全文获取类型
收费全文 | 2644篇 |
免费 | 42篇 |
国内免费 | 6篇 |
专业分类
化学 | 1633篇 |
晶体学 | 10篇 |
力学 | 45篇 |
数学 | 550篇 |
物理学 | 454篇 |
出版年
2020年 | 26篇 |
2019年 | 22篇 |
2016年 | 35篇 |
2015年 | 43篇 |
2014年 | 37篇 |
2013年 | 70篇 |
2012年 | 48篇 |
2011年 | 63篇 |
2010年 | 43篇 |
2009年 | 47篇 |
2008年 | 67篇 |
2007年 | 64篇 |
2006年 | 63篇 |
2005年 | 52篇 |
2004年 | 41篇 |
2003年 | 49篇 |
2002年 | 36篇 |
2001年 | 32篇 |
2000年 | 39篇 |
1999年 | 33篇 |
1998年 | 32篇 |
1997年 | 33篇 |
1996年 | 35篇 |
1995年 | 29篇 |
1994年 | 28篇 |
1993年 | 29篇 |
1992年 | 26篇 |
1991年 | 41篇 |
1990年 | 39篇 |
1989年 | 32篇 |
1988年 | 34篇 |
1987年 | 28篇 |
1986年 | 25篇 |
1985年 | 35篇 |
1984年 | 37篇 |
1983年 | 27篇 |
1982年 | 44篇 |
1981年 | 45篇 |
1980年 | 46篇 |
1979年 | 46篇 |
1978年 | 43篇 |
1977年 | 28篇 |
1976年 | 23篇 |
1975年 | 30篇 |
1973年 | 25篇 |
1970年 | 21篇 |
1933年 | 22篇 |
1929年 | 28篇 |
1928年 | 21篇 |
1927年 | 21篇 |
排序方式: 共有2692条查询结果,搜索用时 15 毫秒
71.
Flowers of Jasminum rincospernum convert deuterium-labeled jasmonic acid [2H5]- 4a and methyl 1,2-didehy-drojasmonate [2H4]- 8 into labeled cis-jasmone [2H4]- 1. The labeling pattern of the resulting cis-jasmone ( 1 ) is consistent with a Grob fragmentation of the didehydrojasmonic acid 8a by decarboxylation after protonation of the keto group. The pathway is also operative in leaves of several higher plants, including mono- and dicotyledonous specimens. In Lima beans besides cis-jasmone ( 1 ) an equimolar mixture of trans- and cis-isomers of methyl jasmonate ( 4 ) and epi- 4 , is emitted after treatment with Jasmonic acid ( 4a ). The relative ratio of 1 and 4 /epi- 4 is critically dependent on the concentration of the administered jasmonic acid ( 4a ) and the ambient temperature of the plant. Unlike 4a , the 1,2-didehydrojasmonic acid ( 8a ) is not able to induce volatile biosynthesis. Therefore, the transformation of 4a via 8 a into 1 appears to have a special importance for the irreversible inactivation and disposal of the plant stress hormone jasmonic acid to the gas phase and may serve, besides other modes of inactivation, as a shunt in case of high internal of the stress hormone 4a. The conversion of the biologically active jasmonic acid ( 4a ) into the inactive and volatile cis-jasmone (1) is the first example of a disposal of an inactive metabolite of a phytohormone to the gas phase as an infinite sink. 相似文献
72.
Silvia Stumpf Gudrun Goretzki Kerstin Gloe Karsten Gloe Wilhelm Seichte Edwin Weber Jan W. Bats 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):225-233
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects. 相似文献
73.
McGuinness DS Wasserscheid P Keim W Morgan D Dixon JT Bollmann A Maumela H Hess F Englert U 《Journal of the American Chemical Society》2003,125(18):5272-5273
Cr(III) complexes of tridentate SNS ligands have been prepared and evaluated as catalysts for ethylene trimerization, with several giving very high activity and excellent selectivity toward 1-hexene when activated with methylaluminoxane. The new complexes illustrate the potential of sulfur-based ligands on early transition metals for catalysis. 相似文献
74.
75.
Thomas Prenveille Cyrielle Garreau Mathias Matner Dirk Dijkstra Wilhelm Oppermann Diethelm Johannsmann 《Journal of polymer science. Part A, Polymer chemistry》2019,57(5):621-629
The reactivity of urethanes based on 1,6‐hexamethylene diisocyanate (HDI) and 4,4′‐methylene diphenyl diisocyanate (MDI) was investigated at temperatures between 190 °C and 235 °C. Diurethane model compounds end‐capped with either 1‐dodecanol (D‐core‐D) or 1‐hexadecanol (H‐core‐H) were mixed and annealed at high temperature. The core was either MDI or HDI. The transurethanization reaction was followed based on the formation of the compounds (H‐core‐D). The amount of H‐core‐D and of side products, which had formed after variable annealing times, were identified with 1H NMR, FTIR, SEC, and MALDI‐TOF. Transurethanization was considerably faster for MDI‐based urethanes than for HDI‐based urethanes. Only traces of side products were formed during annealing of MDI‐based urethanes, whereas a significant amount of allophanates was formed from HDI‐based urethanes under the same conditions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 621–629 相似文献
76.
