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排序方式: 共有192条查询结果,搜索用时 15 毫秒
1.
Maria Benedetta Fadda Nicoletta Curreli Raffaello Pompei Antonio Rescigno Augusto Rinaldi Enrico Sanjust 《Applied biochemistry and biotechnology》1994,44(3):263-270
A highly active thermostable β-glucosidase was purified to homogeneity from a strain ofTrichoderma sp. The enzyme was an extracellular glycoprotein and showed hydrolytic activity toward several β-glucosides.
Cellobiose was found to be the substrate of choice for this enzyme. This finding could suggest future technological applications
of the purified protein. 相似文献
2.
P. Homem-de-Mello B. Mennucci J. Tomasi A. B. F. da Silva 《Theoretical chemistry accounts》2005,113(5):274-280
We present a quantum-mechanical study on the solvent effects in the structure and electronic spectra of some cationic dyes: acridine orange, proflavine, safranine, neutral red, thionine and methylene blue. The geometry optimizations were carried out with the AM1 and DFT (with B3LYP functional) methods and the theoretical spectra of the dyes under study were obtained with Zindo time-dependent methods (TD–DFT and TD–HF). The solvation methodology adopted was the integral equation formulation (IEF) version of the polarizable continuum model (PCM). 相似文献
3.
Ingrosso F Ladanyi BM Mennucci B Elola MD Tomasi J 《The journal of physical chemistry. B》2005,109(8):3553-3564
The solvent reorganization process after electronic excitation of a polar solute in a polar solvent such as acetonitrile is related mainly to the time evolution of the solute-solvent electrostatic interaction. Modern laser-based techniques have sufficient time resolution to follow this decay in real time, providing information to be confirmed and interpreted by theories and models. We present here a study aimed at the investigation of the different steps involved in the process taking place after a vertical S(0) --> S(1) excitation of a large size chromophore, coumarin 153 (C153), in acetonitrile, from both the solute and the solvent points of view. To do this, we use accurate quantum mechanical calculations for the solute properties within the polarizable continuum model (PCM) and classical molecular dynamics (MD) simulations, both equilibrium and nonequilibrium, for C153 in the presence of the solvent. The geometry of the solute is allowed to change in order to study the role of internal motions in the time-dependent solvation process. The solvent response function has been obtained from the simulation data and compared to experiment, while the comparison between equilibrium and nonequilibrium MD results for the solvation response confirms the validity of the linear response approximation in the C153-acetonitrile system. The MD trajectories have also been used to monitor the structure of the solvation shell and to determine its change in response to the change in the solute partial charges. 相似文献
4.
Castagnola M Rossetti DV Inzitari R Vitali A Lupi A Zuppi C Cabras T Fadda MB Petruzzelli R Giardina B Messana I 《Electrophoresis》2003,24(5):801-807
Measurements by capillary electrophoresis (CE) of bacitracin A(1) effective mobility at different pH values permitted to estimate the five acidic dissociation constants and the Stokes radii at different protonation stages of the macrocyclic dodecapeptide. The pK(a) values were 3.6 and 4.4 for the two carboxylic groups of the lateral chains of D-Asp-11 and D-Glu-4, respectively, 6.4 for the aza-atom of the imidazole ring of His-10, 7.6 for the amino group of N-terminal Ile-1 and 9.7 for the delta-amino group of D-Orn-7, very close to the values obtained by other researchers by titration experiments. In agreement with a rigid macrocyclic structure the Stokes radii of different protonated forms ranged only between 14.3 and 14.8 A. Best fitting procedures performed on experimental mobility measured at two different pH values (5.50 and 6.72) in the presence of increasing Zn(+2) concentration allowed confirming the model that assumes the binding of Zn(+2) to P(0) peptide form with a 1.5 x 10(3) M(-1) intrinsic association constant. Following to Zn(+2) binding, the pK(a) of the amino group of N-terminal Ile-1 is shifted from 7.6 to 5.9 and the Stokes radius is reduced of about 3 A. The mean charge of the bacitracin A(1)-Zn(+2) complex resulted +1.67 and +1.12 at pH 5.50 and 6.72, respectively. These results suggest that the amino group of N-terminal Ile-1 is not essential for Zn(+2) binding. 相似文献
5.
Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study 下载免费PDF全文
Dr. Benedetta Carlotti Dr. Enrico Benassi Prof. Vincenzo Barone Dr. Giuseppe Consiglio Prof. Fausto Elisei Dr. Alessandra Mazzoli Prof. Anna Spalletti 《Chemphyschem》2015,16(7):1440-1450
Three (donor–π–acceptor)+ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials. 相似文献
6.
