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991.
Samuel M. Hudson John A. Cuculo 《Journal of polymer science. Part A, Polymer chemistry》1982,20(2):499-511
The melting temperatures of thermoreversible gels formed from solutions of cellulose in liquid ammonia/ammonium thiocyanate mixtures were measured over a volume fraction range of .01–.004. Three samples of cellulose with Mw ranging from 1 × 105 to 1.64 × 105 were used. The findings show that the structural makeup of the gels is strongly reflected in their time-dependent behavior. The reciprocal of their melting temperature is a nearly linear function of the logarithm of the cellulose concentration. The relation between the logarithm of Mw and the reciprocal temperature of gel melting was also nearly linear. Exothermic heats of reaction ranging from 150 to 460 kcal/mol were calculated from the Ferry-Eldridge relationship (? ln C/?) = ΔHx/R for the formation of cross-links, assuming that they result from a binary association of chains. It is inferred that the cross-linking loci in the gel were crystallites that consisted of glucose units. In addition, an initial study is reported of the fiber-forming potential of the liquid ammonia/ammonium thiocyanate system. Rudimentary fiber extrusion from a modified syringe was readily demonstrated. Operable coagulation systems involved proton-donating agents as well as methanol. Tenacities of these unstretched, as spun fibers, ranged as high as 0.89 g/d. 相似文献
992.
The combined techniques of inductively coupled plasma mass spectrometry (ICP-MS) and isotope dilution yield as much as a three-fold improvement in precision for trace-level rubidium determinations in geological materials over conventional isotope dilution using thermal ionization mass spectrometry (TIMS). Rubidium determinations by TIMS, precise to 0.6% (1 s.d.), are hindered by uncorrectable fractionation effects, whereas fractionation can be monitored during ICP-MS determinations, providing results as precise as 0.17% (1 s.d.). Precise rubidium data are critical for high-precision RbSr geochronology. 相似文献
993.
Capella-Peiró ME Bose D Gil-Agustí M Esteve-Romero J Carda-Broch S 《Journal of chromatography. A》2005,1073(1-2):277-283
A simple and sensitive direct injection chromatographic procedure is developed for the determination of heroin, two of its metabolites (morphine and 6-monoacetylmorphine (6-MAM)), and benzoylecgonine (a metabolite of cocaine) in serum samples. The proper resolution of the four substances is obtained with a chemometrics approach, where the retention is modelled as a first step using the retention factors obtained in a limited number of mobile phases. Afterwards, an optimisation criterion that takes into account the position and shape of the chromatographic peaks is applied. The mobile phase selected to carry out the analysis was 0.1 mol L(-1) SDS-4% (v/v) butanol buffered at pH 7, in which the separation is performed in less than 18 min. The limits of quantification were in the 17-36 ng mL(-1) range. Intra- and inter-day assay accuracy and precision (below 3%) were obtained following ICH guidelines. The method developed was applied to the determination of the drugs studied in serum samples with good recoveries (90-104%). Serum samples from subjects that have been ingested cocaine and heroin were also analysed. The samples were injected directly in the chromatographic system without any pretreatment. 相似文献
994.
Ignatova M Voccia S Gilbert B Markova N Mercuri PS Galleni M Sciannamea V Lenoir S Cossement D Gouttebaron R Jérôme R Jérôme C 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10718-10726
Novel copolymer brushes have been synthesized by a two-step "grafting from" method that consists of the electrografting of poly(2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-ethylacrylate) onto stainless steel, followed by the nitroxide-mediated radical polymerization of 2-(dimethylamino ethyl)acrylate and styrene or n-butyl acrylate, initiated from the electrografted polyacrylate chains. The grafted copolymers were quaternized in order to endow them with antibacterial properties. Peeling tests have confirmed the strong adhesion of the grafted copolymer onto the stainless steel substrate. Quartz crystal microbalance experiments have proven that fibrinogen adhesion is lower on the hydrophilic quaternized films compared to the nonionic counterpart. Such quaternized copolymers exhibit significant antibacterial activity against the Gram-positive bacteria S. aureus and the Gram-negative bacteria E. coli. 相似文献
995.
