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101.
The properties of porphyrinogen as a new chromogenic reagent were examined. 5,10,15,20-Tetrahydro-tetraphenylporphyrinogen (TPPN) is changed to 5,10,15,20-tetraphenylporphine (TPP) by the oxidative reaction involving six electrons, and its formation of the porphine ring significantly increased the absorbance in the Soret band.The horseradish peroxidase (HRP) accelerated the oxidative reaction as a catalyst and the increment of absorbance depended upon the increase in the concentration of HRP. The reaction proceeded in the presence of dissolved oxygen and in the neighborhood of pH 7. Based on these findings, a chemical analysis by catalytic action using HRP was developed.In the procedure for this determination, the difference in absorbance at 419 nm (ΔA419=As−Ab, where As and Ab are the absorbances of the sample solution containing HRP and the blank solution without HRP after 30 min, respectively), was measured. The determination range of HRP, which was obtained from the ΔA419—HRP concentration curve, was 0.05-1.0 mg/l. The relative standard deviation in the median of the calibration curve was 3.19% (seven determinations), and the detection limit (S/N=3) was 29 ng/l. Furthermore, when the proposed method was applied to the enzyme immunoassay, bisphenol A (BPA) was selectively and sensitivity determined. 相似文献
102.
Petra A W Van Den Berg Koert Grever Arie Van Hoek Willem J H Van Berkel Antonie J W G Visser 《Journal of Chemical Sciences》2007,119(2):123-133
Conformational heterogeneity of the FAD cofactor in p-hydroxybenzoate hydroxylase (PHBH) was investigated with time-resolved polarized flavin fluorescence. For binary enzyme/substrate
(analogue) complexes of wild-type PHBH and Tyr222 mutants, crystallographic studies have revealed two distinct flavin conformations;
the ‘in’ conformation with the isoalloxazine ring located in the active site, and the ‘out’ conformation with the isoalloxazine
ring disposed towards the protein surface. Fluorescence-lifetime analysis of these complexes revealed similar lifetime distributions
for the ‘in’ and ‘out’ conformations. The reason for this is twofold. First, the active site of PHBH contains various potential
fluorescence-quenching sites close to the flavin. Fluorescence analysis of uncomplexed PHBH Y222V and Y222A showed that Tyr222
is responsible for picosecond fluorescence quenching free enzyme. In addition, other potential quenching sites, including
a tryptophan and two tyrosines involved in substrate binding, are located nearby. Since the shortest distance between these
quenching sites and the isoalloxazine ring differs only little on average, these aromatic residues are likely to contribute
to fluorescence quenching. Second, the effect of flavin conformation on the fluorescence lifetime distribution is blurred
by binding of the aromatic substrates: saturation with aromatic substrates induces highly efficient fluorescence quenching.
The flavin conformation is therefore only reflected in the small relative contributions of the longer lifetimes. 相似文献
103.
Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO+, COH+, and HCOH2+ from CO by protonation. The protonation of N2 to give NNH+ and HNNH2+ and of NO+ to form HNO2+ and NOH2+ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed. 相似文献
104.
Aqueous polymerization of acrylonitrile (M) initiated by the Ce(IV)-glucose (R) redox system has been studied under nitrogen in the temperature range of 30–40 °C. The rate of polymerization (Rp) is proportional to [M]2, [R] and inversely proportional to [Ce(IV)]. The rate of ceric ion disappearance is proportional to [R] and [Ce(IV)]. The end group in the polymer is characterised by IR spectra. A suitable kinetic scheme has been proposed and explained in the light of these experimental findings. 相似文献
105.
T. N. Rostovshchikova M. S. Korobov D. A. Pankratov G. Yu. Yurkov S. P. Gubin 《Russian Chemical Bulletin》2005,54(6):1425-1432
Nanosized iron oxides stabilized on the surface of ultradispersed poly(tetrafluoroethylene) (UPTFE) granules were synthesized
by the thermal destruction of iron formate in boiling bed of UPTFE on the surface of heated mineral oil. The particle size
of nanoparticles (∼6 nm) containing 5, 10, and 16 wt.% Fe depends weakly on the temperature of synthesis and iron to polymer
ratio. The metal state is determined by the synthesis conditions. The nanoparticles synthesized at 280 °C consist mainly of
the Fe3O4 and Fe2O3 phases. The samples obtained at 320 °C also contain iron(II) oxide. The catalytic properties of the obtained samples were tested in dichlorobutene isomerization. Unlike isomerization
on the iron oxide nanoparticles supported on silica gel, reaction over the UPTFE supports proceeds without an induction period.
