全文获取类型
收费全文 | 1148篇 |
免费 | 44篇 |
国内免费 | 1篇 |
专业分类
化学 | 840篇 |
晶体学 | 10篇 |
力学 | 36篇 |
数学 | 156篇 |
物理学 | 151篇 |
出版年
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 15篇 |
2020年 | 39篇 |
2019年 | 19篇 |
2018年 | 16篇 |
2017年 | 18篇 |
2016年 | 27篇 |
2015年 | 32篇 |
2014年 | 19篇 |
2013年 | 52篇 |
2012年 | 58篇 |
2011年 | 76篇 |
2010年 | 34篇 |
2009年 | 47篇 |
2008年 | 68篇 |
2007年 | 61篇 |
2006年 | 48篇 |
2005年 | 64篇 |
2004年 | 51篇 |
2003年 | 42篇 |
2002年 | 42篇 |
2001年 | 16篇 |
2000年 | 14篇 |
1999年 | 10篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 24篇 |
1995年 | 11篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 9篇 |
1991年 | 6篇 |
1990年 | 12篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1986年 | 9篇 |
1985年 | 13篇 |
1984年 | 21篇 |
1982年 | 14篇 |
1981年 | 15篇 |
1980年 | 11篇 |
1979年 | 12篇 |
1977年 | 11篇 |
1976年 | 6篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 11篇 |
1972年 | 5篇 |
1970年 | 5篇 |
排序方式: 共有1193条查询结果,搜索用时 63 毫秒
101.
Sonia Morante-Zarcero Alfredo Sánchez Mariano Fajardo Isabel del Hierro Isabel Sierra 《Mikrochimica acta》2010,169(1-2):57-64
A hexagonal mesoporous silica (HMS) functionalized with a 5-mercapto-1-methyltetrazole derivative was employed to prepare a chemically modified carbon paste electrode for Pb(II) detection in aqueous solution by square wave adsorptive stripping voltammetry. The optimal operating conditions were 5 min preconcentration time at pH 6.5, and 120 s electrolysis time in 0.2 mol L?1 HCl. Under these conditions, the voltammetric signal increased linearly with the preconcentration time in the range 1 to 10 min and with the Pb(II) concentration in the range 1 to 100?µg L?1. The electrode was reproducible and sensitive. Simultaneous determination of Pb, Cd and Cu was also carried out with the electrode. The accuracy of the method was validated by analysing Pb(II) in tap water and groundwater samples. 相似文献
102.
Jarrod J. M. Amoore Dr. Suzanne M. Neville Dr. Boujemaa Moubaraki Dr. Simon S. Iremonger Dr. Keith S. Murray Prof. Jean‐François Létard Dr. Cameron J. Kepert Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(6):1973-1982
We previously reported the dinuclear material [FeII2(ddpp)2(NCS)4] ? 4 CH2Cl2 ( 1? 4 CH2Cl2; ddpp=2,5‐di(2′,2′′‐dipyridylamino)pyridine) and its partially desolvated analogue ( 1? CH2Cl2), which undergo two‐ and one‐step spin‐crossover (SCO) transitions, respectively. Here, we manipulate the type and degree of solvation in this system and find that either a one‐ or two‐step spin transition can be specifically targeted. The chloroform clathrate 1? 4 CHCl3 undergoes a relatively abrupt one‐step SCO, in which the two equivalent FeII sites within the dinuclear molecule crossover simultaneously. Partial desolvation of 1? 4 CHCl3 to form 1? 3 CHCl3 and 1? CHCl3 occurs through single‐crystal‐to‐single‐crystal processes (monoclinic C2/c to P21/n to P21/n) in which the two equivalent FeII sites become inequivalent sites within the dinuclear molecule of each phase. Both 1? 3 CHCl3 and 1? CHCl3 undergo one‐step spin transitions, with the former having a significantly higher SCO temperature than 1? 4 CHCl3 and the latter, and each has a broader SCO transition than 1? 4 CHCl3, attributable to the overlap of two SCO steps in each case. Further magnetic manipulation can be carried out on these materials through reversibly resolvating the partially desolvated material with chloroform to produce the original one‐step SCO, or with dichloromethane to produce a two‐step SCO reminiscent of that seen for 1? 4 CH2Cl2. Furthermore, we investigate the light‐induced excited spin state trapping (LIESST) effect on 1? 4 CH2Cl2 and 1? CH2Cl2 and observe partial LIESST activity for the former and no activity for the latter. 相似文献
103.
104.
