role of both the oxide activation and the intermediate steps (silanization and linker molecule deposition) to obtain uniform immobilized enzyme coverage. Finally, enzymatic activity measurements confirmed the suitability of the optimized protocol. 相似文献
132.
Heinze K Beckmann M Hempel K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(31):9468-9480
This overview highlights recent progress in the field of selective construction of linear, oligonuclear transition-metal complexes by using solid-phase synthesis procedures. Two general protocols have been identified: formation of coordinative bonds between metal centres and bridging ligands and formation of covalent bonds between preformed kinetically inert transition-metal-containing building blocks in the chain growth step. Currently available suitable building blocks for the second approach are based on ferrocene units, bis(terpyridine)-ruthenium(II) moieties or metal porphyrins. 相似文献
133.
Frömel T Peschka M Fichtner N Hierse W Ignatiev NV Bauer KH Knepper TP 《Rapid communications in mass spectrometry : RCM》2008,22(23):3957-3967
In search of fluorinated functional groups which could undergo defluorination, and therefore be included in novel non-polluting fluorinated surfactants, omega-(bis(trifluoromethyl)amino)alkane-1-sulfonates (BTFMA-AS) with a homologue distribution from seven to thirteen methylene groups were synthesized and investigated for aerobic biodegradation applying both a standardized test and a fixed-bed bioreactor (FBBR). These compounds were prepared as part of a screening study for potentially mineralizable fluorinated endgroups.Application of hybrid triple quadrupole-linear ion trap mass spectrometry (QqQ(LIT)-MS) coupled to high-performance liquid chromatography (HPLC) allowed the tracking of primary degradation as well as the detection and structural elucidation of biotransformation intermediates. An understanding of the fragmentation pathway of the test compounds allowed selective precursor ion scans to reveal the presence of stable fluorinated metabolites. Structures were confirmed by enhanced product ion scans and MS(3) scans in the linear ion trap mode.The primary biodegradation rate and the extent of biodegradation were found to be chain-length dependent, with higher homologues being completely primarily degraded within 10 days. For the first time, two simultaneous metabolic pathways for substituted linear alkane-1-sulfonates were discovered: Desulfonation, oxidation to a carboxylic acid and subsequent chain-length shortening by beta-oxidation dominated the metabolism. This pathway resulted in the formation of 3-(bis(trifluoromethyl)amino)propionic acid and bis(trifluoromethyl)aminoacetic acid, which showed recalcitrance in this experiment. Oxidation of the alkyl chain to the respective carbonyl derivative represents the minor pathway. Only the long-chain homologues of these oxidized species were partially degraded; the short-chain homologues were not attacked. 相似文献
134.
Alesi S Brancolini G Melucci M Capobianco ML Venturini A Camaioni N Barbarella G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(2):513-521
Quaterthiophene-dinucleotide conjugates 5'TA3'-t4-3'AT5', 5'AA3'-t4-3'AA5', and 5'TT3'-t4-3'TT5' (TA: thymidine-adenosine, AA: adenosine-adenosine, TT: thymidine-thymidine) were synthesized and analyzed by a combination of spectroscopy and microscopy, electrical characterization, and theoretical calculations. Circular dichroism (CD) experiments demonstrated a transfer of chirality from the dinucleotides to quaterthiophene at high ionic strength and in cast films. The films were photoluminescent and electroactive. CD and photoluminescence spectra and current density/voltage plots (measured under dynamic vacuum) displayed significant variation on changing the dinucleotide scaffold. Molecular mechanics and molecular dynamics calculations indicated that the conformation and packing modes of the conjugates are the result of a balance between intra- and intermolecular nucleobase-thiophene stacking interactions and intramolecular hydrogen bonding between the nucleobases. 相似文献
135.
Gándara F Medina ME Snejko N Gómez-Lor B Iglesias M Gutiérrez-Puebla E Monge MA 《Inorganic chemistry》2008,47(15):6791-6795
[C 6H 10(NH 2) 2Ge 3O 6] ICMM9 is a two-dimensional germanate in which the metallic atoms are covalently bonded to chelating diamines. Its layered structure having some similitude with that of the pyroxene mineral, presents a totally new topology with two 4-c nodes. The solvothermal synthesis reaction allows the separation in situ of the two 1,2-diaminocyclohexane isomers by selective coordination of the trans isomer to octahedral Ge atoms of the ICMM9 framework. This material behaves as an active and selective heterogeneous acid-base bifunctional catalyst. 相似文献
136.
