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1.
2.
The three proteins phosphorylase b, calmodulin and fibrinogen are adsorbed onto thioalkyl derivatives of Sepharose much more strongly than onto gels carrying the same alkyl residue coupled via a carbamate linkage. This enhancement of binding onto alkyl-S-Sepharoses compared with alkyl-N-agaroses is not primarily due to an increase in the extent of conformational changes of the proteins occurring on the gel surface. This can be shown in experiments with the tripeptide Trp-Trp-Trp. The Trp tripeptide is also adsorbed with a much higher affinity to butyl-S-Sepharose than to butyl-N-Sepharose, showing that the primary interaction between the immobilized alkyl residue and the amino acids of the protein is decisive for adsorption. A model stressing the strong influence of an atom or a group of atoms at the base of an immobilized alkyl residue is described as "base-atom recognition". 相似文献
3.
Paraskevas D. Tzanavaras Demetrius G. Themelis Anastasios Economou Georgios Theodoridis 《Mikrochimica acta》2003,142(1-2):55-62
Two new simple and rapid methods are reported for the accurate and precise spectrophotometric determination of captopril
(CPL) using flow (FI) and sequential injection (SI) analysis. The methods are based on the fast oxidation of CPL by Fe(III).
The produced Fe(II) reacts with 2,2′-dipyridyl-2-pyridylhydrazone (DPPH) in acidic medium to form a colored complex which
is monitored spectrophotometrically at 535 nm. Both methods allow the determination of the analyte up to 1000 mg L−1 at a sampling rate of 120 and 60 injections per hour for FI and SI, respectively. The methods are very precise [s
r=0.8 and 1.2% at 500 mg L−1 CPL (n=12) for FI and SI, respectively] and the 3σ detection limits (c
L=4.0 and 7.0 mg L1, respectively) are quite satisfactory. Their application to a variety of anti-hypertensive commercial pharmaceutical formulations
showed excellent results (relative errors, e
r, < ± 1.6% in all cases compared to an official HPLC method), while common pharmaceutical excipients were found not to interfere.
Recovery experiments further verified the accuracy of the developed methods, as the percent recoveries were in the range of
98.1–102.5%.
Author for correspondence. E-mail: themelis@chem.auth.gr
Received May 9, 2002; accepted January 8, 2003
Published online May 5, 2003 相似文献
4.
Stavroula Piperaki Anastasios Perakis Maria Parissi-Poulou 《Journal of chromatography. A》1994,660(1-2):339-350
A liquid chromatographic method for the separation of promethazine (PR) and its positional isomer isopromethazine (IPR) is described.PR is an N-substituted phenothiazine with the actions and the uses of the antihistamines (H1-receptor antagonists). IPR is an impurity in the pharmaceutical preparations of PR and must be controlled at a level below 1%. The liquid chromatographic behaviour of PR and IPR on a hydrolytically stable β-cyclodextrin (β-CD) column with respect to mobile phase composition, pH, ionic strength and the nature of the organic modifier was also investigated. Based on the results, conditions were chosen for the isocratic separation of the two isomers. The proposed separation method is simple and rapid and permits the simultaneous determination of PR and IPR. The separation selectivity of a cyclodextrin bonded-phase column was examined. Special attention was devoted to modelling the inclusion complexes of PR and IPR with β-CD in order to predict their optimum orientation within the β-CD cavity. 相似文献
5.
Anastasios Dondos 《European Polymer Journal》2002,38(7):1311-1317
The variation of the viscometric expansion factor of macromolecular chains, αη, as a function of the number of blobs of which these chains consist, N/Nc, obeys a universal law, both for wormlike and for flexible polymers. Using also wormlike and flexible polymers, we show that the factor relating the excluded volume parameter, z, to the static expansion factor, αG, varies with the number of statistical chain segments, in a universal manner. The universalities appear to be valid below chain lengths required for the appearance of a power law, and they do not seem to have an upper limit in molecular weight. For these two universalities concerning flexible and wormlike polymers we use relations derived from the blob theory [Polymer 20 (1979) 1083] and statistical mechanical theory [J. Chem. Phys. 57 (1972) 2843]. 相似文献
6.
