全文获取类型
收费全文 | 34065篇 |
免费 | 1345篇 |
国内免费 | 31篇 |
专业分类
化学 | 23117篇 |
晶体学 | 257篇 |
力学 | 646篇 |
数学 | 5070篇 |
物理学 | 6351篇 |
出版年
2023年 | 275篇 |
2022年 | 223篇 |
2021年 | 405篇 |
2020年 | 592篇 |
2019年 | 558篇 |
2018年 | 775篇 |
2017年 | 719篇 |
2016年 | 1339篇 |
2015年 | 1060篇 |
2014年 | 1124篇 |
2013年 | 2260篇 |
2012年 | 2418篇 |
2011年 | 2606篇 |
2010年 | 1506篇 |
2009年 | 1227篇 |
2008年 | 2137篇 |
2007年 | 2095篇 |
2006年 | 1832篇 |
2005年 | 1668篇 |
2004年 | 1385篇 |
2003年 | 1045篇 |
2002年 | 930篇 |
2001年 | 691篇 |
2000年 | 582篇 |
1999年 | 439篇 |
1998年 | 332篇 |
1997年 | 242篇 |
1996年 | 365篇 |
1995年 | 244篇 |
1994年 | 237篇 |
1993年 | 286篇 |
1992年 | 258篇 |
1991年 | 176篇 |
1990年 | 168篇 |
1989年 | 137篇 |
1988年 | 147篇 |
1987年 | 143篇 |
1986年 | 140篇 |
1985年 | 211篇 |
1984年 | 159篇 |
1983年 | 144篇 |
1982年 | 127篇 |
1981年 | 123篇 |
1980年 | 109篇 |
1979年 | 112篇 |
1978年 | 118篇 |
1977年 | 113篇 |
1976年 | 117篇 |
1975年 | 106篇 |
1973年 | 95篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Nucleophilic vinylic substitutions of 4H-pyran-4-one and 2-methyl-4H-pyran-4-one with ammonia were calculated by the B3LYP method using the 6-31G(d,p) basis set. Bulk solvent effects of aqueous
solution were estimated by the polarized continuum and Poisson–Boltzmann self-consistent reaction field models using the 6-311+G(d,p)
basis set. In the gas phase different mechanisms were found for the two reaction systems calculated. The reaction of 4H-pyran-4-one proceeds through enol, whereas a feasible path for the less reactive 2-methyl-4H-pyran-4-one is the mechanism through a keto intermediate. Addition of ammonia in concert with proton transfer is the rate-determining
step ofthe reaction. The mechanism proceeding either by a bimolecular nucleophilic substitution (SN2) or by one involving a tetrahedral zwitterionic intermediate is shown to be unlikely in the gas phase or nonpolar solution.
The effects of bulk solvent not only consist in a reduction of the various activation barriers by about 25–40 kJ mol−1 but also in a change in the reaction mechanism.
Received 26 May 2002 / Accepted 26 July 2002 /
Published online: 14 February 2003 相似文献
992.
The quantification of volatile organic compounds (VOCs) in flexible multilayer packaging materials using headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) was studied. The analytes imclude 22 compounds such as aldehydes. ketones, carboxylic acids and hydrocarbons formed by thermooxidative degradation of polyethylene during the extrusion coating process in the manufacture of the packaging, and many of them are involved in the unpleasant and undesirable odour of these materials. External standard calibration using a solution of the analytes in an appropriate solvent was the first approach studied. Aqueous solutions of the analytes provided low reproducibility and the reduction of aldehydes to alcohols under the HS-SPME conditions. Hexadecane was chosen as the solvent since its polarity is similar to that of polyethylene and its volatility is lower than that of the analytes. However, hexadecane should be added to the sample before the analysis as it modifies the absorption capacity of the fibre. A 75-microm Carboxen-poly(dimethylsiloxane) fibre was used to extract the VOCs from the headspace above the packaging in a 15-ml sealed vial at 100 degrees C after 5 min of preincubation. The influence of the extraction time on the amount extracted was studied for a standard solution of the analytes in hexadecane, together with the influence of the volume of the standard solution and the amount of the sample placed in the vial. Standard addition and multiple HS-SPME were also studied as calibration methods and the results obtained in the quantitative analysis of a packaging material were compared. 相似文献
993.
