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991.
Hybrid density functional theory (B3LYP) method allows the study of the role of metal ions (Li(+)) in the regioselective opening of 2,3-epoxy alcohols with lithium halides (Cl, Br, I) to the corresponding halohydrins. The theoretical results largely confirm the experimental results, especially with regards to the regioselectivity observed in the opening of the oxirane ring. The C3 halogen attack is always preferred to the C2 attack, with a significant difference in the TS structures with the reaction pathway under kinetic control. The central role of the lithium cation, linked to the oxygen atoms of the epoxy alcohol, is well documented in the reaction mechanisms presented. The energy differences between the two structures of the proposed TS appear to be ascribed to the different contribution of the X-H-O hydrogen bond between the hydroxyl groups of the reactant and the incoming halogen nucleophile. 相似文献
992.
The protolytic equilibria of piperazine (C4H10N2) and phosphate have been investigated in the presence of cobalt or nickel chloride or nitrate by potentiometric titrations between pH 2 and 8. Potentiometric titrations suggest the presence of [M2+(H2O)5(C4H11N2+)]3+ and [M2+(H2O)5(C4H10N2)]2+ in solution with stability constants logK of 3.1 and 3.8 for M = Co and 3.1 and 3.6 for M = Ni, respectively. Crystallization experiments were then conducted at selected pH values to isolate desired species from the known solution composition. Crystallization afforded [M(H2O)6]2+(C4H12N22+)(HPO42—)2 at pH 3.5 and 6.2 (M = Co, Ni), and Co3(PO4)2·8H2O at pH 10.5. No crystals with the dihydrogenphosphate anion or a metal‐bound piperazine ligand could be isolated under the reaction conditions. The solid‐state assembly in the isomorphous structures of [M(H2O)6](C4H12N2)(HPO4)2 with M = Co and Ni is based on an extended hydrogen bonded network between the three ionic building blocks. 相似文献
993.
Jae‐Woon Nah Mi‐Kyeong Jang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3796-3803
Low molecular, water‐soluble chitosan (LMWSC) with a free amine group was prepared by the novel salts‐removal method described in this study. A weight‐average molecular weight and degree of deacetylation (DDA) of LMWSC were determined by viscometry and Kina titration, resulting in 18,579 Da and 93% DDA, respectively. In the Fourier transform infrared spectroscopic, 1H NMR, and 13C NMR spectra the absorption band by the carboxyl group derived from lactic acid and the impurities formed in the enzymatic process disappeared or were significantly lower than that of the control chitosan. Also, from the 1H NMR and 13C NMR spectra the empirical value for the area ratio of the proton and carbon corresponds nearly to its theoretical values. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrum identified the difference in the two adjacent peaks as 161. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3796–3803, 2002 相似文献
994.
Ying Wang Sheng‐Ping Yang Jian‐Min Yue Sharon Chow William Kitching 《Helvetica chimica acta》2003,86(7):2424-2433
Four novel sesquiterpenes, namely 7α,8β,13‐trihydroxy‐5,13‐marasmanolide ( 2 ), isoplorantinone ( 5 ), 4,8,14‐trihydroxyilludala‐2,6,8‐triene ( 6 ), and 8‐hydroxy‐8,9‐secolactara‐1,6‐dien‐5,13‐olide ( 10 ), together with six known ones, 7α,8β‐dihydroxy‐5,13‐marasmanolide ( 1) , 7α,8α‐dihydroxy‐5,13‐marasmanolide ( 3 ), isolactarorufin ( 4 ), blennin A ( 7 ), blennin D ( 8 ), and lactarorufin ( 9 ), were isolated from the ethanolic extract of Lactarius piperatus. The structures of these sesquiterpenes, representing diversified structural types, were determined mainly by spectroscopic methods, especially 2D‐NMR techniques. The structure of 6 was further confirmed by a single‐crystal X‐ray‐diffraction determination. 相似文献
995.
屠树江   朱晓彤   房芳   章晓镜   朱松磊   李团结   史达清 王香善   纪顺俊 《中国化学》2005,23(5):596-598
A simple effective synthesis of bis(dihydropyrimidinone-4-yl)benzene derivatives, using boric acid as catalyst,from isophthalic aldehyde or terephthalic aldehyde, 1,3-dicarbonyl compounds and urea or thiourea in glacial acetic acid was described. As the expansion of the classical Biginelli reaction, this method has the advantage of excellent yields 83%-94% and short reaction time 0.5-1.5 h. 相似文献
996.
