全文获取类型
收费全文 | 1275篇 |
免费 | 36篇 |
专业分类
化学 | 1110篇 |
晶体学 | 12篇 |
力学 | 6篇 |
数学 | 64篇 |
物理学 | 119篇 |
出版年
2024年 | 2篇 |
2023年 | 19篇 |
2022年 | 116篇 |
2021年 | 108篇 |
2020年 | 35篇 |
2019年 | 31篇 |
2018年 | 37篇 |
2017年 | 35篇 |
2016年 | 78篇 |
2015年 | 44篇 |
2014年 | 56篇 |
2013年 | 93篇 |
2012年 | 80篇 |
2011年 | 93篇 |
2010年 | 64篇 |
2009年 | 48篇 |
2008年 | 71篇 |
2007年 | 70篇 |
2006年 | 41篇 |
2005年 | 47篇 |
2004年 | 36篇 |
2003年 | 26篇 |
2002年 | 24篇 |
2001年 | 8篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有1311条查询结果,搜索用时 6 毫秒
51.
Dr. Susana Ibáñez Dr. Katarzyna Świderek Prof. Eduardo Peris 《Angewandte Chemie (International ed. in English)》2023,62(18):e202301914
Mechanically interlocked molecules (MIMs) have gained increasing interest during the last decades, not only because of their aesthetic appeal, but also because their unique properties have allowed them to find applications in nanotechnology, catalysis, chemosensing and biomedicine. Herein we describe how a pyrene molecule with four octynyl substituents can be easily encapsulated within the cavity of a tetragold(I) rectangle-like metallobox, by template formation of the metallo-assembly in the presence of the guest. The resulting assembly behaves as a mechanically interlocked molecule (MIM), in which the four long limbs of the guest protrude from the entrances of the metallobox, thus locking the guest inside the cavity of the metallobox. The new assembly resembles a metallo-suit[4]ane, given the number of protruding long limbs and the presence of the metal atoms in the host molecule. However, unlike normal MIMs, this molecule can release the tetra-substituted pyrene guest by the addition of coronene, which can smoothly replace the guest in the cavity of the metallobox. Combined experimental and computational studies allowed the role of the coronene molecule in facilitating the release of the tetrasubstituted pyrene guest to be explained, through a process that we named “shoehorning”, as the coronene compresses the flexible limbs of the guest so that it can reduce its size to slide in and out the metallobox. 相似文献
52.
Magdalena Kurdziel Elżbieta Szczepaniec-Cięciak Barbara Dąbrowska Wojciech Nitek Katarzyna Paliś Edyta Ślusarska 《Journal of solution chemistry》2003,32(7):601-615
The solubilities of solid 2,3-dimethylbutane and cyclopentene in liquid argon at a temperature of 87.3 K and in liquid nitrogen at 77.4 K have been measured by the filtration method. The hydrocarbon contents in solutions were determined using gas chromatography. GC–MS was used to identify impurities in solutes. The experimental value of the mole fraction solubility of solid 2,3-dimethyl-butane in liquid argon at 87.3 K is (8.26 ± 1.60) × 10–6 and (2.77 ± 0.94) × 10–8 in liquid nitrogen at 77.4 K. The experimental value of the mole fraction solubility of solid cyclopentene in liquid argon at 87.3 K is (5.11 ± 0.44) × 10–6 and (4.60 ± 0.76) × 10–8 in liquid nitrogen at 77.4 K. The Preston–Prausnitz method was used for calculation of the solubilities of solid hydrocarbons in liquid argon in the temperature range 84.0–110.0 K and in liquid nitrogen from 64.0 to 90.0 K. The solvent–solute interaction parameters l
12 were also calculated. At 90.0 K liquid argon is a better solvent for investigated solid hydrocarbons than is liquid nitrogen. 相似文献
53.
A series of new neutral dicarboxylatoplatinum(II) complexes, containing D(+), L(−) or DL-malate dianion and ethylenediamine,
1-ethylimidazole or 1-propylimidazole as amine ligands, have been synthesized and characterized by elemental analysis, t.l.c.,
conductance, i.r., n.m.r., mass spectra (m/z) and electronic spectra. The new cytotoxic malatoplatinum(II) complexes are very soluble in water and resist hydrolysis.
Their reactivity against glutathione is comparable with the reactivity of carboplatin, which suggests that these new complexes
may be promising candidates in the search for low toxicity platinum cytostatics.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
54.
The lipophilicity of some antiarrhythmic and antihypertensive active 1-[2-hydroxy- or 1-[2-acetoxy-3-(4-aryl-1-piperazinyl)propyl]pyrrolidin-2-one derivatives (1-12) has been investigated. Their lipophilicity (R(MO) and log k') was determined by reversed-phase thin-layer chromatography and reversed-phase high-performance liquid chromatography with mixtures of acetonitrile and Tris buffer as mobile phases. The partition coefficients of compounds 1-12 (log P(ScilogP)) were also calculated with the ScilogP program. Comparison of R(MO), log k' and calculated log D(7.0 ScilogP) values enabled calculation of clog D(7.0 TLC) and clog D(7.0 HPLC) values. Preliminary quantitative structure-activity relationship studies indicated that for active compounds there is a dependence between affinity for alpha(2)-adrenoceptors and their clog D(7.0 HPLC) values. 相似文献
55.
