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121.
Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(−)‐MS/MS 下载免费PDF全文
Danny E. García Marrero Wolfgang G. Glasser Antonio Pizzi Sebastian Paczkowski Marie‐Pierre G. Laborie 《Journal of mass spectrometry : JMS》2014,49(10):1050-1058
The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative‐ion mode electrospray ionization tandem mass spectrometry (ESI(?)‐MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C15, catechin). The oligomer sizes were detected to be dimers to heptamers. The derivatives showed typical phenyl‐propyl ether mass fragmentation by substituent elimination (58 amu) and inherent C15 flavonoid fissions. The relative abundance of the product ions revealed a preferential triple, tetra‐/penta‐ and octa‐ hydroxypropylation substitution pattern in the monomer, dimer and trimer derivatives, respectively. A defined order of –OH reactivity towards propylene oxide was established by means of multistage experiments (A‐ring ≥ B‐ring > C‐ring). A high structural heterogeneity of the modified oligomers was detected. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
122.
Mihaela Badea Larisa Calu Mariana Carmen Chifiriuc Coralia Bleotu Alexandra Marin Sebastian Ion Gabriela Ioniţă Nicolae Stanică Luminiţa Măruţescu Veronica Lazăr Dana Marinescu Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2014,118(2):1145-1157
A series of complexes of type [ML(CH3COO)(OH2)2] (M: Co, Ni; HL: 2-[(E)-1H-1,2,4-triazol-3-ylimino)methyl]phenol)) and [M2L2(CH3COO)2(OH2)n] (M: Cu, n = 2; M: Zn, n = 0) were synthesised by template condensation. The compounds were characterised with microanalytical, ESI–MS, IR, electronic, EPR spectra and magnetic data at room temperature. Based on the IR and ESI–MS spectra, a dinuclear structure with the acetate as bridge was proposed for Cu(II) and Zn(II) complexes. The dinuclear structure of Cu(II) complex is also consistent with both magnetic behaviour and EPR spectrum. The thermal analyses have evidenced processes as water elimination, acetate decomposition, as well as oxidative degradation of the Schiff base. The final decomposition product was the most stable metal oxide as indicated by powder X-ray diffraction. The cobalt and copper compounds exhibited a broad spectrum of antibacterial activity towards both planktonic and biofilm-embedded cells. The complexes exhibit a low cytotoxicity except for Cu(II) species that induces the early apoptosis for the HEp 2 cells. 相似文献
123.
Inside Cover: Ruthenium Complexes of Tripodal Ligands with Pyridine and Triazole Arms: Subtle Tuning of Thermal,Electrochemical, and Photochemical Reactivity (Chem. Eur. J. 3/2014) 下载免费PDF全文
124.
Chiral Modification of Platinum by Co‐Adsorbed Cinchonidine and Trifluoroacetic Acid: Origin of Enhanced Stereocontrol in the Hydrogenation of Trifluoroacetophenone 下载免费PDF全文
Fabian Meemken Prof. Dr. Alfons Baiker Dr. Sebastian Schenker Prof. Dr. Konrad Hungerbühler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1298-1309
Cinchonidine (CD) adsorbed onto a platinum metal catalyst leads to rate acceleration and induces strong stereocontrol in the asymmetric hydrogenation of trifluoroacetophenone. Addition of catalytic amounts of trifluoroacetic acid (TFA) significantly enhances the enantiomeric excess from 50 to 92 %. The origin of the enantioselectivity bestowed by co‐adsorbed CD and TFA is investigated by using in situ attenuated total reflection infrared spectroscopy and modulation excitation spectroscopy. Molecular interactions between the chiral modifier (CD), acid additive (TFA) and the trifluoro‐activated substrate at the solid–liquid interface are elucidated under conditions relevant to catalytic hydrogenations, that is, on a technical Pt/Al2O3 catalyst in the presence of H2 and solvent. Monitoring of the unmodified and modified surface during the hydrogenation provides an insight into the phenomenon of rate enhancement and the crucial interactions of CD with the ketone, corresponding product alcohol, and TFA. Comparison of the diastereomeric interactions occurring on the modified surface and in the liquid solution shows a striking difference for the chiral preferences of CD. The spectroscopic data, in combination with calculations of molecular structures and energies, sheds light on the reaction mechanism of the heterogeneous asymmetric hydrogenation of trifluoromethyl ketones and the involvement of TFA in the diastereomeric intermediate surface complex: the quinuclidine N atom of the adsorbed CD forms an N?H?O‐type hydrogen‐bonding interaction not only with the trifluoro‐activated ketone but also with the corresponding alcohol and the acid additive. Strong evidence is provided that it is a monodentate acid/base adduct in which the carboxylate of TFA resides at the quinuclidine N‐atom of CD, which imparts a better stereochemical control. 相似文献
125.
