全文获取类型
收费全文 | 62917篇 |
免费 | 19283篇 |
国内免费 | 1466篇 |
专业分类
化学 | 69322篇 |
晶体学 | 171篇 |
力学 | 3178篇 |
综合类 | 88篇 |
数学 | 4730篇 |
物理学 | 6177篇 |
出版年
2024年 | 486篇 |
2023年 | 4890篇 |
2022年 | 2050篇 |
2021年 | 3250篇 |
2020年 | 5546篇 |
2019年 | 2992篇 |
2018年 | 2932篇 |
2017年 | 1043篇 |
2016年 | 6589篇 |
2015年 | 6626篇 |
2014年 | 6141篇 |
2013年 | 6585篇 |
2012年 | 4533篇 |
2011年 | 2237篇 |
2010年 | 4490篇 |
2009年 | 4400篇 |
2008年 | 1930篇 |
2007年 | 1549篇 |
2006年 | 792篇 |
2005年 | 633篇 |
2004年 | 462篇 |
2003年 | 395篇 |
2002年 | 354篇 |
2001年 | 325篇 |
2000年 | 257篇 |
1999年 | 306篇 |
1998年 | 287篇 |
1997年 | 283篇 |
1996年 | 311篇 |
1995年 | 395篇 |
1994年 | 297篇 |
1993年 | 407篇 |
1992年 | 253篇 |
1991年 | 236篇 |
1990年 | 209篇 |
1988年 | 229篇 |
1987年 | 191篇 |
1980年 | 217篇 |
1979年 | 216篇 |
1978年 | 227篇 |
1977年 | 344篇 |
1976年 | 400篇 |
1975年 | 482篇 |
1974年 | 507篇 |
1973年 | 332篇 |
1972年 | 458篇 |
1971年 | 419篇 |
1970年 | 625篇 |
1969年 | 460篇 |
1968年 | 502篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Dr. Chao Xu Dr. Guoxin Tian Dr. Simon J. Teat Dr. Guokui Liu Dr. Linfeng Rao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16690-16698
The complexation of NpO22+ and PuO22+ with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO4 by spectrophotometry, microcalorimetry, and single crystal diffractometry. Formation of 1:1 and 1:2 (metal/ligand molar ratio) complexes of DPA with NpO22+ and PuO22+ were identified and the thermodynamic parameters were determined and compared with those of UO22+. All three hexavalent actinyl cations form strong 1:1 DPA complexes with slightly decreasing but comparable stability constants from UO22+ to PuO22+, whereas the stability constants of the 1:2 complexes (log β2) decrease substantially along the series (16.3 for UO2L22?, 15.17 for NpO2L22?, and 14.17 for PuO2L22? at 25 °C). The enthalpies of complexation for the 1:2 complexes become less exothermic from UO2L22? (?28.9 kJ mol?1), through NpO2L22? (?27.2 kJ mol?1), and to PuO2L22? (?22.7 kJ mol?1). The trends in the thermodynamic parameters are discussed in terms of the effective charge of the cations and the steric constraints in the structures of the complexes. In addition, the features of the absorption spectra, including the wavelength and intensity of the absorption bands, are related to the perturbation of the ligand field and the symmetry of the actinyl complexes. 相似文献
992.
Dr. Jacorien Coetzee Dr. Deborah L. Dodds Prof. Jürgen Klankermayer Sandra Brosinski Prof. Walter Leitner Prof. Alexandra M. Z. Slawin Prof. David J. Cole‐Hamilton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):11039-11050
Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)3], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ1O)2(H2O)(triphos)], [Ru(OAc‐κ2O,O′)(CH3SO3‐κ1O)(triphos)], [Ru(CH3SO3‐κ1O)2(H2O)(triphos)] and [Ru2(μ‐CH3SO3)3(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc‐κ1O)(OAc‐κ2O,O′)(triphos)], [Ru(CH3SO3‐κ1O)(CH3SO3‐κ2O,O′)(triphos)], H[Ru(CH3SO3‐κ1O)3(triphos)], [RuH(CH3SO3‐κ1O)(CO)(triphos)] and [RuH(CH3SO3‐κ2O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed. 相似文献
993.