Direct determination of thermodynamic data has always been a complicated and troublesome experimental task. Gas chromatography is among long-established working tools well suited to performing this particular task indirectly. Our own results were first presented in the papers by Ciazynska-Halarewicz and Kowalska (1,2), and this article is Part III in the series. Present experiments are carried out on low- and medium-polarity stationary phases at five different temperatures ranging from 323K to 423K. They enable determination of two thermodynamic properties of the alkylbenzenes, molar enthalpy of vaporization (DeltaH(vap)), and the chemical potential of partitioning of the methylene group between the two phases of the chromatographic system (Delta micro (p(-CH2-))). These properties are obtained from eight nonempirical models and, as is apparent from their derivation (3-7), the terms of the models have clearly defined physical meaning, which enables calculation of thermodynamic properties. 相似文献
56.
JPC – Journal of Planar Chromatography – Modern TLC - Fatty acids from pentanoic to tricosanoic have been separated on RP-18 HPTLC plates, with and without concentrating zone, with... 相似文献
57.
Sobierajska K Fabczak H Fabczak S 《Journal of photochemistry and photobiology. B, Biology》2005,79(2):135-143
We have previously reported that motile photophobic response in ciliate Blepharisma japonicum correlates with dephosphorylation of a cytosolic 28 kDa phosphoprotein (PP28) exhibiting properties similar to those of phosducin. Here we demonstrate in in vivo phosphorylation assay that the light-elicited dephosphorylation of the PP28 is significantly modified by cell incubation with substances known to modulate protein phosphatase and kinase activities. Immunoblot analyses showed that incubation of ciliates with okadaic acid and calyculin A, potent inhibitors of type 1 or 2A protein phosphatases, distinctly increased phosphorylation of PP28 in dark-adapted cells and markedly weakened dephosphorylation of the ciliate phosducin following cell illumination. An enhancement of PP28 phosphorylation was also observed in dark-adapted ciliates exposed to 8-Br-cAMP and 8-Br-cGMP, slowly hydrolysable cyclic nucleotide analogs and 3-isobutyryl-1-methylxanthine (IBMX), a non-specific cyclic nucleotide phosphodiesterase (PDEs) inhibitor. Only slight changes in light-evoked dephosphorylation levels of PP28 were observed in cells treated with the cyclic nucleotide analogs and IBMX. Incubation of ciliates with H 89 or KT 5823, highly selective inhibitor of cAMP-dependent protein kinase (PKA) and cGMP-dependent protein kinase (PKG), respectively, decreased PP28 phosphorylation levels in dark-adapted cells, whereas the extent of light-evoked dephosphorylation of the phosphoprotein was only slightly influenced. Cell treatment with higher Ca2+ concentration together with ionophore A23187 in culture medium resulted in marked increase in PP28 phosphorylation levels, while quite an opposite effect was observed in cells exposed to Ca2+ chelators, EGTA or BAPTA/AM as well as calmodulin antagonists, such as trifluoperazine (TFP), W-7 or calmidazolium. Light-dependent dephosphorylation was not considerably affected by these treatments. The experimental findings presented here suggest that an endogenous light-dependent protein kinase-phosphatase system may be engaged in the alteration of phosducin phosphorylation in ciliate B. japonicum thereby to modulate the cell motile photophobic behavior. 相似文献
58.
Grzegorz Mlostoń Katarzyna Urbaniak Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》2012,95(4):577-585
The attempted ethenylation at C(2) of 2‐unsubstituted 1H‐imidazole N‐oxides with ethyl acrylate (=prop‐2‐enoate) in the presence of Pd(OAc)2 does not occur. In contrast to the other aromatic N‐oxides, the [2+3] cycloaddition of imidazole N‐oxides predominates, and 3‐hydroxyacrylates, isomeric with the cycloadducts, are key products for the subsequent reaction. The final products were identified as dehydrated 2+1 adducts of 1H‐imidazole N‐oxide and ethyl acrylate. The role of the catalyst is limited to the dehydration of the intermediate 3‐hydroxypropanoates to give 1H‐imidazol‐2‐yl‐substituted acrylates. 相似文献
59.
60.
Efficient Solvent‐Free Synthesis of Benzothiazine‐Fused Pyrrolo[3,4‐c]coumarins: Cycloaddition Reactions between Coumarin‐Based Dihydrobenzothiazoles and Isocyanides 下载免费PDF全文
Mehdi Khoobi Ali Ramazani Mohammad Mahdavi Alireza Foroumadi Saeed Emami Sang Woo Joo Katarzyna Ślepokura Tadeusz Lis Abbas Shafiee 《Helvetica chimica acta》2014,97(6):847-853
A new and unusual synthesis of benzothiazine‐fused pyrrolo[3,4‐c]coumarins, involving the ring‐opening of coumarin‐based dihydrobenzothiazoles and subsequent [4+1] cycloaddition reaction with isocyanides, was described. Thus, simple heating of various 3‐(2,3‐dihydro‐2‐methylbenzo[d]thiazol‐2‐yl)coumarins with isocyanides produced the title compounds in good yields under solvent‐free conditions. 相似文献