The reagent 4-sulfophenyl isothiocyanate (SPITC) is an effective, stable, and inexpensive alternative to commercially available reagents used in the N-terminal sulfonation of peptides for enhanced postsource decay (PSD) in matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analyses. However, suppression of ionization of sulfonated peptides due to sample and matrix contaminants such as sodium can be a problem when using prestructured MALDI target sample supports, such as the Bruker Daltonics AnchorChip. We show that use of the salt-tolerant matrix 2,4,6-trihydroxyacetophenone containing diammonium citrate (THAP/DAC) as an alternative to alpha-cyanohydroxycinnamic acid (HCCA) reduces the need for extensive washing of ZipTip-bound peptides or additional on-target sample clean-up steps. Use of the THAP/DAC matrix results in selective ionization of sulfonated peptides with greater peptide coverage, as well as detection of higher mass derivatized peptides, than was observed for HCCA or THAP alone. The THAP/DAC matrix is quite tolerant of sodium contamination, with SPITC-peptides detectable in preparations containing up to 50 mM NaCl. In addition, THAP/DAC matrix was found to promote efficient PSD fragmentation of sulfonated peptides. We demonstrated the utility of using the THAP/DAC MALDI matrix for peptide sequencing with DNA polymerase beta tryptic peptide mixture, as well as tryptic peptides derived from Xiphophorus maculatus brain extract proteins previously separated by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE). 相似文献
997.
Vaso Dokorou Dimitra Kovala‐Demertzi JerryP. Jasinski Angeliki Galani MavroudisA. Demertzis 《Helvetica chimica acta》2004,87(8):1940-1950
The novel triphenyl adduct of 2‐[(2,6‐dimethylphenyl)amino]benzoic acid (HDMPA; 1 ), i.e., [SnPh3(DMPA)] ( 2 ), the dimeric tetraorganostannoxane [Ph2(DMPA)SnOSn(DMPA)Ph2]2 ( 3 ), and the monomeric adduct [SnPh2(DMPA)2] ( 4 ), where DMPA is monodeprotonated HDMPA, have been prepared and structurally characterized by means of IR, 1H‐NMR, and 13C‐NMR spectroscopy. The structures of 1 and 2 have been determined by X‐ray crystallography. Single‐crystal X‐ray‐diffraction analysis of 1 revealed that there are two molecules in the asymmetric unit, HD1 and HD2 , differing in conformation, both forming centrosymmetric dimers linked by H‐bonds between the carboxylic O‐atoms. X‐Ray analysis of 2 revealed a pentacoordinate structure containing Ph3Sn coordinated to the carboxylato group. Significant C? H/π interactions and intramolecular H‐bonds stabilize the structures of 1 and 2 , which self‐assembled via C? H/π and π/π‐stacking interactions. The Ph3Sn adduct 2 was found to be a promising antimycobacterial lead compound, displaying activity against Mycobacterium tuberculosis H37Rv. The cytotoxiciy in the Vero cell line is also reported. 相似文献
998.
The reaction of Co(NO3)2·6H2O with two equivalents of PPz (PPz = piperazine hexahydrate) and two equivalents of NH4SCN in CH3OH afforded the complex [Co(NCS)2(PPz)2(CH3OH)2]. The reaction of Ni(NO3)2·6H2O with two equivalents of PPz and four equivalents of NH4SCN in CH3OH afforded the complex [Ni(NCS)4(PPz)2]. Their IR spectra have been recorded and the structures have been determined. Crystal data for 1 : space group P&1bar;, a = 6.7208(6) Å, b = 8.4310(8) Å, c = 8.5923(8) Å, a = 77.881(2)°, β = 76.342(2)°, γ = 83.936(2)°, V = 461.75(1) Å3, Z = 1 with final residuals R1 = 0.0650 and wR2 = 0.1725. Crystal data for 2 : space group P2(1)/n, a = 7.4209(6) Å, b = 11.0231(9) Å, c = 12.317(1) Å, β = 96.642(9)°, V = 1000.9(2) Å3, Z = 2 with final residuals R1 = 0.0378 and wR2 = 0.0809. Important NCS—H‐N and O‐H—N(PPz) hydrogen‐bonding interactions in compound 1 and NCS···H‐N hydrogen‐bonding interactions and NCS—SCN interactions in compound 2 play a significant role in aligning the polymer strands in crystalline solids. 相似文献
999.
One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF6 was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated. 相似文献
1000.
The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain. 相似文献