James S. Parascandolo Dr. Judith Havemann Helen K. Potter Dr. Fanglu Huang Dr. Elena Riva Jack Connolly Dr. Ina Wilkening Dr. Lijiang Song Prof. Peter F. Leadlay Dr. Manuela Tosin 《Angewandte Chemie (International ed. in English)》2016,55(10):3463-3467
Chemical probes capable of reacting with KS (ketosynthase)‐bound biosynthetic intermediates were utilized for the investigation of the model type I iterative polyketide synthase 6‐methylsalicylic acid synthase (6‐MSAS) in vivo and in vitro. From the fermentation of fungal and bacterial 6‐MSAS hosts in the presence of chain termination probes, a full range of biosynthetic intermediates was isolated and characterized for the first time. Meanwhile, in vitro studies of recombinant 6‐MSA synthases with both nonhydrolyzable and hydrolyzable substrate mimics have provided additional insights into substrate recognition, providing the basis for further exploration of the enzyme catalytic activities. 相似文献
137.
Pablo Ruiz Manuela Castro Steffanía López Ángela Zapata Jairo Quijano Rafael Notario 《Structural chemistry》2016,27(5):1373-1381
In this work, a theoretical study at the MP2/6-31G(d) level of the thermal decomposition retro-ene reaction of 2-methylbutyraldehyde was carried out at a pressure of 1.5 atm. and temperatures ranging from 1110 to 1190 K. The progress of the reaction has been followed by means of the Wiberg bond indices which in turn allowed the calculation of the reaction synchronicity. Transition state theory was used to calculate the theoretical rate constant at 1150 K which was compared with the previously reported experimental value at the same conditions. We found that both values show a close agreement. The obtained computational evidence allowed us to support a reaction mechanism which proceeds in two steps: the first one with the formation of ethylene and 1-propenol via a six-membered cyclic transition state and the second one involving keto-enol equilibrium of 1-propenol to propionaldehyde via a four-membered cyclic transition state. It was found that the reaction is a highly synchronous and concerted process. The results obtained for the thermolysis of 2-methylbutyraldehyde were compared with those obtained for the thermolysis of 2-pentanone. A comparison of our results with those reported for their corresponding β-hydroxy counterparts, 3-hydroxy-2-methylpropionaldehyde and 4-hydroxy-2-butanone has also been made. A study of the thermochemistry of the compounds involved in the reactions studied has been carried out at the G3 level. 相似文献
138.
Tamara Mengoni Dolores Vargas Peregrina Roberta Censi Manuela Cortese Massimo Ricciutelli 《Natural product research》2016,30(3):268-275
The aim of this work was to provide a characterisation of volatile constituents from different commercial batches of henna (Lawsonia inermis) leaves of different geographic origin. Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC–MS) was used for the purpose. A total of 72 components were identified by GC–MS in the headspace of different henna samples which proved to differ considerably from each other, because they were characterised by different classes of components, mainly aliphatic compounds (9.0–64.7%), terpenoids (5.8–45.5%) and aromatics (7.9–45.2%), with alkanes (0.9–18.5%), aldehydes (2.1–18.8%) and carboxylic acids (3.1–29.3%), monoterpenes (3.4–30.0%) and sesquiterpenes (0.8–23.7%) and phenyl propanoids (0.6–43.1%), being the most abundant, respectively. Major representatives of these groups were n-hexadecane (0.5–4.7%), (2E)-hexenal (0.5–11.7%) and acetic acid (2.8–24.5%), limonene (0.8–14.7%), carvol (3.8–7.1%), geranyl acetone (1.4–7.9%) and (E)-caryophyllene (3.3–8.4%), and (E)-anethole (0.6–35.0%), respectively. We assume that factors such as the manufacturing process, the storage conditions and the different geographic origin of the samples may contribute to such variability. 相似文献
139.
Serrano-Pérez JJ Gonzalez-Luque R Merchan M Serrano-Andrés L 《The journal of physical chemistry. B》2007,111(41):11880-11883
The population of the lowest triplet state of thymine after near-UV irradiation has been established, on the basis of CASPT2//CASSCF quantum chemical calculations, to take place via three distinct intersystem crossing mechanisms from the initially populated singlet bright 1pipi* state. Two singlet-triplet crossings have been found along the minimum-energy path for ultrafast decay of the singlet state at 4.8 and 4.0 eV, involving the lowest 3npi* and 3pipi* states, respectively. Large spin-orbit coupling elements predict efficient intersystem crossing processes in both cases. Another mechanism involving energy transfer from the lowest 1npi* state with much larger spin-orbit coupling terms can also be proposed. The wavelength dependence measured for the triplet quantum yield of pyrimidine nucleobases is explained by the location and accessibility of the singlet-triplet crossing regions. 相似文献
140.
Novel colorimetric receptors for fluoride ion sensing containing anthraquinone as a chromogenic signaling unit and imidazo-2,2'-bithiophene binding sites are reported. Well-defined color change was observed upon addition of fluoride ions to acetonitrile solutions of receptors 2. Compounds 2a-c, deprotonated after fluoride ion addition, were studied as metal ion chemosensors in the presence of Zn(II), Hg(II), and Cu(II) in acetonitrile solutions, especially compound 2a which displayed a marked change from pink to yellow-gold colors upon complexation. 相似文献