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171.
Luis M. Mateo Qiang Sun Shi‐Xia Liu Jesse J. Bergkamp Kristjan Eimre Carlo A. Pignedoli Pascal Ruffieux Silvio Decurtins Giovanni Bottari Roman Fasel Tomas Torres 《Angewandte Chemie (International ed. in English)》2020,59(3):1334-1339
On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV. 相似文献
172.
Yao Y Li G Gray KA Lueptow RM 《Langmuir : the ACS journal of surfaces and colloids》2008,24(14):7072-7075
We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations. 相似文献
173.
Cho H Shaw WJ Parvanov V Schenter GK Karkamkar A Hess NJ Mundy C Kathmann S Sears J Lipton AS Ellis PD Autrey ST 《The journal of physical chemistry. A》2008,112(18):4277-4283
Variable temperature 2H NMR experiments on the orthorhombic phase of selectively deuterated NH3BH3 spanning the static to fast exchange limits of the borane and amine motions are reported. New values of the electric field gradient (EFG) tensor parameters have been obtained from the static 2H spectra of V(zz) = 1.652 (+/-0.082) x 10(21) V/m(2) and eta = 0.00 +/- 0.05 for the borane hydrogens and V(zz) = 2.883 (+/-0.144) x 10(21) V/m(2) and eta = 0.00 +/- 0.05 for the amine hydrogens. The molecular symmetry inferred from the observation of equal EFG tensors for the three borane hydrogens and likewise for the three amine hydrogens is in sharp contrast with the C(s) symmetry derived from diffraction studies. The origin of the apparent discrepancy has been investigated using molecular dynamics methods in combination with electronic structure calculations of NMR parameters, bond lengths, and bond angles. The computation of parameters from a statistical ensemble rather than from a single set of atomic Cartesian coordinates gives values that are in close quantitative agreement with the 2H NMR electric field gradient tensor measurements and are more consistent with the molecular symmetry revealed by the NMR spectra. 相似文献
174.
Matthew L. Gettings Michael T. Thoenen Dr. Edward F. C. Byrd Dr. Jesse J. Sabatini Dr. Matthias Zeller Prof. Dr. Davin G. Piercey 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14530-14535
This work reports the first compound containing both a tetrazole and an azasydnone ring, a unique energetic material. Several energetic salts of the tetrazole azasydnone were synthesized and characterized, leading to the creation of new secondary and primary explosives. Molecular structures are confirmed by 1H and 13C NMR, IR spectroscopy, and X-ray crystallographic analysis. The high heats of formation, fast detonation velocities, and straight-forward synthesis of energetic azasydnones should capture the attention of future energetics research. 相似文献
175.
Dr. Santosh K. Singh Jesse La Jeunesse Vasant Vuppuluri Prof. Steven F. Son Dr. Bing-Jian Sun Mr. Yue-Lin Chen Prof. Agnes H. H. Chang Prof. Alexander M. Mebel Prof. Dr. Ralf I. Kaiser 《Chemphyschem》2020,21(9):837-842
Understanding of the fundamental mechanisms involved in the decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) still represents a major challenge for the energetic materials and physical (organic) chemistry communities mainly because multiple competing dissociation channels are likely involved and previous detection methods of the products are not isomer selective. In this study we exploited a microsecond pulsed infrared laser to decompose thin RDX films at 5 K under mild conditions to limit the fragmentation channels. The subliming decomposition products during the temperature programed desorption phase are detected using isomer selective single photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). This technique enables us to assign a product signal at m/z=42 to ketene (H2CCO), but not to diazomethane (H2CNN; 42 amu) as speculated previously. Electronic structure calculations support our experimental observations and unravel the decomposition mechanisms of RDX leading eventually to the elusive ketene (H2CCO) via an exotic, four-membered ring intermediate. This study highlights the necessity to exploit isomer-selective detection schemes to probe the true decomposition products of nitramine-based energetic materials. 相似文献
176.
Dr. Jaebong Jang Dr. Ciric To Dr. Dries J. H. De Clercq Dr. Eunyoung Park Charles M. Ponthier Bo Hee Shin Mierzhati Mushajiang Dr. Radosław P. Nowak Dr. Eric S. Fischer Dr. Michael J. Eck Dr. Pasi A. Jänne Dr. Nathanael S. Gray 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14589-14597
Targeting epidermal growth factor receptor (EGFR) through an allosteric mechanism provides a potential therapeutic strategy to overcome drug-resistant EGFR mutations that emerge within the ATP binding site. Here, we develop an allosteric EGFR degrader, DDC-01-163, which can selectively inhibit the proliferation of L858R/T790M (L/T) mutant Ba/F3 cells while leaving wildtype EGFR Ba/F3 cells unaffected. DDC-01-163 is also effective against osimertinib-resistant cells with L/T/C797S and L/T/L718Q EGFR mutations. When combined with an ATP-site EGFR inhibitor, osimertinib, the anti-proliferative activity of DDC-01-163 against L858R/T790M EGFR-Ba/F3 cells is enhanced. Collectively, DDC-01-163 is a promising allosteric EGFR degrader with selective activity against various clinically relevant EGFR mutants as a single agent and when combined with an ATP-site inhibitor. Our data suggests that targeted protein degradation is a promising drug development approach for mutant EGFR. 相似文献
177.
178.
Liam J. R. McGeachie Cameron L. Carpenter-Warren David B. Cordes Michael Bühl Steven J. Gray Guoxiong Hua Alexandra M. Z. Slawin J. Derek Woollins 《无机化学与普通化学杂志》2020,646(22):1795-1798
An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar3Sb(NSO)2), and copper examples [CuBipy(PPh3)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding. 相似文献
179.
Timothy R. Totsch Victoria L. Stanford Oleksander Klep Mary K. Burdette Benjamin Grant Stephen H. Foulger Gary M. Gray 《Journal of polymer science. Part A, Polymer chemistry》2020,58(13):1825-1842
Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2 and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2) –[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2 with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, TGA, DSC, and SEC. 31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and Tg profiles. The polymers have weight average MWs of up to 3.8 × 104 Da. 相似文献
180.