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971.
Microdroplets display distinctive interfacial chemistry, manifested as accelerated reactions relative to those observed for the same reagents in bulk. Carbon dioxide undergoes C–N bond formation reactions with amines at the interface of droplets to form carbamic acids. Electrospray ionization mass spectrometry displays the reaction products in the form of the protonated and deprotonated carbamic acid. Electrosonic spray ionization (ESSI) utilizing carbon dioxide as nebulization gas, confines reaction to the gas–liquid interface where it proceeds much faster than in the bulk. Intriguingly, trace amounts of water accelerate the reaction, presumably by formation of superacid or superbase at the water interface. The suggested mechanism of protonation of CO2 followed by nucleophilic attack by the amine is analogous to that previously advanced for imidazole formation from carboxylic acids and diamines.Microdroplets display distinctive interfacial chemistry, manifested as accelerated reactions relative to those observed for the same reagents in bulk. 相似文献
972.
Methylmaleic (citraconic, CTA) acid and methylfumaric (measaconic, MSA) acid in aqueous sulfuric acid solution undergo bromine-catalyzed reversible cis-trans isomerization in the presence of ceric and bromide ions. The positional isomerization of CTA or MSA to itaconic acid (ITA) is not observed. The method of high performance liquid chromatography (HPLC) was applied to study the kinetics of this catalyzed isomerization. The major catalytic species is best expressed as the Br?2 · radical anion. Under suitable catalytic conditions, there is a tendency for the [MSA]/[CTA] ratio to reach an equilibrium value of 4.10 at 25° for the CTA+Br?2 · ? MSA+Br?2 · reaction. Chloromaleic (CMA) and chlorofumaric (CFA) acids undergo similar isomerization with an equilibrium [CFA]/[CMA] ratio of 10.3 at 25°. The isomerization of maleic acid (MA) to fumaric acid (FA) is essentially irreversible with 50 as the lower limit of the equilibrium [FA]/[MA] ratio. The substituent has an important effect on the reversibility of this catalyzed isomerization of butenedicarboxylic acids. The thermodynamic parameters ΔH° and ΔS° at 25° for the CTA+Br?2 · ? MSA+Br?2 · reaction were found to be ?5.1±0.7 kj/mol and ?6.0±3.3 J/mol K, respectively. The present method gives a plausible way to measure the differences in enthalpy and entropy between the trans- and cis-isomers of butenedicarboxylic acids (CRCO2H=CR'CO2H) in aqueous solution. 相似文献
973.
PreparationandCrystalStructureofPrNb_5O_(14)¥MaoJiang-Gao;ZhuangHong-Hui;HuangJin-Shun(StateKeyLaboratoryofStructuralChemistry... 相似文献
974.
A new series of vanadates with the general formula M Ba2V3O11, where M may be Bi, In, or a rare earth, has been synthesized and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction. The general formula may be rewritten as M Ba2(VO4)(V2O7) to emphasize that there is one orthovanadate group and one pyrovanadate group in each formula unit. Up to one-third of the vanadium may be replaced by phosphorous, leading to the general formula M Ba2V2PO11. However, phosphorous shows no preference between the ortho and pyro groups. Both M Ba2V3O11 and M Ba2V2PO11 crystallize in the monoclinic system with the space group P21/c and Z = 4. The cell parameters from single crystal X-ray data of BiBa2V3O11 are a = 12.332(4) Å, b = 7.750(4) Å, c = 11.279(4) Å, β = 103.22(3)°, V = 1049(1) Å3; and for BiBa2PO11 are a = 12.266(2) Å, b = 7.615(2) Å, c = 11.312(2) Å, β = 103.32(2)°, V = 1028.2(2) Å3. The Bi atom coordinates to six oxygen atoms forming a distorted octahedron, and the edge sharing of BiO6 octahedra results in a BiO4 chain along the b axis. There are two types of Ba atoms with coordination numbers of 10 and 11. There are three types of tetrahedral (T) atoms in these structures. The nonequivalent T atoms of the pyro group give T-O-T angles of 167 and 171° in BiBa2V3O11 and BiBa2V2PO11, respectively. Isostructural M Ba2V3O11 compounds were prepared in which M is In, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu. 相似文献
975.
Wengang Huang 《应用数学学报(英文版)》1991,7(3):279-283
In this paper, the author considered the stability of zero solution of linear RDDE $$\begin{gathered} \ddot x(t) + p_1 (t)\dot x(t) + q_1 (t)x(t) + p_2 (t)\dot x(t - r(t)) + q_2 (t)x(t - r(t)) = O, \hfill \\ \ddot x(t) + p_1 (t)\dot x(t) + q_1 (t)x(t) + p_2 (t)\dot x(t - r(t)) = O \hfill \\ \end{gathered} $$ using Liapunov-Razumikhin functional and transformations and obtained some sufficient conditions for the stability of Eqs.(1) and (2). These results are suitable both for boundedp i (t),q i (t) andr(t).i=1,2. 相似文献
976.
Huang Baofa 《International Journal of Theoretical Physics》1991,30(6):783-787
The BRST formalism is employed to quantize a scalar particle and interactions with an external scalar field (x
) and vector gauge fieldA
(x
) in the background of an arbitrary gravitational field. The second-quantized actions are obtained. 相似文献
977.
978.
979.