Biuret is an intermediate in the bacterial metabolism of s-triazine ring compounds and is occasionally used as a ruminant feed supplement. We used bioinformatics to identify a biuret hydrolase, an enzyme that has previously resisted efforts to stabilize, purify and characterize. This newly discovered enzyme is a member of the cysteine hydrolase superfamily, a family of enzymes previously not found to be involved in s-triazine metabolism. The gene from Rhizobium leguminosarum bv. viciae strain 3841 encoding biuret hydrolase was synthesized, transformed into Escherichia coli, and expressed. The enzyme was purified and found to be stable. Biuret hydrolase catalyzed the hydrolysis of biuret to allophanate and ammonia. The k(cat)/K(M) of 1.7 × 10(5) M(-1)s(-1) and the relatively low K(M) of 23 ± 4 μM together suggested that this enzyme acts uniquely on biuret physiologically. This is supported by the fact that of the 34 substrate analogs of biuret tested, only two demonstrated reactivity, both at less than 5% of the rate determined for biuret. Biuret hydrolase does not react with carboxybiuret, the product of the enzyme immediately preceding biuret hydrolase in the metabolic pathway for cyanuric acid. This suggests an unusual metabolic strategy of an enzymatically-produced intermediate undergoing non-enzymatic decarboxylation to produce the substrate for the next enzyme in the pathway. 相似文献
105.
Goran N. Kaluđerović Valentina Tayurskaya Reinhard Paschke Sanjiv Prashar Mariano Fajardo Santiago Gómez‐Ruiz 《应用有机金属化学》2010,24(9):656-662
The carboxylate compounds [Ti(η5‐C5H5)(η5‐C5H4{CMe2(CH2CH2CH?CH2)})(O2CCH2SXyl)2] (2; Xyl = 3,5‐Me2C6H3) and [Ti(η5‐C5H5)(η5‐C5H4{CMe2(CH2CH2CH?CH2)})(O2CCH2SMesl)2] (3; Mes 1 = 2,4,6‐Me3C6H2) were synthesized by the reaction of [Ti(η5‐C5H5)(η5‐C5H4{CMe2(CH2CH2CH?CH2)})Cl2] (1) with 2 equivalents of xylylthioacetic acid or mesitylthioacetic acid, respectively. Compounds 2 and 3 were characterized by spectroscopic methods. The cytotoxic activity of 1–3 was tested against human tumor cell lines from four different histogenic origins—8505C (anaplastic thyroid cancer), DLD‐1 (colon cancer) and the cisplatin sensitive A253 (head and neck cancer) and A549 (lung carcinoma)—and compared with those of the reference complex [Ti(η5‐C5H5)2Cl2] (R1) and cisplatin. Surprisingly, the cytotoxic activities of the carboxylate derivatives were lower than those of their corresponding dichloride analogue (1). However, complexes 1–3 were more active than titanocene dichloride against all the studied cells with the exception of complex 2 against A253 and A549 cell lines. DNA‐interaction tests were also carried out. Solutions of all the studied complexes were treated with different concentrations of fish sperm DNA, observing modifications of the UV spectra with intrinsic binding constants of 2.99 × 105, 2.45 × 105, and 2.35 × 105 M ?1 for 1–3. Structural studies based on density functional theory calculations of 2 and 3 were also carried out. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
106.
H. Bustos Rodríguez Y. Rojas Martínez D. Oyola Lozano G. A. Pérez Alcázar M. Fajardo J. Mojica Y. J. C. Molano 《Hyperfine Interactions》2005,161(1-4):61-68
In this work a study on gold mineral samples is reported, using optical microscopy, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The auriferous samples are from the El Diamante mine, located in Guachavez-Nariño (Colombia) and were prepared by means of polished thin sections. The petrography analysis registered the presence, in different percentages that depend on the sample, of pyrite, quartz, arsenopyirite, sphalerite, chalcopyrite and galena. The XRD analysis confirmed these findings through the calculated cell parameters. One typical Rietveld analysis showed the following weight percent of phases: 85.0% quartz, 14.5% pyrite and 0.5% sphalerite. In this sample, MS demonstrated the presence of two types of pyrite whose hyperfine parameters are δ 1 = 0.280 ± 0.002 mm/s and Δ 1 = 0.642 ± 0.002 mm/s, δ 2 = 0.379 ± 0.002 mm/s and Δ 2 = 0.613 ± 0.002 mm/s. 相似文献
107.