Auchère F Raleiras P Benson L Venyaminov SY Tavares P Moura JJ Moura I Rusnak F 《Inorganic chemistry》2003,42(4):938-940
Superoxide reductases catalyze the monovalent reduction of superoxide anion to hydrogen peroxide. Spectroscopic evidence for the formation of a dinuclear cyano-bridged adduct after K(3)Fe(CN)(6) oxidation of the superoxide reductases neelaredoxin from Treponema pallidum and desulfoferrodoxin from Desulfovibrio vulgaris was reported. Oxidation with K(3)Fe(CN)(6) reveals a band in the near-IR with lambda(max) at 1020 nm, coupled with an increase of the iron content by almost 2-fold. Fourier transform infrared spectroscopy provided additional evidence with CN-stretching vibrations at 2095, 2025-2030, and 2047 cm(-)(1), assigned to a ferrocyanide adduct of the enzyme. Interestingly, the low-temperature electronic paramagnetic resonance (EPR) spectra of oxidized TpNlr reveal at least three different species indicating structural heterogeneity in the coordination environment of the active site Fe ion. Given the likely 6-coordinate geometry of the active site Fe(3+) ion in the ferrocyanide adduct, we propose that the rhombic EPR species can serve as a model of a hexacoordinate form of the active site. 相似文献
994.
García-Santos Mdel P González-Mancebo S Hernández-Benito J Calle E Casado J 《Journal of the American Chemical Society》2002,124(10):2177-2182
Nitrosation reactions of amino acids with an -NH(2) group [namely, six alpha-amino acids (glycine, alanine, alpha-aminobutyric acid, alpha-aminoisobutyric acid, valine, and norvaline); two beta-amino acids (beta-alanine and beta-aminobutyric acid), and one gamma-amino acid (gamma-aminobutyric acid)] were studied. Nitrosation was carried out in aqueous acid media, mimicking the conditions of the stomach lumen. The rate equation was r = k(3)(exp)[amino acid][nitrite](2), with a maximum k(3)(exp) value in the 2.3-2.7 pH range. The existence of an isokinetic relationship supports the argument that all the reactions share a common mechanism. A nitrosation mechanism is proposed, and the following conclusions are drawn: (i) Nitrosation reactions of amino acids with a primary amino group in acid media occur with dinitrogen trioxide as the main nitrosating agent. The finding that the nitrosation rate is proportional to the square of the nitrite concentration suggests that the yield of nitrosation products in the stomach would increase sharply with higher nitrate/nitrite intakes. (ii) Stomach hypochlorhydria could be a potential enhancer of in vivo amino acid nitrosation. (iii) The reactivity (k(3)()(exp)) [alpha-amino acids > beta-amino acids > gamma-amino acids] is the same as that found in a previous work for the alkylating potential of lactones formed from nitrosation products of the same amino acids. This implies that the nitrosation reactions of the most common natural amino acids are the most efficient precursors of the most powerful alkylating agents. (iv) The order of magnitude (10(7)-10(8) M(-1) s(-1)) of the bimolecular rate constants of nitrosation shows that such reactions occur through an encounter process. 相似文献
995.
From extraction experiments with 133Ba as a tracer, the extraction constant corresponding to the equilibrium Ba2+(aq) + 2A-(aq) + 2L(nb) BaL2
2+(nb) + 2A-(nb) in the two-phase water-nitrobenzene system (A- = picrate, L = benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K
ex (BaL2
2+, 2A-) = 5.7. Furthermore, the stability constant of the benzo-15-crown-5 - barium complex in nitrobenzene saturated with water was calculated: log bnb (BaL2
2+) = 14.6. 相似文献
996.
Mas-Ballesté R Capdevila M Champkin PA Clegg W Coxall RA Lledós A Mégret C González-Duarte P 《Inorganic chemistry》2002,41(12):3218-3229
The nucleophilicity of the [Pt(2)S(2)] core in [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH(2)Cl(2) solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged [Pt(2)S(2)] central ring. The reaction of 1 and 2 with CH(2)Cl(2) has been followed by means of (31)P, (1)H, and (13)C NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt[Ph(2)P(CH(2))(n)PPh(2)](S(2)CH(2))], n = 3 (7), 2 (8), and [Pt[Ph(2)P(CH(2))(n)PPh(2)]Cl(2)], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the [Pt(2)S(2)] ring. Only in the case of 1, the reaction proceeds further yielding [Pt(2)(dppp)(2)[mu-(SCH(2)SCH(2)S)-S,S']]Cl(2) (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH(2) groups that participate in the expansion of the (SCH(2)S)(2-) ligand in 7 to afford the bridging (SCH(2)SCH(2)S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged [(dppp)Pt(mu-S)(2)Pt(dppp)] core capped by a CH(2)SCH(2) fragment. 相似文献
997.