Christos Kokkinos Anastasios Economou Ioannis Raptis Constantinos E. Efstathiou Thanasis Speliotis 《Electrochemistry communications》2007,9(12):2795-2800
This work describes a novel type of bismuth electrode for stripping voltammetry based on coating a silicon substrate with a thin bismuth film by means of sputtering. The bismuth-based sensors were characterized by optical methods (scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD)) and as well as by linear sweep voltammetry. Subsequently, the electrodes were tested for the detection of low concentrations of trace metals (Cd(II), Pb(II) and Ni(II)) by stripping voltammetry. Well-formed stripping peaks were observed for trace concentrations of the target analytes demonstrating “proof-of-principle” for these sensors. This type of electrochemical device, utilizing thin-film technology for the formation of the bismuth film, holds promise for future applications in trace metal analysis. 相似文献
7.
QUANTITATION OF PHOTOSYSTEM II ACTIVITY IN SPINACH CHLOROPLASTS. EFFECT OF ARTIFICIAL QUINONE ACCEPTORS 总被引:1,自引:0,他引:1
Quantitation of photosystem II (PSII) activity in spinach chloroplasts is presented. Rates of PSII electron-transport were estimated from the concentration of PSII reaction-centers (Chl/PSII = 380:1 when measured spectrophotometrically in the ultraviolet [ΔA320 ] and green [ΔA540–550 ] regions of the spectrum) and from the rate of light utilization by PSII under limiting excitation conditions. Rates of PSII electron-transport were measured under the same light-limiting conditions using 2,5-dimethylbenzoquinone or 2,5-dichlorobenzoquinone as the PSII artificial electron acceptors. Evaluation is presented on the limitations imposed in the measurement of PSII electron flow to artificial quinones in chloroplasts. Limitations include the static quenching of excitation energy in the pigment bed by added quinones, the fraction of PSII centers (PSIIβ ) with low affinity to native and added quinones, and the loss of reducing equivalents to molecular oxygen. Such artifacts lowered the yield of steady-state electron transport in isolated chloroplasts and caused underestimation of PSII electron-transport capacity. The limitations described could explain the low PSII concentration estimates in higher plant chloroplasts (Chl/PSII = 600 ± 50) resulting from proton flash yield and/or oxygen flash-yield measurements. It is implied that quantitation of PSII by repetitive flash-yield methods requires assessment of the slow turnover of electrons by PSIIβ and, in the presence of added quinones, assessment of the PSII quantum yield. 相似文献
8.
Vassiliki I. Bebeki Anastasios N. Voulgaropoulos 《Fresenius' Journal of Analytical Chemistry》1992,342(4-5):352-356
Summary The spontaneous adsorption of the Co2+ complex with 1,10-phenanthroline on HMDE was utilized for the development of a voltammetric analytical method employing phase selective alternating current, with first harmonic AC1 in phase, =0°, voltammetry. The dependence of the analytical voltammetric response on physical and chemical parameters in various supporting electrolytes was investigated in detail. Optimum conditions for Co2+ determination were established. The method is very sensitive and selective. The determination limit is 205 ng/l Co2+ (adsorption time, tads=20 min). The precision and accuracy were evaluated: 1.84 g/l Co2+, RSD=3.24%, RE=–0.54%; for 205 ng/l Co2+, RSD=4.85%, RE=–3.90%. The results showed good reproducibility and reliabiality. The method was applied to natural waters, wines, mussel tissue and aquatic algae certified reference material. 相似文献
9.
