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121.
Determination of amino acids in a complex matrix without derivatization is advantageous, however, difficulties are found in both the detection and the separation of those compounds. In this study, a rapid and reliable LC-MS-MS method for the quantitation of underivatized amino acids in exocellular media was established. Injections were made directly after centrifugation of the samples, without further preparation. The separation of seven underivatized amino acids was achieved on a reversed-phase C18 column with pentadecafluorooctanoic acid as a volatile ion-pair reagent, and the specific detection of most amino acids was achieved by MS-MS of the specific transitions [M + H]+-->[M + H - 46]+. The calibration curves of all analytes were linear over the range of 1.0-1000 microg ml(-1) and the detection limits ranged from 0.1 to 5 ng ml(-1), with an injection volume of 20 microl. The inter-day and intra-day precisions ranged from 2.6 to 5.7% and 4.8 to 8.2%, respectively; the mean recoveries of the seven analytes were 81-104%, 91-107% and 93-101% respectively at the spiked level of 10, 40 and 200 microg ml(-1). A large number of fermentation samples were analysed using this method. The technique is simple, rapid, selective and sensitive, and shows potential for the high-throughput quantitation of amino acids from other biological matrices. 相似文献
122.
H.-J. Machulla A. Blocher M. Kuntzsch M. Piert R. Wei J.R. Grierson 《Journal of Radioanalytical and Nuclear Chemistry》2000,243(3):843-846
[18F]FLT (3-deoxy-3-[18F]fluorothymidine) turned out to be a tracer particularly suitable for PET imaging of tumor proliferation because of lacking degradation in vivo. To facilitate clinical studies with [18F]FLT, we investigated two new easily accessible precursors, 2,3-anhydrothymidine (AThy) and 5-O-(4,4-dimethoxytriphenylmethyl)-2,3-anhydrothymidine (DMTThy), using a common approach for introducing the label with nucleophilic [18F]fluoride. Radiochemical yields were determined in dependence on substrate concentration, reaction time and temperature. In the case of AThy (10 mg), best FLT yields were 5.3%±1.2 (130 °C, 30 min). Labeling of DMTThy (10 mg) gave 14.3%±3.3 at 160 °C within 10 minutes. Starting with an aqueous solution of 20 GBq [18F]fluoride the new method allows to produce 1.3 GBq [18F]FLT within 90 minutes ready for intravenous injection. The new labeling procedures allow [18F]FLT synthesis without lengthy preparation of the precursor and with high reproducibility mandatory for clinical application. 相似文献
123.
Petrassi HM Johnson SM Purkey HE Chiang KP Walkup T Jiang X Powers ET Kelly JW 《Journal of the American Chemical Society》2005,127(18):6662-6671
Transthyretin (TTR) amyloidogenesis requires rate-limiting tetramer dissociation and partial monomer denaturation to produce a misassembly competent species. This process has been followed by turbidity to identify transthyretin amyloidogenesis inhibitors including dibenzofuran-4,6-dicarboxylic acid (1). An X-ray cocrystal structure of TTR.1(2) reveals that it only utilizes the outer portion of the two thyroxine binding pockets to bind to and inhibit TTR amyloidogenesis. Herein, structure-based design was employed to append aryl substituents at C1 of the dibenzofuran ring to complement the unused inner portion of the thyroxine binding pockets. Twenty-eight amyloidogenesis inhibitors of increased potency and dramatically increased plasma TTR binding selectivity resulted. These function by imposing kinetic stabilization on the native tetrameric structure of TTR, creating a barrier that is insurmountable under physiological conditions. Since kinetic stabilization of the TTR native state by interallelic trans suppression is known to ameliorate disease, there is reason to be optimistic that the dibenzofuran-based inhibitors will do the same. Preventing the onset of amyloidogenesis is the most conservative strategy to intervene clinically, as it remains unclear which of the TTR misassembly intermediates results in toxicity. The exceptional binding selectivity enables these inhibitors to occupy the thyroxine binding site(s) in a complex biological fluid such as blood plasma, required for inhibition of amyloidogenesis in humans. It is now established that the dibenzofuran-based amyloidogenesis inhibitors have high selectivity, affinity, and efficacy and are thus excellent candidates for further pharmacologic evaluation. 相似文献
124.
Wei QH Zhang LY Yin GQ Shi LX Chen ZN 《Journal of the American Chemical Society》2004,126(32):9940-9941
Unusual AuI-AgI heterometallic complexes [Au5Ag8(mu-dppm)4{1,2,3-C6(C6H4R-4)3}(CCC6H4R-4)7]3+ (R = H 1, CH3 2, But 3) were isolated by reactions of polymeric silver arylacetylides (AgCCC6H4R-4)n with binuclear gold component [Au2(mu-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane), in which cyclotrimerization of arylacetylide -CCC6H4R-4 affords trianion {1,2,3-C6(C6H4R-4)3}3- with an unprecedented mu5-bonding mode. Compounds 1(SbF6)3-3(SbF6)3 exhibit intense photoluminescence derived from an MLCT (Au5Ag8 --> CCC6H4R-4) transition, mixed with a metal cluster-centered excited states. 相似文献
125.
Zhiyong Jiang 《Tetrahedron letters》2007,48(1):51-54
The direct addition of P(O)-H bonds (dialkyl phosphites and diphenyl phosphonite) across various activated alkenes was catalyzed effectively by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). This is a mild, rapid and efficient protocol to generate P-C bonds. This simple procedure allows a series of dialkyl alkylphosphonates and trisubstituted phosphine oxides to be prepared in high yields. Further investigation resulted in a convenient one-pot, three-component reaction containing diphenyl phosphonite, malononitrile and an aldehyde. 相似文献
126.
