全文获取类型
收费全文 | 1872篇 |
免费 | 48篇 |
国内免费 | 6篇 |
专业分类
化学 | 866篇 |
晶体学 | 9篇 |
力学 | 89篇 |
数学 | 399篇 |
物理学 | 563篇 |
出版年
2023年 | 9篇 |
2022年 | 31篇 |
2021年 | 38篇 |
2020年 | 33篇 |
2019年 | 44篇 |
2018年 | 40篇 |
2017年 | 41篇 |
2016年 | 64篇 |
2015年 | 41篇 |
2014年 | 60篇 |
2013年 | 105篇 |
2012年 | 112篇 |
2011年 | 127篇 |
2010年 | 81篇 |
2009年 | 81篇 |
2008年 | 109篇 |
2007年 | 82篇 |
2006年 | 87篇 |
2005年 | 85篇 |
2004年 | 57篇 |
2003年 | 61篇 |
2002年 | 49篇 |
2001年 | 21篇 |
2000年 | 21篇 |
1999年 | 36篇 |
1998年 | 25篇 |
1997年 | 25篇 |
1996年 | 27篇 |
1995年 | 23篇 |
1994年 | 20篇 |
1993年 | 15篇 |
1992年 | 12篇 |
1991年 | 17篇 |
1990年 | 20篇 |
1989年 | 11篇 |
1987年 | 10篇 |
1986年 | 13篇 |
1984年 | 14篇 |
1980年 | 8篇 |
1979年 | 13篇 |
1978年 | 8篇 |
1977年 | 16篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1974年 | 7篇 |
1972年 | 9篇 |
1969年 | 8篇 |
1968年 | 8篇 |
1967年 | 7篇 |
1938年 | 7篇 |
排序方式: 共有1926条查询结果,搜索用时 15 毫秒
81.
The new ternary carbodiimide LiY(CN2)2 was synthesized by solid state metathesis reaction between YF3 and Li2(CN2) in a silica tube at 550 °C. The X‐ray single‐crystal structure determination yielded an orthorhombic crystal system (Pbcn, Z = 4, a = 982.0(3), b = 698.5(2), c = 613.4(2) pm). The crystal structure can be considered related to the NiAs structure. The carbodiimide ions are arranged in layers following the motif of a hexagonal closest packing of sticks. Lithium and yttrium cations occupy all octahedral voids in an ordered fashion, alternating on top of each other along the hcp stacking direction. 相似文献
82.
The new carbodiimide compounds Li2RE2Sr(CN2)5 (RE = Sm, Gd, Eu, Tb) were prepared by a straight forward solid state metathesis reaction of REF3, SrF2, and Li2(CN2) at around 600 °C. The crystal structure of Li2Gd2Sr(CN2)5 was solved based on X‐ray single‐crystal diffraction data. Corresponding Li2RE2Sr(CN2)5 compounds were analyzed by isotypic indexing of their powder patterns. The crystal structure of Li2Gd2Sr(CN2)5 can be well related to that of Gd2(CN2)3, because both structures are based on layered structures composed of close packed layers of [N=C=N]2– sticks, alternating with layers of metal ions. The crystal structure of Li2Gd2Sr(CN2)5 can be considered to contain an ABC layer sequence of [N = C=N]2– layers with the interlayer voids being occupied by (three) distinct types of cations. 相似文献
83.
84.
Nikolay E. Nifant'ev Yury E. Tsvetkov Alexander S. Shashkov Leonid O. Kononov Vladimir M. Menshov Alexander B. Tuzikov 《Journal of carbohydrate chemistry》2013,32(8):939-953
ABSTRACT Synthesis of two isomeric tetrasaccharides, namely Neu5Acα(2→3)Galβ(1→3)[Fucα(1→4)GlcNAcβ (sLea) and Neu5Acα(2→3)Galβ(1→4)[Fucα(1→3)]GlcNAcβ (sLex) as 3-aminopropyl glycosides is described. Preparation of these compounds was performed by sialylation of selectively protected trisaccharides Lea and Lex which contain three unsubstituted OH groups at positions 2, 3 and 4 of Gal residue. Glycosylation of Lex trisaccharide with ethylthio sialoside under promotion by NIS and TfOH in acetonitrile was effective and regio- and stereoselective to give sLex derivative in 81% yield. In contrast, sialylation of the Lca acceptor was accompanied by a variety of undesirable by-processes, namely. N-thioethylation of the GlcNAc residue, β-sialylation, and lactonisation. In order to improve the yield of sLca tetrasaccharide the glycosylation of Lea acceptor by sialyl donors of ethyl and phenyl thioglycoside (promoted by NIS-TfOH or NBS-Bu4NBr), xanthate (promotion by NIS-TfOH mixture or MeOTf) and phosphite (promoted by TMSOTf) types was also studied. Among the reactions investigated the glycosylation by phenyl thioglycoside sialoside promoted by NIS-TfOH gives the best yield (39%) of sLea tetrasaccharide product. 相似文献
85.
