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51.
A novel design for initiating radical-based chemistry in a catalytic fashion is described. The design of the concept is based on the phenylselenyl group transfer reaction from alkyl phenyl selenides by utilizing PhSeSiR(3) (1) as a catalytic reagent. The reaction is initiated by the homolytic cleavage of -C-Se- bond of an alkyl phenyl selenide by the in situ generated alkylsilyl radical (R(3)Si(*)), obtained by the mesolysis of PhSeSiR(3)](*)(-)( )()(1(*)(-)). The oxidative dimerization of counteranion PhSe(-) to PhSeSePh functions as radical terminator. The generation of 1(*)(-) is achieved by the photoinduced electron transfer (PET) promoted reductive activation of 1 through a photosystem comprising of a visible-light (410 nm)-absorbing electron rich DMA as an electron donor and ascorbic acid as a co-oxidant (Figure 1). The optimum mole ratio between the catalyst 1 and alkyl phenyl selenides for successful reaction is established to be 1:10. The generality of the concept is demonstrated by carrying out variety of radical reactions such as cyclization (10, 15-18), intermolecular addition (25), and tandem annulations (32). 相似文献
52.
Ritu Pandey Sanjay Chauhan Gauri S. Singhal 《Journal of photochemistry and photobiology. B, Biology》1997,40(3):228-232
The effect of UVB irradiation on the phycobilisomes (PBSs) of Synechococcus sp. PCC 7942 cells was studied. The sucrose density-gradient-isolated PBSs from in vivo UVB-treated (280–320 nm) cells showed a strong decrease in β-phycocyanin (βPC) and -phycocyanin (PC) polypeptides. In addition to a decrease in the linker polypeptides LCM 75 (linker connecting the core to the thylakoid membranes), LR 33 (linker in the rod structure), LRC 31.5 (linker connecting the rod to the core) and LRC 29. In vitro UVB treatment of gradient-isolated intact PBSs for 1 h had no effect on any of the constituent polypeptides, and only after 2 h was a degradation of LCM 75 and LR 33 and a decrease in βPC evident. Further investigation of phycobiliproteins (4 h of UVB irradiation) using polyclonal antibody directed against purified whole PBSs revealed that, in vivo, there was a gradual decline in the levels of LCM 75, LR 33, LRC 31.5, LRC 29, βPC and PC. 相似文献
53.
PHOTOCHEMICAL INACTIVATION OF SINGLE-STRANDED VIRAL DNA IN THE PRESENCE OF UROCANIC ACID* 总被引:3,自引:0,他引:3
Irwin Tessman† H. Morrison † C. Bernasconi † G. Pandey † L. Ekanayake† † 《Photochemistry and photobiology》1983,38(1):29-35
Abstract— Urocanic acid (UA) has previously been shown to react photochemically in vitro with N,N-dimethylthymine. In this study, mixtures of UA and phage G4 single-stranded DNA have been irradiated with UV light (λ≥ 254 nm) and the DNA assayed for infectivity. At the concentrations of UA employed (typically 5.4 × 10-3 M ) there is extensive absorption of the incident light by the UA. The DNA is inactivated at rates greater than that predicted from the calculated shielding by UA, indicating that photosensitization is occurring. Photosensitization is also indicated by the fact that at high UA concentrations the inactivation rate does not decrease to zero but approaches a residual value. Furthermore, the ability to photoreactivate DNA that has been photolyzed in the presence of UA is much reduced relative to that observed upon photolysis of the DNA alone. UA is therefore responsible for the production of UV-induced DNA lesions, which are resistant to photoreactivation.
A general analysis of the effects of photosensitization on the kinetics of UV inactivation is presented in an appendix. 相似文献
A general analysis of the effects of photosensitization on the kinetics of UV inactivation is presented in an appendix. 相似文献
54.
The force constants, Coriolis coupling constants and mean amplitudes of vibration at 0, 298.16 and 500 K for GaF63?FeF63? have been reported for the first time employing recent vibrational data. The results are discussed in the light of available information. 相似文献
55.
Bhagwan R. Pandey Sushil Kumar Shiva P. Singh Surendra S. Parmar 《Journal of heterocyclic chemistry》1980,17(5):1119-1120
Several 4-(arylaminothiocarbonyl)-1-(1-o-methoxyphenylcarbamido)-ethylpiperazines were synthesized and evaluated for their anticonvulsant activity against pentylenetetrazol-induced seizures in mice. The ability of substituted piperazines to inhibit in vitro respiratory activity of rat brain homogenates was also determined to study their structure-activity relationship. 相似文献
56.