The sample with 10 wt.% Fe containing magnetically ordered γ-Fe2O3 nanoparticles possesses the highest catalytic activity. Fast electron exchange between the iron ions in different oxidation
states and high defectiveness of the nanoparticles contribute, most likely, to the catalytic activity.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1383–1390, June, 2005. 相似文献
106.
A. Manjon J. A. Ferragut J. C. Garcia-Borron J. L. Iborra 《Applied biochemistry and biotechnology》1984,9(2):173-185
Fluorescence spectra and soluble quenching of intrinsic protein fluorescence were used as indexes of conformational changes
suffered by frog epidermis tyrosinase. The activation process and the immobilization of the enzyme involving either free amino
groups or its carbohydrate moiety were studied. The conformational changes resulting from denaturation of each one of the
protein derivatives, as well as the effect of active center copper extraction, were followed by fluorescence studies.
The results showed that: (a) both activation and immobilization were accompanied by conformational changes of the protein
leading to more unfolded states; (b) neither enzyme nor immobilized enzyme were fully unfolded upon denaturation although
enzymic activity was lost; (c) the enzyme immobilized through its carbohydrate moiety was more unfolded upon denaturation
than the enzyme immobilized through amino groups, thus pointing to a higher conformational stabilization in the last situation;
and (d), that tryptophyl residues moved to a localization near the active site upon activation. 相似文献
107.
The mobile phase of a fraction eluted from a first LC column is removed by an on-line evaporator in order to reconcentrate the solute material or to exchange the eluent before performing a subsequent LC separation. Evaporation essentially occurs by concurrent evaporation, i.e. the solvent evaporates at a rate equal to the flow rate of the incoming eluent, and is driven by the overflow principle, i.e. vapors leave the tube as a result of the expansion resulting from evaporation. The liquid is introduced into a small tube (e.g., 4 cm × 1.3 mm i.d.) which is packed, e.g., with a coarse silica gel. The outlet of the evaporator is connected to vacuum in order to enable evaporation at reduced temperature and to increase retention of the volatile components. With normal phase eluents, evaporation rates may approach 1 ml/min; n-dodecane was the most volatile n-alkane fully retained by the evaporator. 相似文献
108.
Seven homologous symmetric dimeric liquid crystals are presented where two three-ring mesogenic units are connected by a bis(carbonyloxy)alkylene spacer. For homologues with terminal heptyloxy, octyloxy and nonyloxy chains, the unusual phase sequence SmA-SmC with increasing temperature was detected by the study of the optical textures and by X-ray diffraction measurements. This unusual behaviour is discussed on the basis of the molecular structure of these compounds. 相似文献
109.
Ultra‐high pressure LC for astaxanthin determination in shrimp by‐products and active food packaging
A. Sanches‐Silva T. Ribeiro T. G. Albuquerque P. Paseiro R. Sendón A. Bernaldo de Quirós J. López‐Cervantes D. I. Sánchez‐Machado H. Soto Valdez I. Angulo G. P. Aurrekoetxea H. S. Costa 《Biomedical chromatography : BMC》2013,27(6):757-764
Nowadays, there is increasing interest in natural antioxidants from food by‐products. Astaxanthin is a potent antioxidant and one of the major carotenoids in crustaceans and salmonids. An ultra‐high pressure liquid chromatographic method was developed and validated for the determination of astaxanthin in shrimp by‐products, and its migration from new packaging materials to food simulants was also studied. The method uses an UPLC® BEH guard‐column (2.1 × 5 mm, 1.7 µm particle size) and an UPLC® BEH analytical column (2.1 × 50 mm, 1.7 µm particle size). Chromatographic separation was achieved using a programmed gradient mobile phase consisting of (A) acetonitrile–methanol (containing 0.05 m ammonium acetate)–dichloromethane (75:20:5, v/v/v) and (B) ultrapure water. This method was evaluated with respect to validation parameters such as linearity, precision, limit of detection, limit of quantification and recovery. Low‐density polyethylene films were prepared with different amounts of the lipid fraction of fermented shrimp waste by extrusion, and migration was evaluated into food simulants (isooctane and ethanol 95%, v/v). Migration was not detected under the tested conditions. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
110.
Abstract Solids like layer silicates (kaolinite and montmorillonite) as well as ZnO are in use in pharmacy. They are pressure treated and subsequently analyzed by means of ESR spectroscopy. The structural changes indicated by Fe3+ ions and paramagnetic defects are reponsible for the enhanced chemical activity of the pressurized systems. Especially active Fe-O-species are formed which can react with intercacalated organic molecules. The most probable first step of such reactions will be a solid state single electron transfer. Spin probes and spin traps were used to prove this statements. The activation of the drug delivery systems by mechanical treatments is of importance for the stability of the drugs incorporated. 相似文献