Peter C. Junk Cameron J. Kepert Lioubov I. Semenova Brian W. Skelton Allan H. White 《无机化学与普通化学杂志》2006,632(7):1293-1302
A number of salts of 2,2′:6′,2″ ‐terpyridyl (‘tpy’) with univalent anions (halides : X = Cl, Br, I; oxyanions of increasing basicity: ClO4, NO3, ‘tfa’ = trifluoroacetate, ‘tca’ = trichloroacetate), variously solvated, have been structurally characterized by single crystal X‐ray studies. In all cases the tpy moieties are found to be doubly protonated [tpyH2]2+, the hydrogen atoms being associated with the nitrogen atoms of the peripheral rings, these together with the central nitrogen atom being directed towards a common focus, in most cases ‘chelating’ one of the counter‐ion components in diverse ways. Thus the chloride and bromide compounds are isomorphous [(tpyH2)X]+X−·H2O arrays; a second dihydrate phase is also described for the chloride, the two forms having the unchelated anion and water molecules engaged in hydrogen‐bonded networks essentially independent of [(tpyH2)X]+. The iodide is anhydrous, and of a different structural type, the anions, presumably too large for chelation, lying out of plane to either side, and linking different cations into a one‐dimensional polymer; in the perchlorate, the unsolvated aggregate is now discrete [(tpyH2)X2], a pair of perchlorate ions disposed to either side of the tpy plane, lying each with one oxygen atom interacting with both of the two protonating hydrogen atoms. In the anhydrous X = NO3, tfa, tca arrays, the lattices are solvated by the parent acids; one oxygen atom of each anion is chelated by the [tpyH2]2+ as in the chlorides, the other anion, with the acid, forming an independent ‘acid salt’ counterion [XHX]− in each case, retaining the additional protonic hydrogen rather than further protonating the central ring, all being of the form [(tpyH2)X]X·HX = [(tpyH2)X][X(HX)]. 相似文献
108.
109.
Dr. Lucy Clark Dr. Farida H. Aidoudi Dr. Cameron Black Dr. Kasun S. A. Arachchige Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Russell E. Morris Prof. Dr. Philip Lightfoot 《Angewandte Chemie (International ed. in English)》2015,54(51):15457-15461
The ionothermal synthesis, structure, and magnetic susceptibility of a novel inorganic–organic hybrid material, imidazolium vanadium(III,IV) oxyfluoride [C3H5N2][V9O6F24(H2O)2] (ImVOF) are presented. The structure consists of inorganic vanadium oxyfluoride slabs with kagome layers of V4+ S=${{ 1/2 }}$ ions separated by a mixed valence layer. These inorganic slabs are intercalated with imidazolium cations. Quinuclidinium (Q) and pyrazinium (Pyz) cations can also be incorporated into the hybrid structure type to give QVOF and PyzVOF analogues, respectively. The highly frustrated topology of the inorganic slabs, along with the quantum nature of the magnetism associated with V4+, means that these materials are excellent candidates to host exotic magnetic ground states, such as the highly sought quantum spin liquid. Magnetic susceptibility measurements of all samples suggest an absence of conventional long‐range magnetic order down to 2 K despite considerable antiferromagnetic exchange. 相似文献
110.
Inversion twinning in a second polymorph of the hydrochloride salt of the recreational drug ethylone
T. Stanley Cameron J. Stuart Grossert Chad R. Maheux Idralyn Q. Alarcon Catherine R. Copeland Anthony Linden 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(4):266-270
A second polymorph of the hydrochloride salt of the recreational drug ethylone, C12H16NO3+·Cl−, is reported [systematic name: (±)‐2‐ethylammonio‐1‐(3,4‐methylenedioxyphenyl)propane‐1‐one chloride]. This polymorph, denoted form (A), appears in crystallizations performed above 308 K. The originally reported form (B) [Wood et al. (2015). Acta Cryst. C 71 , 32–38] crystallizes preferentially at room temperature. The conformations of the cations in the two forms differ by a 180° rotation about the C—C bond linking the side chain to the aromatic ring. Hydrogen bonding links the cations and anions in both forms into similar extended chains in which any one chain contains only a single enantiomer of the chiral cation, but the packing of the ions is different. In form (A), the aromatic rings of adjacent chains interleave, but pack equally well if neighbouring chains contain the same or opposite enantiomorph of the cation. The consequence of this is then near perfect inversion twinning in the structure. In form (B), neighbouring chains are always inverted, leading to a centrosymmetric space group. The question as to why the polymorphs crystallize at slightly different temperatures has been examined by density functional theory (DFT) and lattice energy calculations and a consideration of packing compactness. The free energy (ΔG) of the crystal lattice for polymorph (A) lies some 52 kJ mol−1 above that of polymorph (B). 相似文献