N. N. Panina T. A. Grebeneva Ya. M. Gurevich A. I. Tkachuk M. A. Kim 《Polymer Science Series D》2014,7(2):105-111
The influence of epoxy imide cycloaliphatic epoxy resin EPOX-01 on the rheological properties of the epoxy amine system was investigated. The effect of the amount of amine hardener for solidification process of modified system is evaluated. It is shown that the use of epoxy imide cycloaliphatic resin allows one to obtain materials with improved technological characteristics of film technology (RFI). 相似文献
86.
Atom-economic Approach to the Synthesis of α-(Hetero)aryl-substituted Furan Derivatives from Biomass
Leonid V. Romashov Kirill S. Kozlov Matvey K. Skorobogatko Alexander Y. Kostyukovich Valentine P. Ananikov 《化学:亚洲杂志》2022,17(1):e202101227
An atom-economic ring construction approach to the synthesis of α-(hetero)arylfurans based on renewable furanic platform chemicals has been developed. Corresponding compounds have been prepared in good to excellent yields via [2+2+2] and [4+2] cycloaddition reactions using metal-catalyzed or photoredox protocols. Easily available HMF-based 2-hydroxymethyl-5-ethynylfuran and 2-hydroxymethyl-5-cyanofuran were used as starting materials. A synthetic route with an improved carbon economy factor has been implemented to achieve sustainability aim. The possible application of arylfurans as molecular conductors has been investigated by DFT calculations, which revealed excellent charge transfer properties. As a future perspective, integration of biomass processing strategy into manufacturing of molecular electronics was pointed out to achieve the aim of sustainability. 相似文献
87.
Dr. Anna Pakhomova Birgit Fuchs Prof. Dr. Leonid S. Dubrovinsky Prof. Dr. Natalia Dubrovinskaia Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):6007-6014
Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO4(OH), the behavior of the isostructural borates β-HfB2O5 and β-ZrB2O5 have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB2O5 features a rearrangement of the corner-sharing BO4 tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB2O5 contains ten-membered rings including the rare structural motif of edge-sharing BO4 tetrahedra with exceptionally short B−O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf4+, and tenfold coordinated Zr4+, respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs. 相似文献
88.
Olga Kirichenko Gennadiy Kapustin Vera Nissenbaum Igor Mishin Leonid Kustov 《Journal of Thermal Analysis and Calorimetry》2014,118(2):749-758
The applications of zerovalent iron nanoparticles (nZVI) exploit their high reactivity which decreases due to oxidation in aerobic conditions during manufacture, application, and storage. In this study, we present the new procedure for estimation of the nZVI stability to oxidation in air. The procedure is suitable for characterization of the novel materials based on the supported nZVI. Nanoscale particles were synthesized inside porous silica supports by incipient wetness impregnation with the metal precursor solutions followed by thermal treatment. The TG–DTA studies revealed the decomposition temperature of the supported precursors, as well as the interaction of Fe and precious metal precursors, which resulted in the formation of alloy nanoparticles. Characterization of the samples by XRD confirmed the formation of the nanoparticles of the metallic Pd, Pt, and Fe phases supported on SiO2 carriers, as well as the formation of solid solutions based on the structure of precious metals. The new procedure for estimation of the nZVI stability included (1) TPR with hydrogen up to 400–425 °C followed by isothermal reduction at these temperatures; (2) in situ reoxidation with oxygen at room temperature. The samples were reduced “as obtained” and after in situ reoxidation. The results of the TPR studies exhibited that introduction of both Pd and Pt protected the Fe nanoparticles from oxidation with oxygen and air at ambient conditions. 相似文献
89.
Vasyl Hreb Vira Shved Oleh Buryy Olga Pekinchak Leonid Vasylechko 《无机化学与普通化学杂志》2020,646(14):1138-1143
Crystal structure parameters of the mixed cobaltite–chromite SmCo0.5Cr0.5O3 in the temperature range of 298–1173 K were derived from in situ high-resolution X-ray synchrotron powder diffraction data. Similar to the parent SmCoO3 compound, SmCo0.5Cr0.5O3 reveals anomalous thermal expansion reflected in abnormal temperature dependence of the unit cell dimensions and the selected interatomic distances and angles. These anomalies are associated with temperature induced changes of spin state of Co3+ ions and coupled insulator-metal transition. Observed decreasing behavior of the bandwidth W points on the increasing population of the exited spin states of Co3+ ions in SmCo0.5Cr0.5O3 with increasing temperature. First principle calculations revealed antiferromagnetic ground state of SmCo0.5Cr0.5O3 as the most stable. 相似文献
90.
Alexander A. Larin Dmitry M. Bystrov Leonid L. Fershtat Alexey A. Konnov Nina N. Makhova Konstantin A. Monogarov Dmitry B. Meerov Igor N. Melnikov Alla N. Pivkina Vitaly G. Kiselev Nikita V. Muravyev 《Molecules (Basel, Switzerland)》2020,25(24)
In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid. 相似文献