Copper(II)-catalyzed aerobic oxidation of primary alcohols to aldehydes in ionic liquid [bmpy]PF6 总被引:1,自引:0,他引:1
A room-temperature aerobic oxidation of primary alcohols to aldehydes catalyzed by the three-component system acetamido-TEMPO/Cu(ClO(4))(2)/DMAP in the ionic liquid [bmpy]PF(6) has been developed, and the catalysts can be recycled and reused for five runs without any significant loss of catalytic activity. [reaction: see text] 相似文献
127.
Rao PV Bhaduri S Jiang J Hong D Holm RH 《Journal of the American Chemical Society》2005,127(6):1933-1945
The construction of a synthetic analogue of the A-cluster of carbon monoxide dehydrogenase/acetylcoenzyme synthase, the site of acetylcoenzyme A formation, requires as a final step the formation of an unsupported [Fe(4)S(4)]-(mu(2)-SR)-Ni(II) bridge to a preformed cluster. Our previous results (Rao, P. V.; Bhaduri, S.; Jiang, J.; Holm, R. H. Inorg. Chem. 2004, 43, 5833) and the work of others have addressed synthesis of dinuclear complexes relevant to the A-cluster. This investigation concentrates on reactions pertinent to bridge formation by examining systems containing dinuclear and mononuclear Ni(II) complexes and the 3:1 site-differentiated clusters [Fe(4)S(4)(LS(3))L'](2-) (L' = TfO(-) (14), SEt (15)). The system 14/[{Ni(L(O)-S(2)N(2))}M(SCH(2)CH(2)PPh(2))](+) results in cleavage of the dinuclear complex and formation of [{Ni(L(O)-S(2)N(2))}Fe(4)S(4)(LS(3))]- (18), in which the Ni(II) complex binds at the unique cluster site with formation of a Ni(mu(2)-SR)(2)Fe bridge rhomb. Cluster 18 and the related species [{Ni(phma)}Fe(4)S(4)(LS(3))](3)- (19) are obtainable by direct reaction of the corresponding cis-planar Ni(II)-S(2)N(2) complexes with 14. The mononuclear complexes [M(pdmt)(SEt)]- (M = Ni(II), Pd(II)) with 14 in acetonitrile or Me(2)SO solution react by thiolate transfer to give 15 and [M(2)(pdmt)(2)]. However, in dichloromethane the Ni(II) reaction product is interpreted as [{Ni(pdmt)(mu(2)-SEt)}Fe(4)S(4)(LS(3))](2-) (20). Reaction of Et(3)NH(+) and 15 affords the double cubane [{Fe(4)S(4)(LS(3))}(2)(mu(2)-SEt)](3-) (21). Cluster 18 contains two mutually supportive Fe-(mu(2)-SR)-Ni(II) bridges, 19 exhibits one strong and one weaker bridge, 20 has one unsupported bridge (inferred from the (1)H NMR spectrum), and 21 has one unsupported Fe-(mu(2)-SR)-Fe bridge. Bridges in 18, 19, and 21 were established by X-ray structures. This work demonstrates that a bridge of the type found in the enzyme A-clusters is achievable by synthesis and implies that more stable, unsupported single thiolate bridges may require reinforcement by an additional covalent linkage between the Fe(4)S(4) and nickel-containing components. (LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-); L(O)-S(2)N(2) = N,N'-diethyl-3,7-diazanonane-1,9-dithiolate(2-); pdmt = pyridine-2,6-methanedithiolate(2-); phma = N,N'-1,2-phenylenebis(2-acetylthio)acetamidate(4-); TfO = triflate.). 相似文献
128.
Based on Takayama-Lin-Liu-Maki model, analytical expressions for the third-harmonic generation, dc Kerr effect, dc-induced second-harmonic optical Kerr effect, optical Kerr effect or intensity-dependent index of refraction, and dc-electric-field-induced optical rectification are derived under the static current-current (J0J0) correlation for one-dimensional infinite chains. The results of hyperpolarizabilities under J0J0 correlation are then compared with those obtained using the dipole-dipole correlation. The comparison shows that the conventional J0J0 correlation, albeit quite successful for the linear case, is incorrect for studying the nonlinear optical properties of periodic systems. 相似文献
129.
Zhang B Wang X Lou N Zhang B Wei J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2001,57(9):1759-1765
The mass resolved multiphoton ionization (MPI) spectra of methyl iodide were obtained in the 430-490 nm region using a time-of-flight (TOF) mass spectrometer. They have the same vibrational structure, which testifies that the fragment species, in the wavelength region under study, are from the photodissociation of multiphoton ionized molecular parent ions. Some features in the spectra are identified as three-photon excitations to 6p and 7s Rydberg states of methyl iodide. Two new vibrational structures of some Rydberg states are observed. The mechanism of ionization and dissociation is also discussed. 相似文献
130.
为探讨急性心肌梗死(AMI)患者血清中K+、Na+、Ca2+、Fe2+、Mg2+含量变化,并研究其与心肌梗死患者之间的关系。选取2022年5月至2023年2月收治的AMI患者37例,同时选取健康体检者35例作为对照组。依据入院时或体检时收集的抽血样本进行临床生化分析,比较两组间血清K+、Na+、Ca2+、Fe2+、Mg2+含量,采用判别方程、主成分分析法(PCA),判断分析哪种金属离子对于心肌梗死的诊断价值大。结果表明,AMI患者的血清中Ca2+和Fe2+含量低于健康对照组,差异具有统计学意义。基于血钙、铁水平两组具有显著性差异,以它们为基础进行判别分析,获得判别函数式。将血清中K+、Na+、Ca2+、Fe2+、Mg2+ 相似文献