A solid state copper(II) ion sensor is reported based on the application of electropolymerized undoped (neutral) polycarbazole
(PCz) and polyindole (PIn) modified electrodes. The new sensor shows high selectivity to Cu2+ ions with a detection limit of 10–5 M. PCz and PIn are formed respectively by the anodic oxidation of 50 mM carbazole and 5 mM indole monomers in dichloromethane
containing 0.1 M tetrabutylammonium perchlorate on a platinum electrode using a single compartment cell. Potentiostatic polymerization
of both the monomers are carried out at 1.3 V and 1.0 V vs. Ag/AgCl, respectively. Perchlorate ions were electrochemically
removed from the polymer films by applying – 0.2 V vs. Ag/AgCl. Polymer-coated electrodes are incubated in 1 M KCl solution
for 8 h followed by incubation in distilled water for 2 h before using as a metal ion sensor. The undoped PCz and PIn electrodes
were found to be highly selective and sensitive for Cu2+ ions with little selectivity for Pb2+ and negligible response towards Ag+, Hg2+, Cu+, Ni2+, Co2+, Fe2+, Fe3+ or Zn2+. Potentiometric responses for Cu2+ ions are recorded for both the sensor electrodes together with a double-junction Ag/AgCl reference electrode. Calibration
curves for Cu2+ are reported for both ion sensors. The polymer-modified electrodes were found to be stable for several weeks.
Electronic Publication 相似文献
57.
A review is presented on thiocyanate methods for the estimation of molybdenum in a wide variety of samples. They include conventional thiocyanate methods in which molybdenum forms an orange red complex with the thiocyanate ions and improved thiocyanate methods where the sensitivity is increased through the formation of ternary ion association complex. 相似文献
58.
H Morrison B Mauclair R M Deibel G Pandey W M Baird 《Photochemistry and photobiology》1985,41(3):251-257
Abstract— Urocanic acid (UA) has previously been shown to photochemically react with N, N-dimethylthymine and with phage G4 single-stranded DNA. In this study, E-[ring-2-14C]-U A and calf thymus DNA have been irradiated with UV light (Λ > 270 nm) in buffered, aqueous solutions. Rc-isolation of the DNA indicates covalent binding of UA at levels of up to 80 nmol UA/mg DNA. Binding is observed for both native and heat denatured DNA. Equilibrium dialysis studies give no evidence for complexation of UA to either form of DNA in the dark. Enzymatic cleavage of the UA bound DNA and analysis by HPLC shows peaks for l4C-labelled products with retention volumes identical to those of a marker mixture prepared by irradiating UA with [3H-methyl]thymidine. Photolysis of the DNA before irradiation with U A leads to the formation of a second product with a retention volume corresponding to that for a deoxyadenosine/UA marker. 相似文献
59.
Summary Ruthenium(III) complexes of types [Ru(L)3], [Ru(L)Cl(H2O)2], [Ru(L)Cl2]n, [Ru(L)Cl(H2O)]n(LH =Schiff bases derived from anthranilic acid and benzaldehyde, acetophenone, vanillin, cinnamaldehyde orm-hydroxyacetophenone; LH2=Schiff bases derived from anthranilic acid and salicylaldehyde oro-hydroxyacetophenone; LH=Schiff bases derived fromp-aminobenzoic acid and benzaldehyde, acetophenone, vanillin, cinnamaldehyde orm-hydroxyacetophenone; LH2=Schiff bases derived fromp-aminobenzoic acid and salicylaldehyde oro-hydroxyacetophenone) have been synthesized and characterized on the basis of elemental analyses, conductance, magnetic moment and spectral (electronic, i.r. and1H n.m.r.) data. The wavelengths of the principal electronic absorption peaks have been accounted for quantitatively in terms of crystal field theory and various parameters have been evaluated. On the basis of the electronic spectra, an octahedral geometry has been established for all these complexes except [Ru(L)Cl2]n. The complexes [Ru(L)Cl2]n are pentacoordinate and a trigonal-bipyramidal environment, D3h, is suggested for the ruthenium(III) ion. The thermal behaviour of these complexes has also been studied by t.g., d.t.g and d.s.c techniques. Heats of reaction for the decomposition steps were calculated from the d.s.c. curves. The antifungal and antiviral activities of the complexes with Schiff bases derived from anthranilic acid were also investigated. 相似文献
60.
Kinetics of the oxidation of methyl n-propyl ketone and methyl isobutyl ketone by N-bromosuccinimide (NBS) have been studied in perchloric acid media in presence of mercuric acetate. A zero order dependence to N-bromosuccinimide and a first order dependence to both ketones and hydrogen ion concentrations have been observed. Sodium perchlorate, mercuric acetate and succinimide additions have negligible effect while methanol addition has a positive effect on the reaction rate. A solvent isotope effect (k0D2O/K0H2O = 2.3-2.7 and 2.4-2.8 for MeCOn.pr and MeCoi-Bu, respectively) has been observed at 35°. Kinetic investigations have revealed that the order of reactivity is methyl n-propyl ketone > methyl isobutyl ketone. Various thermodynamic parameters have been computed and corresponding 1,2-diketones were found to be the products. A suitable mechanism in conformity with the above observations has been proposed. 相似文献