Dr. Debabrata Maity Dr. Khaleel I. Assaf Wilhelm Sicking Dr. Christoph Hirschhäuser Prof. Dr. Werner M. Nau Prof. Dr. Carsten Schmuck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(57):13088-13093
A convenient supramolecular strategy for constructing a ratiometric fluorescent chemosensing ensemble, consisting of a macrocyclic host (cucurbit[8]uril CB[8]), and a pyrene-tagged amphiphilic peptide beacon (AP 1), is reported. AP 1 unfolds upon encapsulation of the pyrene termini into the hydrophobic CB[8] cavity. This changes pyrene excimer to monomer emission. Substrates with higher affinity for the CB[8] cavity can displace AP 1 from the ensemble. The released AP 1 folds again to form a pyrene excimer, which allows for the ratiometric fluorescence monitoring of the substrate. In this report, the ensemble capacity for ratiometric fluorescence monitoring of biological substrates, such as amino acid derivatives, specific peptides, and proteins, in aqueous media is demonstrated. 相似文献
77.
N-(17-Phosphonooxylinolenoyl)glutamine (1) and N-(17-phosphonooxylinoleoyl)glutamine (2) were isolated from the regurgitate of Spodoptora exigua and identified as the first natural alkyl chain-phosphorylated fatty acid derivatives. The compounds were characterized by HPLC-MS/MS and the assigned structures confirmed by synthesis via a dissymmetric bis-Wittig approach as the key reaction. Rearing of the larvae on a diet enriched with inorganic phosphate increased the amount of the phosphorylated N-acyl glutamines in the regurgitate. 相似文献
78.
Thevis M Beuck S Höppner S Thomas A Held J Schäfer M Oomens J Schänzer W 《Journal of the American Society for Mass Spectrometry》2012,23(3):537-546
Structure elucidation of steroids by mass spectrometry has been of great importance to various analytical arenas and numerous
studies were conducted to provide evidence for the composition and origin of (tandem) mass spectrometry-derived product ions
used to characterize and identify steroidal substances. The common product ion at m/z 97 generated from androst-4-ene-3-one analogs has been subject of various studies, including stable isotope-labeling and
(high resolution/high accuracy) tandem mass spectrometry, but its gas-phase structure has never been confirmed. Using high
resolution/high accuracy mass spectrometry and low resolution tandem mass spectrometry, density functional theory (DFT) calculation,
and infrared multiple photon dissociation (IRMPD) spectroscopy employing a free electron laser, the structure of m/z 97 derived from testosterone was assigned to protonated 3-methyl-2-cyclopenten-1-one. This ion was identified in a set of
six cyclic C6H9O+ isomers as computed at the B3LYP/6-311++G(2d,2p) level of theory (protonated 3-methyl-2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one
and 2-cyclohexen-1-one). Product ions of m/z 97 obtained from MS2 and MS3 experiments of protonated 3-methyl-2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one, 2-cyclohexen-1-one, and testosterone
corroborated the suggested gas-phase ion structure, which was eventually substantiated by IRMPD spectroscopy yielding a spectrum
that convincingly matched the predicted counterpart. Finally, the dissociation pathway of the protonated molecule of testosterone
to m/z 97 was revisited and an alternative pathway was suggested that considers the exclusion of C-10 along with the inclusion of
C-5, which was experimentally demonstrated with stable isotope labeling. 相似文献
79.
Ga8Ir4B – a Gallium Iridium Boride with isolated, nearly square planar Ir4B Groups in a Structure derived from the CaF2 Type The new compound Ga8Ir4B (tetragonal, I41/acd, a = 853.69(2) pm, c = 2 105.69(6) pm, Z = 8, 614 reflections, 31 parameters, R = 0.034) was prepared by reaction of the elements at 1 100°C. The structure is derived from the CaF2 type. It contains isolated Ir4B groups with boron in an unusual, nearly square planar coordination. 相似文献
80.
Bis(diphenylphosphano)alkane- and 1-Diphenylphosphano-2-(2-pyridino)ethane-N-arylsulfinylamine Nickel(0) Complexes Synthesis and properties of the bis(diphenylphosphano)alkane-N-phenyl-sulfinylamine-nickel(0) complexes [Ni{Ph2P(CH2)nPPh2}(PhNSO)] (n = 2 dppe, n = 3 dppp, n = 4 dppb) as well as of the 1-(diphenylphosphano)-2-(2-pyridino)ethane nickel(0) complexes [Ni(dpppe)2], [Ni(dpppe)(p-TolNSO)] and [Ni(dpppe)(PPh3)2] are described. These compounds have been characterized by i. r. and 31P n.m.r. spectroscopy. The N-arylsulfinylamine ligands are η2-(N, S)-side on coordinated. 相似文献