Gil-Agustí M Capella-Peiró E Monferrer-Pons L García-Alvarez-Coque MC Esteve-Romero J 《The Analyst》2001,126(4):457-464
The chromatographic behaviour of binary and ternary mixtures of several phenethylamines (phenylephrine, phenylpropanolamine, ephedrine, pseudoephedrine and methoxyphenamine) and antihistamines (pheniramine, carbinoxamine, doxylamine, chlorpheniramine, dexchlorpheniramine, dexbrompheniramine, diphenhydramine, tripolidine, azatadine and phenyltoloxamine), found in cough-cold pharmaceutical preparations, was studied using C8, C18 and cyano columns, micellar mobile phases of sodium dodecyl sulfate (SDS) and pentanol and UV detection. Using a C8 column and mobile phases of 0.05 mol l-1 SDS-6% v/v pentanol or 0.15 mol l-1 SDS-2% v/v pentanol at pH 7, more than 30 different phenethylamine-antihistamine combinations can be resolved in < 15 min. Intra- and inter-day repeatabilities and reproducibilities evaluated at three different drug concentrations (0.5, 5 and 25 micrograms ml-1, n = 10) were below 1.6, 2.5 and 2.4%, respectively. The drug amounts found in 18 formulations agreed with those declared by the manufacturers within the tolerance limits, and with those obtained using a mobile phase of 55% v/v methanol at pH 7. No interference was observed from other accompanying drugs such as acetylsalicylic acid, ascorbic acid, betamethasone, bromhexine, caffeine, codeine, dextromethorphan, paracetamol, prednisolone, salicylamide and tartrazine. The proposed procedure has the advantage over the conventional aqueous-organic procedure of using a small amount of organic solvent, which is highly retained in the SDS solution. The efficiencies are also greater. On the other hand, in the micellar system, the retentions of phenethylamines and antihistamines are similar, although the compounds can be easily resolved. In contrast, using the methanol-water mobile phase, the phenethylamines are weakly retained, whereas the antihistamines usually show a high retention. 相似文献
998.
Meseguer B Alonso-Díaz D Griebenow N Herget T Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(21):3943-3957
Protein kinaseC (PKC) is linked to the signal-induced modulation of a wide variety of cellular processes, such as growth, differentiation, secretion, apoptosis, and tumor development. The design and synthesis of small molecules that regulate these different cellular signaling systems is at the forefront of modern drug design. Herein we report a) an efficient method for the synthesis of indolactamV (6), a PKC activator, and its N13-des(methyl) analogues (19) using a regioselective organometallic transformation, a convenient aminomalonate derivative (10) to introduce the appropriate functionality and an enantiospecific enzymic hydrolysis as key steps; b) the use of this method in the first solid-phase synthesis of a teleocidin library modifying the N-13, C-12 and C-7 alkyl chains, and, therefore, producing a library of potential activators and/or inhibitors of PKC of the general structure (32); c) the activation of PKC by selected members of the library using a MARCKS translocation in vivo assay system; d) the observation that some of these analogues are nearly as effective as the natural PKC activators phorbol dibutyrate and (-)-indolactam V (6), and e) the observation that some of these analogues have different potential to induce down-regulation of members of the PKC gene family after chronic stimulation. 相似文献
999.
C. Gutiérrez-Wing J. A. Ascencio M. Pérez-Alvarez M. Marín-Almazo M. José-Yacamán 《Journal of Cluster Science》1998,9(4):529-545
The structure and ordering of nanoparticles of gold functionalized with n-alkyl thiol molecules are studied both experimentally and theoretically. Samples where produced using n=6 to n=16 alkyl thiol molecules. High Resolution Electron Microscopy coupled with image processing was used to study the gold particle structure. The details of the particle structure are discussed. We found that when the gold surface is saturated with thiol molecules there is some tendency to produce molecules with a disulphide structure. We also show that ordered arrays of particles can be produced using Langmuir-Blodgett techniques. The crystal structure of the films produced is studied and found to be 3D hcp. We also report that thiol covered gold particles with a size of 5 nm present a rounded shape suggesting that thiol molecules might induce an isotropic surface energy. It is found in the theoretical calculations that a strong bond between gold and sulphur is required to stabilize the complex metal-n-alkyl thiol. It is predicted that otherwise a heavily distorted nanocore will be formed. This is contrary to the observed structure of the particles. 相似文献
1000.
An improved version of the disposable multichannel immunochemical biosensor for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) based on a screen-printed amperometric transducer and monoclonal antibodies (MAb) against 2,4-D is reported. Entrapment within a thin Nafion film was used for the direct immobilization of MAb at the electrode surface. The amount of the tracer (2,4-D conjugated to acetylcholinesterase) bound in a competitive immunochemical reaction was determined amperometrically using acetylthiocholine iodide as substrate. The measuring procedure (times of incubation with tracer and substrate, pH, tracer concentration) was optimized. The sensor was able to detect less than 0.01 μg/L of free 2,4-D in water. One analysis (8 samples) was completed in 30 min (20 min for immunochemical reaction, 5 min incubation with substrate, 5 min measurement). The performance of the immunosensor (two configurations) was evaluated on real samples (tap water) with added 2,4-D. The determined amounts (mean values 0.097 to 0.105 and 0.89 to 1.13) corresponded well with the added contents of 2,4-D (0.100 and 1.00 μg/L, respectively). 相似文献