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101.
Hołyst R Staniszewski K Patkowski A Gapiński J 《The journal of physical chemistry. B》2005,109(18):8533-8537
We observed a very unusual kinetic pathway in a separating C(12)E(6)/PEG/H(2)O ternary mixture. We let the mixture separate above the spinodal temperature (cloud point temperature) for some time and next cool it into a metastable region of a phase diagram, characterized by two minima of the Gibbs potential, one corresponding to the homogeneous mixture and one to the fully separated PEG-rich and C(12)E(6)-rich phases. Despite the fact that in the metastable region the thermodynamic equilibrium corresponds to the separated phases (global minimum of the Gibbs free energy), we observe perfect mixing of the initially separated phase. The homogeneous state, obtained in this way, does not separate, if left undisturbed. However, many cooling-heating cycles or full separation with visible meniscus above the cloud point temperature induce the phase separation in the metastable region. The metastable region can exist tens of degrees below the cloud point temperature. This effect is not observed in the binary mixture of C(12)E(6)/H(2)O. 相似文献
102.
Yoshihisa Kurasawa Waka Satoh Izumi Matsuzaki Yuka Maesaki Yoshihisa Okamoto Ho Sik Kim 《Journal of heterocyclic chemistry》2003,40(5):837-843
The reaction of the quinoxaline N‐oxides 7a,b with diethyl ethoxymethylenemalonate gave the 1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 8a,b , whose reaction with N‐bromosuccinimide or N‐chlorosuccinimide afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 9a‐d. The reaction of compounds 9a‐d with hydrazine hydrate resulted in hydrolysis and decarboxylation to provide the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 10a‐d , whose reaction with nitrous acid effected oxidation to furnish the 3‐halogeno‐4‐hydroxy‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 11a‐d , respectively. The reaction of compounds 11a‐d with hydrazine hydrate afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4‐ols 12a‐d , whose oxidation provided the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones 6a‐d , respectively. Compounds 6a‐d had antifungal activities in vitro. 相似文献
103.
J. Hošek 《Czechoslovak Journal of Physics》1977,27(9):959-966
The spontaneous symmetry breakdown is treated by means of a variational approach. Use is made of coherent states of Glauber and of pairing states of BCS-type as the translationally invariant vacuum states for the discussion of the real scalar field 4 withm
0
2
0. The first type of trial states reproduces the usual approach to spontaneous symmetry breakdown (-) in the tree approximation (which is possible only form
0
2
<0), while the second type of trial states offers the possibility of spontaneous symmetry breakdown even form
0
2
=0. 相似文献
104.
Abstract— C4 -- Photocycloaddition of 5,7-dimethoxycoumarin (DMC) to thymine (λ≥ 300 nm) was studied in dioxane-water solution, in aqueous frozen state, and solid film state. The major product was isolated and characterized by physical methods. Elemental analysis data, spectral analyses, and photo-splitting of the product indicate the product to be a 1:l C4 -- cycloadduct of DMC and thymine. 相似文献
105.
Two 60-residue snake toxins with four disulfide bridges, cardiotoxin II and IV, of Taiwan cobra (Naja naja atra) have been rapidly prepared in overall yields of 3.9% (cardiotoxin II) and 3.7% (cardiotoxin IV) within three weeks using the chemical method. Physicochemical characterization of these synthetic cardiotoxins was carried out by amino acid analysis, mass spectroscopy, capillary electrophoresis, peptide mapping, circular dichroism spectroscopy, and lethal toxicity. As compared with natural cardiotoxins, the results indicated that the synthetic cardiotoxins possessed the same physicochemical properties as those of natural ones. Therefore, in addition to preparation of various important toxins with satisfactory quantities for biochemical and pharmacological studies within a short lime, this rapid method also provides an important route to obtain many interesting toxins and designed toxin analogues for structure/function relationship studies in the near further. 相似文献
106.
Oh JY Moon JH Lee YH Hyung SW Lee SW Kim MS 《Rapid communications in mass spectrometry : RCM》2005,19(10):1283-1288
Photodissociation (PD) tandem mass spectra have been obtained at 266 nm for the protonated molecules of a tryptic peptide, ASHLGLAR, and of its phenyl isothiocyanate and 4-sulfophenyl isothiocyanate derivatives, generated by matrix-assisted laser desorption/ionization. Derivatization with the aromatic chromophores greatly reduced the intensity of the laser required for efficient PD. Major fragment ions observed in the three spectra are quite similar. General features of the PD tandem mass spectra and their potential utility for analytical purposes are discussed. 相似文献
107.