del Giacco T Carlotti B De Solis S Barbafina A Elisei F 《Physical chemistry chemical physics : PCCP》2011,13(6):2188-2195
The crown thioether 9-[4-(4,7,10,13-tetrathia-1-azacyclopentadecyl]phenyl-N-methylacridinium perchlorate (TCMA) was synthesized and characterized with the aim to verify its ability to interact selectively with metal ions and substantiate the possibility to detect easily the presence of heavy metals in fluid samples. The spectroscopic properties of TCMA, alone and in the presence of metal ions, were therefore studied in polar solvents (MeCN and H(2)O); in particular, steady-state UV-Vis spectrophotometric and fluorimetric techniques were used together with transient absorption spectroscopy with fs time resolution to investigate the spectral and dynamic properties of the lowest excited singlet state of TCMA and of TCMA/metal ion complexes. The absorption in the Vis region is characterized by a charge-transfer nature with the methylacridinium moiety acting as the electron-acceptor and the anilic group as the electron-donor. No emission from the S(1) was detected both in MeCN and H(2)O, while a small S(2)→ S(0) fluorescence emission (λ(max) = 485 nm and ?(F) = 0.0011) was detected in water. Time-resolved measurements with fs resolution of TCMA in MeCN have shown that the relaxed S(1) state is reached ~0.6 ps after the laser pulse, while the S(1)→ S(0) time constant is 3.7 ps. Among the investigated metal ions, only Fe(3+) (in MeCN) and Hg(2+) (in MeCN and H(2)O) were able to form stable complexes (association constant, K(ass) = 1-11 × 10(4) M(-1)) with TCMA. The S(1) state of the TCMA/M(n+) complexes emits with low quantum yield (?(F) = 0.0023-0.014) and decays with time constants much longer than TCMA itself, at least in the case of TCMA/Hg(2+) in MeCN. This study showed that TCMA is a good candidate for colorimetric/fluorimetric sensing of Hg(2+) in aqueous media owing to its high selectivity towards metal ions. 相似文献
7.
Top-down patterning of zeolitic imidazolate framework composite thin films by deep X-ray lithography
Dimitrakakis C Marmiroli B Amenitsch H Malfatti L Innocenzi P Grenci G Vaccari L Hill AJ Ladewig BP Hill MR Falcaro P 《Chemical communications (Cambridge, England)》2012,48(60):7483-7485
For the first time a top-down process was used to control the spatial location of Metal-Organic Frameworks on a surface. Deep X-ray lithography was utilised to micropattern a Zeolitic Imidazolate Framework layer on a sol-gel surface, with exposure hardening the sol-gel by inducing crosslinking while leaving the frameworks intact. 相似文献
8.
The feasibility of microwave-accelerated derivatization for capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection was evaluated. The derivatization reaction was performed in a domestic microwave oven. Histidine (His), 1-methylhistidine (1-MH) and 3-methylhistidine (3-MH) were selected as test analytes and fluorescein isothiocyanate (FITC) was chosen as a fluorescent derivatizing reagent. Parameters that may affect the derivatization reaction and/or subsequent CE separation were systematically investigated. Under optimized conditions, the microwave-accelerated derivatization reaction was successfully completed within 150 s, compared to 4-24 h in a conventional water-bath derivatization process. This will remarkably reduce the overall analysis time and increase sample throughput of CE-LIF. The detection limits of this method were found to be 0.023 ng/mL for His, 0.023 ng/mL for 1-MH, and 0.034 ng/mL for 3-MH, respectively, comparable to those obtained using traditional derivatization protocols. The proposed method was characterized in terms of precision, linearity, accuracy and successfully applied for rapid and sensitive determination of these analytes in human urine. 相似文献
9.
Dr. Benedetta Carlotti Dr. Ilijana Kikaš Prof. Irena Škorić Prof. Anna Spalletti Prof. Fausto Elisei 《Chemphyschem》2013,14(5):970-981
Time‐resolved transient absorption and fluorescence spectroscopy with nano‐ and femtosecond time resolution were used to investigate the deactivation pathways of the excited states of distyrylfuran, thiophene and pyridine derivatives in several organic solvents of different polarity in detail. The rate constant of the main decay processes (fluorescence, singlet–triplet intersystem crossing, isomerisation and internal conversion) are strongly affected by the nature [locally excited (LE) or charge transfer (CT)] and selective position of the lowest excited singlet states. In particular, the heteroaromatic central ring significantly enhances the intramolecular charge‐transfer process, which is operative even in a non‐polar solvent. Both the thiophene and pyridine moieties enhance the S1→T1 rate with respect to the furan one. This is due to the heavy‐atom effect (thiophene compounds) and to the 1(π,π)*→3(n,π)* transition (pyridine compounds), which enhance the spin‐orbit coupling. Moreover, the solvent polarity also plays a significant role in the photophysical properties of these push–pull compounds: in fact, a particularly fast 1LE*→1CT* process was found for dimethylamino derivatives in the most polar solvents (time constant, τ≤400 fs), while it takes place in tens of picoseconds in non‐polar solvents. It was also shown that the CT character of the lowest excited singlet state decreased by replacing the dimethylamino side group with a methoxy one. The latter causes a decrease in the emissive decay and an enhancement of triplet‐state formation. The photoisomerisation mechanism (singlet/triplet) is also discussed. 相似文献
10.