Dr. Jörg Wagler Dr. Erica Brendler Prof. Dr. Thomas Heine Dr. Lyuben Zhechkov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14296-14303
The reaction of 1‐methyl‐3‐trimethylsilylimidazoline‐2‐thione with hexachlorodisilane proceeds toward substitution of four of the disilane Cl atoms during the formation of disilicon complexes with two neighboring hexacoordinate Si atoms. The N,S‐bidentate methimazolide moieties adopt a buttressing role, thus forming paddlewheel‐shaped complexes of the type ClSi(μ‐mt)4SiCl (mt=methimazolyl). Most interestingly, three isomers (i.e., with (ClN4)Si? Si(S4Cl), (ClN3S)Si? Si(S3NCl), and (ClN2S2)Si? Si(S2N2Cl) skeletons as so‐called (4,0), (3,1), and cis‐(2,2) paddlewheels) were detected in solution by using 29Si NMR spectroscopic analysis. Two of these isomers could be isolated as crystalline solids, thus allowing their molecular structures to be analyzed by using X‐ray diffraction studies. In accord with time‐dependent NMR spectroscopy, computational analyses proved the cis‐(2,2) isomer with a (ClN2S2)Si? Si(S2N2Cl) skeleton to be the most stable. The compounds presented herein are the first examples of crystallographically evidenced disilicon complexes with two Si? Si‐bonded octahedrally coordinated Si atoms and representatives of the still scarcely explored class of Si coordination compounds with sulfur donor atoms. 相似文献
994.
Konrad Hindelang Alexander Kronast Dr. Sergei I. Vagin Prof. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(25):8244-8252
For the first time, the adaptability of the C?C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin‐tagged 4,4′‐bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10‐triptycenedicarboxylate (TDC) zinc paddle‐wheel metal–organic framework (MOF) through microwave‐assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO4) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy‐functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol–ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90 % were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre‐synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis. 相似文献
995.
Dr. Anna‐Barbara Gerber Prof. Christian J. Leumann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):6990-7006
We present the synthesis of the isobicyclo‐DNA building blocks with the nucleobases A, C, G and T, as well as biophysical and biological properties of oligonucleotides derived thereof. The synthesis of the sugar part was achieved in 5 steps starting from a known intermediate of the tricyclo‐DNA synthesis. Dodecamers containing single isobicyclo‐thymidine incorporations, fully modified A‐ and T‐containing sequences, and fully modified oligonucleotides containing all four bases were synthesized and characterized. Isobicyclo‐DNA forms stable duplexes with natural nucleic acids with a pronounced preference for DNA over RNA as complements. The most stable duplexes, however, arise by self‐pairing. Isobicyclo‐DNA forms preferentially B‐DNA‐like duplexes with DNA and A‐like duplexes with complementary RNA as determined by circular dichroism (CD) spectroscopy. Self‐paired duplexes show a yet unknown structure, as judged from CD spectroscopy. Biochemical tests revealed that isobicyclo‐DNA is stable in fetal bovine serum and does not elicit RNaseH activity. 相似文献
996.
Anne‐Catherine Bédard Prof. Dr. Shawn K. Collins 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2108-2113
The aggregation properties of poly(ethylene glycol) (PEG) can be exploited in organic synthesis to control dilution effects. Through the use of solvent mixtures containing PEG400/MeOH, macrocyclization by Glaser–Hay coupling can be conducted at high concentrations. The origin of the selectivity has been studied by using surface tension measurements, UV spectroscopy, and chemical tagging and demonstrates the dependence of the yield and selectivity on the aggregation of PEG400 and its ability to preferentially solubilize organic substrates, resulting in a phase separation from the catalyst system. 相似文献
997.
Fangyuan Zheng Prof. Fang Zeng Changmin Yu Xianfeng Hou Prof. Shuizhu Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):936-942
Owing to the considerable significance of fluoride anions for health and environmental issues, it is of great importance to develop methods that can rapidly, sensitively and selectively detect the fluoride anion in aqueous media and biological samples. Herein, we demonstrate a robust fluorescent turn‐on sensor for detecting the fluoride ion in a totally aqueous solution. In this study, a biocompatible hydrophilic polymer poly(ethylene glycol) (PEG) is incorporated into the sensing system to ensure water solubility and to enhance biocompatibility. tert‐Butyldiphenylsilyl (TBDPS) groups were then covalently introduced onto the fluorescein moiety, which effectively quenched the fluorescence of the sensor. Upon addition of fluoride ion, the selective fluoride‐mediated cleavage of the Si? O bond leads to the recovery of the fluorescein moiety, resulting in a dramatic increase in fluorescence intensity under visible light excitation. The sensor is responsive and highly selective for the fluoride anion over other common anions; it also exhibits a very low detection limit of 19 ppb. In addition, this sensor is operative in some real samples such as running water, urine, and serum and can accurately detect fluoride ions in these samples. The cytotoxicity of the sensor was determined to be Grade I toxicity according to United States Pharmacopoeia and ISO 10993‐5, suggesting the very low cytotoxicity of the sensor. Moreover, it was found that the senor could be readily internalized by both HeLa and L929 cells and the sensor could be utilized to track fluoride level changes inside the cells. 相似文献
998.