Chen SH Su AC Chang CS Chen HL Ho DL Tsao CS Peng KY Chen SA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8909-8915
Morphological effects in luminescence properties of a representative semiconducting polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), has recently attracted much attention. Previous studies indicated that short-term heat treatment of solution-cast MEH-PPV films may result in the formation of mesomorphic order that is responsible for the "red" emission around 640 nm, in contrast to the single-chromophore "yellow" emission near 590 nm from the disordered matrix. On the basis of microscopic and spectroscopic evidence for films cast from freshly prepared and aged solutions, here we show that prolonged storage of MEHyellowPPV solutions at room temperature or lower may result in retardation of the thermally induced mesophase formation in the subsequently cast films. According to small-angle neutron scattering and differential scanning calorimetric observations over aged MEH-PPV/toluene solutions, we propose that the suppressed transformation into mesomorphic order is due to further development of nanocrystalline aggregates that serve as physical cross-links among MEH-PPV chains in the solution state upon long-term storage. These solvent-induced nanocrystalline aggregates, however, do not exhibit new spectroscopic features beyond the suppression of "red" emission at 640 nm from the mesomorphic phase. 相似文献
108.
The pretreatment of waste-activated sludge (WAS) by electron beam irradiation was studied in order to improve anaerobic sludge
digestion. The irradiation dose of the electron beam was varied from 0.5 to 10 kGy. Batch and continuous-flow stirred tank
reactors (CFSTRs) were operated to evaluate the effect of the electron beam pretreatment on anaerobic sludge digestion. Approximately
30–52% of the total chemical oxygen demand (COD) content of the WAS was solubilized within 24 h after electron beam irradiation.
A large quantity of soluble COD, protein, and carbohydrates leached out from cell ruptures caused by the electron beam irradiation.
Volatile fatty acids production from the irradiated sludge was approx 90% higher than that of the unirradiated sludge. The
degradation of irradiated sewage sludge was described by two distinct first-order decay rates (k
1 and k
2). Most initial decay reaction accelerated within 10 d, with an average k
1 of 0.06/d for sewage sludge irradiated at all dosages. The mean values for the long-term batch first-order decay coefficient
(k
2) were 0.025/d for irradiated sewage sludge and 0.007/d for unirradiated sludge. Volatile solids removal efficiency of the
control reactor fed with unirradiated sewage sludge at a hydraulic retention time (HRT) of 20 d was almost the same as that
of the CFSTRs fed with irradiated sludge at an HRT of 10 d. Therefore, disintegration of sewage sludge cells using electron
beam pretreatment could reduce the reactor solid retention time by half. 相似文献
109.
To isolate epigallocatechin gallate (EGCG) of catechin compounds from Korean green tea (Bosung, Chonnam), a C18 reversed-phase preparative column (250x22 mm) packed with packings of three different sizes (15, 40-63, and 150 microm) was used. The sample extracted with water was partitioned with chloroform and ethyl acetate to remove the impurities including caffeine. The mobile phases in this experiment were composed of 0.1% acetic acid in water, acetonitrile, methanol and ethyl acetate. The injection volume was fixed at 400 microl and the flow rate was increased as the particle size becomes larger. The isolation of EGCG with particle size was compared at a preparative scale and the feasibility of separation of EGCG at larger particle sizes was confirmed. The optimum mobile phase composition for separating EGCG was experimentally obtained at the particle sizes of 15 and 40-63 microm in the isocratic mode, but EGCG was not purely separated at the particle size of 150 microm. 相似文献
110.
A rapid, sensitive, precise and accurate high-performance liquid chromatographic assay with fluorescence detection was developed for the determination of buprenorphine in human, rabbit, pig and dog plasma. It is comprised of only a one-step extraction procedure with hexane-isoamyl alcohol at pH 9.25 and reversed-phase chromatography on a muPorasil column. The recoveries of buprenorphine and nalbuphine (internal standard) were greater than 90%. Calibration graphs were linear over the concentration range 3-300 ng/ml with a coefficient of variation, both within-day and between-day, of less than 9% at any level. The limit of detection was 1.0 ng/ml of plasma based on a signal-to-noise ratio of 3. Eight other clinically used narcotics were investigated to check for potential interferences and their analytical conditions. The possible decomposed compounds of buprenorphine were also checked for the specificity of this assay. The method has been successfully applied to the stability and pharmacokinetic studies of buprenorphine. Buprenorphine in plasma did not decompose significantly at -20 degrees C for four weeks. Pharmacokinetic application in six rabbits and a surgical patient revealed that buprenorphine followed a linear three-compartment model with two distribution phases. The two distribution and elimination half-lives and the clearance of buprenorphine were 1.32, 24.8 and 230 min and 224 ml/min in human plasma, and 0.94, 12.5 and 232 min and 30 ml/min in rabbit plasma. 相似文献