Kim Søholm Halskov Bjarke S. Donslund Dr. Sebastian Barfüsser Prof. Karl Anker Jørgensen 《Angewandte Chemie (International ed. in English)》2014,53(16):4137-4141
A novel and simple one‐step approach for the construction of optically active steroids in a highly stereoselective manner by using organocatalysis is presented. The reaction of (di)enals with cyclic dienophiles in the presence of a TMS‐protected prolinol catalyst leads to the construction of important 14 β‐steroids. This new reaction allows an easy access to optically active steroids with a variety of substituents in the A ring in high yields and up to greater than 99 % ee. The reaction has been extended to include the construction of B‐ and D ‐homosteroids as well as steroids containing heteroatoms in the B ring. The angular substituent at C13 can be varied and alkyl, ester, and sulfone functionalities are introduced with excellent stereoselectivities. Simple synthetic procedures provide access to a range of naturally occurring steroids such as estrone and related analogues. 相似文献
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128.
Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon 下载免费PDF全文
Tom van Dijk Dr. Sebastian Burck Mark K. Rong Amos J. Rosenthal Dr. Martin Nieger Dr. J. Chris Slootweg Prof. Dr. Koop Lammertsma 《Angewandte Chemie (International ed. in English)》2014,53(34):9068-9071
Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3‐P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X‐ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht=tetrahydrothiophene) gives a unique P‐bridged gold trimer, while a P,N‐bidentate complex results from [{RhCl(cod)}2]. The nitrilium ion methodology allows extension of the 1,3‐P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β‐diketiminate ligand. 相似文献
129.
Synthesis of a Natural Product‐Like Compound Collection through Oxidative Cleavage and Cyclization of Linear Peptides 下载免费PDF全文
Dr. Rico Petersen Dr. Sebastian T. Le Quement Prof. Dr. Thomas E. Nielsen 《Angewandte Chemie (International ed. in English)》2014,53(44):11778-11782
Massive efforts in molecular library synthesis have strived for the development of synthesis methodology which systematically delivers natural product‐like compounds of high spatial complexity. Herein, we present a conceptually simple approach that builds on the power of solid‐phase peptide synthesis to assemble precursor peptides (oligomers) designed to undergo oxidative cascade reactions. By harnessing the structural side‐chain diversity and inherent stereochemical features offered by readily available amino acids (monomers), a proof‐of‐concept collection of 54 skeletally and stereochemically diverse compounds was generated, and selected compounds were elaborated into isoform‐selective metalloprotease inhibitors. 相似文献
130.
Nickel‐Catalyzed C?H Alkylations: Direct Secondary Alkylations and Trifluoroethylations of Arenes 下载免费PDF全文
Weifeng Song Sebastian Lackner Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2014,53(9):2477-2480
A versatile nickel catalyst allowed for C H alkylations of unactivated arenes with challenging secondary alkyl bromides and chlorides. The high catalytic efficacy also set the stage for direct secondary alkylations of indoles as well as C H trifluoroethylations with ample substrate scope. 相似文献