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971.
Poly(gamma-glutamic acid) (gamma-PGA) is a biosynthetic polymer, and the carboxyl groups are able to undergo a chemical modification. In this study, poly(alpha-propyl gamma-glutamate) (gamma-PGA propylate) was synthesized by the esterification of these carboxyl groups to yield a thermosensitive and biodegradable polymer. In aqueous solution, the gamma-PGA propylate can impart thermosensitivity by controlling the hydrophobic-hydrophilic balance of the gamma-PGA polymeric chains. 相似文献
972.
Antonio Doménech María Teresa Doménech-Carbó María Luisa Vázquez de Agredos Pascual 《Journal of Solid State Electrochemistry》2007,11(9):1335-1346
The preparation of indigo from Indigofera suffruticosa following the procedures attributed to ancient Mayas was electrochemically monitored using the voltammetry-of-microparticles
approach. The mechanism formation of indigotin and indirubin from its precursors, indican and isatan, is discussed. Comparison
of voltammetric profiles for differently prepared and commercial indigos and genuine Maya Blue samples suggests that the preparation
procedure of indigo changed during the Late Classical Maya period.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
973.
The stereocontrolled synthesis of oligodeoxyribonucleoside phosphorothioates (PS-ODNs) using nucleoside 3'-O-oxazaphospholidine derivatives as monomer units is described. 2-Chloro-1,3,2-oxazaphospholidine derivatives were prepared from six kinds of enantiopure 1,2-amino alcohols and used for the phosphitylation reactions of 5'-O-protected nucleosides. A detailed study of these reactions revealed that the diastereoselectivity of the reaction depended on the structure of the enantiopure 1,2-amino alcohol, the reaction temperature, and the amine used as a scavenger of HCl. In addition, ab initio molecular orbital calculations for the 2-chlorooxazaphospholidine derivatives were carried out to elucidate the mechanism of these diastereoselective phosphitylation reactions. The LUMO of the 2-chloro-5-phenyloxazaphospholidine derivatives on the phosphorus atom was found to be almost orthogonal to the P-Cl bond. This LUMO may be involved in the phosphitylation reactions with predominant retention of the P-configuration. A series of dialkyl(cyanomethyl)ammonium salts were developed and used as activators for the condensation reactions of the diastereopure nucleoside 3'-O-oxazaphospholidines with 3'-O-protected nucleosides. In the presence of the new activators, the reactions proceeded rapidly to give the corresponding dinucleoside phosphite triesters. The diastereoselectivity of the condensation reaction did not depend on the counteranion but on the structure of the dialkyl(cyanomethyl)amine. In the presence of the activator, which consists of a relatively small dialkyl(cyanomethyl)amine, the condensation proceeded with excellent diastereoselectivity. After sulfurization and deprotection, diastereopure (R(p))- and (S(p))-dinucleoside phosphorothioates were obtained in excellent yields. The present methodology was also applied to the solid-phase synthesis of stereoregulated PS-ODNs. all-(R(p))-[T(PS)](3)T, all-(S(p))-[T(PS)](3)T, all-(R(p))-d[G(PS)A(PS)C(PS)]T, and all-(R(p))-[T(PS)](9)T were synthesized on a highly cross-linked polystyrene resin. 相似文献
974.
Motoyama T Shimazaki Y Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Journal of the American Chemical Society》2004,126(23):7378-7385
The Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-iepp), 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-miepp), 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]methylindole (Htbu-impp), and 3-(N-2-pyridylmethyl-N-4-hydroxybenzylamino)ethylindole (Hp-iepp) (H denotes a dissociable proton), were synthesized, and the structures of [Pd(tbu-iepp)Cl] (1a), [Pd(tbu-iepp-c)Cl] (1b), [Pd(tbu-miepp)Cl] (3), and [Pd(p-iepp-c)Cl] (4) (tbu-iepp-c and p-iepp-c denote tbu-iepp and p-iepp bound to Pd(II) through a carbon atom, respectively) were determined by X-ray analysis. Complexes 1a prepared in CH(2)Cl(2)/CH(3)CN and 3 prepared in CH(3)CN have a pyridine nitrogen, an amine nitrogen, a phenolate oxygen, and a chloride ion in the coordination plane. Complex 1b prepared in CH(3)CN has the same composition as 1a and was revealed to have the C2 atom of the indole ring bound to Pd(II) with the Pd(II)-C2 distance of 1.973(2) A. The same Pd(II)-indole C2 bonding was revealed for 4. Interconversion between 1a and 1b was observed for their solutions, the equilibrium being dependent on the solvent used. Reaction of 1b and 4 with 1 equiv of Ce(IV) in DMF gave the corresponding one-electron-oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at approximately 550 nm, indicating the formation of the Pd(II)-indole pi-cation radical species. The half-life, t(1/2), of the indole radical species at room temperature was calculated to be 20 s (k(obs) = 3.5 x 10(-)(2) s(-)(1)) for 1b. The cyclic voltammogram for 1b in DMF gave two irreversible oxidation peaks at E(pa) = 0.68 and 0.80 V (vs Ag/AgCl), which were ascribed to the oxidation processes of the coordinated indole and phenolate moieties, respectively. 相似文献
975.