A new synthetic procedure has been developed in Mn cluster chemistry involving reductive aggregation of permanganate (MnO4-) ions in MeOH in the presence of benzoic acid, and the first products from its use are described. The reductive aggregation of NBu(n)4MnO4 in MeOH/benzoic acid gave the new 4Mn(IV), 8Mn(III) anion [Mn12O12(OMe)2(O2CPh)16(H2O)2]2-, which was isolated as a mixture of two crystal forms (NBu(n)4)2[Mn12O12(OMe)2(O2CPh)16(H2O)2].2H2O.4CH2Cl2 (1a) and (NBu(n)4)2[Mn12O12(OMe)2(O2CPh)16(H2O)2].2H2O.CH2Cl2 (1b). The anion of 1 contains a central [Mn(IV)4(mu3-O)2(mu-O)2(mu-OMe)2]6+ unit surrounded by a nonplanar ring of eight Mn(III) atoms that are connected to the central Mn4 unit by eight bridging mu3-O2- ions. This compound is very similar to the well-known [Mn12O12(O2CR)16(H2O)4] complexes (hereafter called "normal Mn12"), with the main difference being the structure of the central cores. Longer reaction times (approximately 2 weeks) led to isolation of polymeric [Mn(OMe)(O2CPh)2]n2, which contains a linear chain of repeating [Mn(III)(mu-O2CPh)2(mu-OMe)Mn(III)] units. The chains are parallel to each other and interact weakly through pi-stacking between the benzoate rings. When KMnO4 was used instead of NBu(n)4MnO4, two types of compounds were obtained, [Mn12O12(O2CPh)16(H2O)4] (3), a normal Mn12 complex, and [Mn4O2(O2CPh)8(MeOH)4].2MeOH (4.2MeOH), a new member of the Mn4 butterfly family. The cyclic voltammogram of 1 exhibits three irreversible processes, two reductions and one oxidation. One-electron reduction of 1 by treatment with 1 equiv of I- in CH2Cl2 gave (NBu(n)4[Mn12O12(O2CPh)16(H2O)3].6CH2Cl2 (5.6CH2Cl2), a normal Mn12 complex in a one-electron reduced state. The variable-temperature magnetic properties of 1, 2, and 5 were studied by both direct current (dc) and alternating current (ac) magnetic susceptibility measurements. Variable-temperature dc magnetic susceptibility studies revealed that (i) complex 1 possesses an S = 6 ground state, (ii) complex 2 contains antiferromagnetically coupled chains, and (iii) complex 5 is a typical [Mn12]- cluster with an S = 19/2 ground state. Variable-temperature ac susceptibility measurements suggested that 5 and both isomeric forms of 1 (1a,b) are single-molecule magnets (SMMs). This was confirmed by the observation of hysteresis loops in magnetization vs dc field scans. In addition, 1a,b, like normal Mn12 clusters, display both faster and slower relaxing magnetization dynamics that are assigned to the presence of Jahn-Teller isomerism. 相似文献
10.
Karam Asad Dr. Anastasios Stergiou Dr. Andreas Kourtellaris Prof. Nikos Tagmatarchis Prof. Nikos Chronakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13879-13886
The multiaddition chemistry of azafullerene C59N has been scarcely explored, and the isolation of pure bisadducts is in its infancy. Encouraged by the recent regioselective synthesis of the inherently chiral equatorialface bisadduct of C59N, we focused on the isolation of the first trans-4 bisadduct in a simple two-step approach. The first regioselective synthesis of the trans-4 bisadduct of C59N by using cyclo-[2]-dodecylmalonate as a tether is now reported. The newly synthesized bisadduct has C1 symmetry, as evidenced by 13C NMR, while X-ray crystallography validated the trans-4′ addition pattern. Furthermore, the inherently chiral trans-4′ C59N bisadduct was enantiomerically resolved, and the mirror-image relation of the two enantiomers was probed by circular dichroism spectroscopy. Finally, UV-Vis and redox assays suggested that the addition pattern has a reflection in the light-harvesting and redox properties of the bisadduct. 相似文献