Dr. Noam Shemesh Dr. Jean‐Nicolas Dumez Prof. Lucio Frydman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):13002-13008
Nuclear magnetic resonance spectroscopy is governed by longitudinal (T1) relaxation. For protein and nucleic acid experiments in solutions, it is well established that apparent T1 values can be enhanced by selective excitation of targeted resonances. The present study explores such longitudinal relaxation enhancement (LRE) effects for molecules residing in biological tissues. The longitudinal relaxation recovery of tissue resonances positioned both down‐ and upfield of the water peak were measured by spectrally selective excitation/refocusing pulses, and compared with conventional water‐suppressed, broadband‐excited counterparts at 9.4 T. Marked LRE effects with up to threefold reductions in apparent T1 values were observed as expected for resonances in the 6–9 ppm region; remarkably, statistically significant LRE effects were also found for several non‐exchanging metabolite resonances in the 1–4 ppm region, encompassing 30–50 % decreases in apparent T1 values. These LRE effects suggest a novel means of increasing the sensitivity of tissue‐oriented experiments, and open new vistas to investigate the nature of interactions among metabolites, water and macromolecules at a molecular level. 相似文献
999.
Qiuqin Zhou Florian Grundmann Marcel Kaiser Matthias Schiell Dr. Sophie Gaudriault Dr. Andreas Batzer Dr. Michael Kurz Prof. Dr. Helge B. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16772-16779
During the search for novel natural products from entomopathogenic Xenorhabdus doucetiae DSM17909 and X. mauleonii DSM17908 novel peptides named xenoamicins were identified in addition to the already known antibiotics xenocoumacin and xenorhabdin. Xenoamicins are acylated tridecadepsipeptides consisting of mainly hydrophobic amino acids. The main derivative xenoamicin A ( 1 ) was isolated from X. mauleonii DSM17908, and its structure elucidated by detailed 1 D and 2 D NMR experiments. Detailed MS experiments, also in combination with labeling experiments, confirmed the determined structure and allowed structure elucidation of additional derivatives. Moreover, the xenoamicin biosynthesis gene cluster was identified and analyzed in X. doucetiae DSM17909, and its participation in xenoamicin biosynthesis was confirmed by mutagenesis. Advanced Marfey’s analysis of 1 showed that the absolute configuration of the amino acids is in agreement with the predicted stereochemistry deduced from the nonribosomal peptide synthetase XabABCD. Biological testing revealed activity of 1 against Plasmodium falciparum and other neglected tropical diseases but no antibacterial activity. 相似文献
1000.
Robert M. Archer Dr. Sylvain F. Royer William Mahy Dr. Caroline L. Winn Prof. Michael J. Danson Dr. Steven D. Bull 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2895-2902
Practical syntheses of 2‐keto‐3‐deoxy‐D ‐xylonate (D ‐KDX) and 2‐keto‐3‐deoxy‐L ‐arabinonate (L ‐KDA) that rely on reaction of the anion of ethyl 2‐[(tert‐butyldimethylsilyl)oxy]‐2‐(dimethoxy phosphoryl) acetate with enantiopure glyceraldehyde acetonide, followed by global deprotection of the resultant O‐silyl‐enol esters, have been developed. This has enabled us to confirm that a 2‐keto‐3‐deoxy‐D ‐gluconate aldolase from the archaeon Sulfolobus solfataricus demonstrates good activity for catalysis of the retro‐aldol cleavage of both these enantiomers to afford pyruvate and glycolaldehyde. The stereochemical promiscuity of this aldolase towards these enantiomeric aldol substrates confirms that this organism employs a metabolically promiscuous pathway to catabolise the C5‐sugars D ‐xylose and L ‐arabinose. 相似文献