A novel class of activators, dialkyl(cyanomethyl)ammonium tetrafluoroborates 1a-c, has been developed and applied to the condensations of diastereopure 5'-O-tert-butyldiphenylsilylthymidine 3'-cyclic phosphoramidites 3a-d with 3'-O-tert-butyldimethylsilylthymidine (4a). Among them, the condensation of 3a with 4a in the presence of 1a completed within 5 min and gave only one diastereoisomer of the corresponding phosphite 5a. After sulfurization and deprtection, almost diastereopure (Rp)-TpsT 7 was obtained (d.r. = 99:1). Next the 5'-O-(DMTr)nucleoside 3'-phosphoramidites 8a-d containing thymine, N6-benzoyladenine, N4-benzoylcytosine, and N2-phenylacetylguanine have been synthesized and allowed to condense with 3'-O-protected thymidine and 2'-deoxyadenosine. The 5'-O-DMTr group and the N-acyl groups of the nucleobases were compatible with the reaction conditions and the condensations completed quickly with excellent diastereoselectivity. 相似文献
976.
JongHwa Moon SangHoon Kang YongSam Chung OkHee Lee 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(1):155-158
Instrumental neutron activation analysis was used to assess the concentration of the inorganic trace elements in Korean women’s
blood serums. It was found that a high concentration of Na and Cl incurs an analytical interference, but the 12 elements such
as Br, Ca, Cl, Co, Cr, Cs, Fe, K, Na, Rb, Se and Zn could be determined under the condition of an interference minimization.
Serum samples collected from 63 women were analyzed and the concentration level and range of the elements were evaluated.
NIST SRMs were analyzed simultaneously for quality control. The average values of the Na and Cl determined in the serum samples
were 3,365 and 3,533 mg/l, Ca was 96.4 mg/l and K was 191 mg/l. Besides, Br, Se and Zn have a concentration level of 6.46,
0.13 and 0.98 mg/l, respectively. It was found that there is no significant difference between the present values and the
reported values. 相似文献
977.
Rasa Pauliukaite Mariana Emilia Ghica Madalina Barsan Christopher M. A. Brett 《Journal of Solid State Electrochemistry》2007,11(7):899-908
The polymer redox mediator, poly(neutral red) (PNR), has been synthesised and characterised electrochemically to investigate
the best electropolymerisation and mediation conditions for application in enzyme biosensors and to clarify the mechanism
of action. Neutral red was electropolymerised by potential cycling on carbon film electrode substrates by allowing the monomer
to be oxidised during the full 20 cycles of polymerisation or reducing the positive limit of the potential window after the
first 2 cycles to impede monomer oxidation with a view to obtaining longer polymer chains and a lesser degree of branching.
Comparison was made with glassy carbon substrates. The PNR films on carbon film electrodes were characterised using cyclic
voltammetry and electrochemical impedance spectroscopy, as well as in glucose biosensors prepared with PNR. Glucose oxidase
enzyme was immobilised by encapsulation in silica sol-gel and compared with that obtained by cross-linking with glutaraldehyde.
The biosensors were evaluated by chronoamperometry in 0.1 M phosphate buffer saline solution, pH 7.0, and showed evidence
of electron transfer between the enzyme cofactor flavin adenine dinucleotide and PNR dissolved in the enzyme layer competing
with PNR-mediated electrochemical degradation of H2O2 formed during the enzymatic process.
This paper is dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday. 相似文献
978.
Ana C. D. Medeiros Lidiane P. Correia Mônica O. da S. Simões R. O. Macêdo 《Journal of Thermal Analysis and Calorimetry》2007,88(2):311-315
A number of disintegrants
are available on the market. They improve tablets’ disintegration. The
objective of this work is the comparison of the technological quality parameters
of disintegrants using different analytical techniques. Three batches of disintegrants
and their binary mixtures (water:disintegrants) were investigated. Cooling
experiments were used from –30 up to 200°C. The data obtained showed
calorimetric differences between the samples. In the binary mixtures water
showed different crystallization behaviour from the one found in the literature.
According to the results DSC technique helped the quality control of different
disintegrants. 相似文献
979.
J. Orbán Sz. Halasi G. Papp Szilvia Barkó Beáta Bugyi 《Journal of Thermal Analysis and Calorimetry》2005,82(1):287-290
Summary The thermodynamic properties of the cardiac and skeletal a-actin isoforms were studied to characterize the molecular bases
of the functional differences between them with the method of differential scanning calorimetry (DSC). The thermal properties
of the actin filaments were described in the presence of calcium and magnesium ions as well. Based on the calculated free
energy changes the α-cardiac actin filaments appeared to be more stable in its physiologically more relevant, magnesium saturated
form. The magnesium saturated form of the α-cardiac actin filaments seemed to be more stable compared to the calcium saturated
form of it. The enthalpy and entropy changes could differentiate between the α-cardiac and α-skeletal actin isoforms and between
the calcium and magnesium saturated cardiac actin isoforms as well. Our results can demonstrate that the few differences between
the amino acid sequences of the α-actin isoforms have an influence on the thermal properties and maybe on the function of
these proteins as well. 相似文献
980.
Large-scale separation of metallic and semiconducting single-walled carbon nanotubes 总被引:6,自引:0,他引:6
Maeda Y Kimura S Kanda M Hirashima Y Hasegawa T Wakahara T Lian Y Nakahodo T Tsuchiya T Akasaka T Lu J Zhang X Gao Z Yu Y Nagase S Kazaoui S Minami N Shimizu T Tokumoto H Saito R 《Journal of the American Chemical Society》2005,127(29):10287-10290
In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way. 相似文献