Martinavarro-Domínguez A Boseb D Durgbanshi A Gil-Agustí M Capella-Peiró ME Broch SC Esteve-Romero J 《Journal of chromatography. A》2005,1073(1-2):309-315
A procedure was developed for the determination of caffeine and theophylline using a C18 column (5 microm, 250 mm x 4.6 mm) and micellar liquid chromatography using hybrid mobile phases containing sodium dodecyl sulfate (SDS) and propanol, butanol or pentanol as modifiers. Detection was performed with a variable wavelength UV-vis detector at 272 nm. After the application of an interpretative strategy for the selection of the optimimum mobile phase, caffeine and theophylline can be resolved and determined in serum samples by direct injection, using a mobile phase made up of 50 mM SDS-2.5% (v/v) propanol-10 mM KH2PO4, pH 7, with an analysis time below 5 min. Calibration was linear in the range 0.05 to 50 microg mL(-1) with r > 0.999. The statistical evaluation of the method was examined by performing intra-day (n = 6) and inter-day calibration (n = 7) and was found to be satisfactory, with highly accurate and precise results. The proposed method was suitably validated and applied to the determination of caffeine and theophylline in serum samples of patients treated with bronchodilators. 相似文献
996.
The nucleobases uracil (U) and thymine (T) offer three hydrogen-bonding sites for double H-bond formation via neighboring N-H and C=O groups, giving rise to the Watson-Crick, wobble and sugar-edge hydrogen bond isomers. We probe the hydrogen bond properties of all three sites by forming hydrogen bonded dimers of U, 1-methyluracil (1MU), 3-methyluracil (3MU), and T with 2-pyridone (2PY). The mass- and isomer-specific S1 <-- S0 vibronic spectra of 2PY.U, 2PY.3MU, 2PY.1MU, and 2PY.T were measured using UV laser resonant two-photon ionization (R2PI). The spectra of the Watson-Crick and wobble isomers of 2PY.1MU were separated using UV-UV spectral hole-burning. We identify the different isomers by combining three different diagnostic tools: (1) Selective methylation of the uracil N3-H group, which allows formation of the sugar-edge isomer only, and methylation of the N1-H group, which leads to formation of the Watson-Crick and wobble isomers. (2) The experimental S1 <-- S0 origins exhibit large spectral blue shifts relative to the 2PY monomer. Ab initio CIS calculations of the spectral shifts of the different hydrogen-bonded dimers show a linear correlation with experiment. This correlation allows us to identify the R2PI spectra of the weakly populated Watson-Crick and wobble isomers of both 2PY.U and 2PY.T. (3) PW91 density functional calculation of the ground-state binding and dissociation energies De and D0 are in agreement with the assignment of the dominant hydrogen bond isomers of 2PY.U, 2PY.3MU and 2PY.T as the sugar-edge form. For 2PY.U, 2PY.T and 2PY.1MU the measured wobble:Watson-Crick:sugar-edge isomer ratios are in good agreement with the calculated ratios, based on the ab initio dissociation energies and gas-phase statistical mechanics. The Watson-Crick and wobble isomers are thereby determined to be several kcal/mol less strongly bound than the sugar-edge isomers. The 36 observed intermolecular frequencies of the nine different H-bonded isomers give detailed insight into the intermolecular force field. 相似文献
997.
Wolfgang Petz Prof. Dr. Samuel Heimann Florian Öxler Bernhard Neumüller Prof. Dr. 《无机化学与普通化学杂志》2007,633(3):365-367
The reaction of the carbodiphosphorane Ph3P=C=PPh3 ( 1 ) with MeI in the presence of iodine gives the oxidation product (IC(PPh3)2)2I[I3]·(I2)2 ( 2 ). In the solid state dimeric units linked by indefinite ···I?···I2···I3?···I2···I?··· chains are found. An additional I···I contact between the cation and the I2 molecule is formed, amounting to 359.23(5) pm. 2 crystallizes in the monoclinic space group P2/c, with the unit cell dimensions a = 2053.9(1), b = 1011.4(1), c = 1889.8(1) pm; β = 105.21(1)° and Z = 4. 相似文献
998.
Fourteen elements can be rapidly determined in whole blood by the neutron activation analysis procedure described. Three of these (Ag, Cl, Se) are measured after a 10-s irradiation and eleven others (Al, Ba, Br, Ca, Cu, I, Mg, Mn, Mo, Rb, V) are determined by a 180-s irradiation of a 1-cm3 sample of whole blood after destruction of organic matter and removal of sodium by hydrated antimony pentoxide. A further 13 elements (As, Au, Co, Cr, Cs, Fe, Hg, K, Na, Ni, Sb, Sc, Zn) are determined after overnight irradiation in the SLOWPOKE reactor. 相似文献
999.
Kemp and Kemp have proposed a scheme of inspection for two types (A and B) of non-conformity. There is serial inspection for type A, continuing until a sequence of k successive As is observed. These k items are discarded, and all previous items (since the last inspection for A) are subject to a Dorfman group-screening inspection procedure for B. We develop formulae for the properties of this scheme, when inspection (for both A and B) may not be perfect, allowing for both false negatives and false positives. Some numerical values given by the formulae are presented, with a view to assessing the robustness of Kemp and Kemp's scheme. 相似文献