全文获取类型
收费全文 | 4019篇 |
免费 | 248篇 |
国内免费 | 30篇 |
专业分类
化学 | 2850篇 |
晶体学 | 36篇 |
力学 | 147篇 |
综合类 | 1篇 |
数学 | 589篇 |
物理学 | 674篇 |
出版年
2023年 | 38篇 |
2022年 | 59篇 |
2021年 | 229篇 |
2020年 | 152篇 |
2019年 | 166篇 |
2018年 | 145篇 |
2017年 | 117篇 |
2016年 | 221篇 |
2015年 | 143篇 |
2014年 | 157篇 |
2013年 | 332篇 |
2012年 | 246篇 |
2011年 | 254篇 |
2010年 | 168篇 |
2009年 | 164篇 |
2008年 | 205篇 |
2007年 | 210篇 |
2006年 | 171篇 |
2005年 | 146篇 |
2004年 | 125篇 |
2003年 | 113篇 |
2002年 | 91篇 |
2001年 | 71篇 |
2000年 | 52篇 |
1999年 | 48篇 |
1998年 | 20篇 |
1997年 | 17篇 |
1996年 | 28篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 19篇 |
1992年 | 19篇 |
1991年 | 16篇 |
1990年 | 15篇 |
1988年 | 9篇 |
1987年 | 12篇 |
1986年 | 14篇 |
1985年 | 18篇 |
1984年 | 25篇 |
1983年 | 17篇 |
1982年 | 13篇 |
1981年 | 12篇 |
1980年 | 27篇 |
1979年 | 17篇 |
1978年 | 19篇 |
1977年 | 8篇 |
1976年 | 11篇 |
1975年 | 9篇 |
1971年 | 8篇 |
1862年 | 8篇 |
排序方式: 共有4297条查询结果,搜索用时 46 毫秒
91.
S. C. Archimandritis Al. K. Tsolis 《Journal of Radioanalytical and Nuclear Chemistry》1987,117(1):35-46
The self life of the freeze-dried formulation kits utilized for the preparation of the new bone imaging radiopharmaceutical99mTc-1,2-dihydroxy-1,2-bis/dihydroxyphosphinyl/ethane /99mTc-DHPE/ has been investigated as well as the toxicity of the DHPE. In a biodistribution investigation of99mTc-DHPE in rats, in comparison to99mTc-methylenediphosphanate /99mTc-MDP/,99mTc-DHPE exhibited a certain extent higher skeleton uptake, a higher blood clearance rate, a very low concentration in other organs, a satisfactory biological stability and excretion primarily through the kidneys. These properties demonstrate that99mTc-DHPE is a new promising skeleton imaging radio-pharmaceutical. 相似文献
92.
Ondřej Linhart Alžběta Kolorosová-Mrázová Jan Kratzer Jakub Hraníček Václav Červený 《Analytical letters》2019,52(4):613-632
An ultraviolet-photochemical generator (UV-PVG) capable of post-column on-line transformation of both organic and inorganic mercury species to cold vapor (Hg0) with subsequent detection by quartz tube-atomic absorption spectrometry (QT-AAS) was developed. Mercury(II), methylmercury(I), ethylmercury(I), and phenylmercury(I) were successfully detected after separation by reversed-phase high-performance liquid chromatography (RP-HPLC). Two types of AAS detectors were compared. The first was a commonly used line-source instrument while the second was a high-resolution continuum source (HR-CS) AAS. The latter provided better limits of detection: 0.47?µg?L?1 for Hg(II), 0.84?µg?L?1 for methylmercury(I), 0.80?µg?L?1 for ethylmercury(I), and 2.0?µg?L?1 for phenylmercury(I). The repeatability at 30?μg?L?1 was 3.6%, 4.1%, 6.2%, and 4.5% for these species (n?=?10). These figures of merit were comparable with those reported for more sensitive atomic fluorescence spectrometry. Nine sample extraction procedures were investigated. Extraction by tetramethylammonium hydroxide and HCl at 75?°C was selected as the only method compatible with the proposed separation and detection steps providing high extraction efficiency and no changes in mercury speciation. The applicability of the proposed high-performance liquid chromatography–ultraviolet-photochemical vapor generation–quartz tube-atomic absorption spectrometry method was demonstrated using fish samples and certified reference materials (CRM) DOLT-4 (dogfish liver) and ERM-CE464 (tuna fish). The results were comparable to those obtained by a reference method based on L-cysteine extraction and high-performance liquid chromatography–inductively coupled plasma-mass spectrometry (HPLC–ICP-MS) determination. 相似文献
93.
Mohammed R. Arshadi 《Journal of mass spectrometry : JMS》1978,13(7):379-381
The 70 eV positive and negative ion mass spectra of the oxygen, sulphur and selenium 2,1,3-benzodiazoles have been studied. The influence of hetero atom on the fragmentation modes of the benzodiazole molecular ions has been discussed. 相似文献
94.
Fettouhi M Ouahab L Boukhari A Cador O Mathonière C Kahn O 《Inorganic chemistry》1996,35(17):4932-4937
The goal of this work was to synthesize new molecular bricks which could be used as precursors of heterobimetallic low-dimensional compounds. Along this line, four compounds have been synthesized and structurally characterized, namely (NBu(4))(2)[Ni(Cl(2)opba)] (1), (NBu(4))(2)[Cu(Cl(2)opba)] (2), (NBu(4))(5)[Mn(Cl(2)opba)(DMSO)(2)](4) (3), and Cu(en)(2)[Mn(Cl(2)opba)(H(2)O)(2)](2).2DMSO (4), with Cl(2)opba = (4,5-dichloro-o-phenylene)bis(oxamato), NBu(4) = tetra-n-butylammonium, en = ethylenediamine, and DMSO = dimethyl sulfoxide. Compounds 1 and 2 are isostructural; they crystallize in the monoclinic system, space group C2/c, Z = 4, with a = 18.708(2) ?, b = 17.525(2) ?, c = 14.763(9) ?, and beta = 92.03(4) degrees for 1 and a = 18.928(2) ?, b = 17.634(2) ?, c = 14.704(9) ?, and beta = 92.38(3) degrees for 2. 3 crystallizes in the tetragonal system, space group P&fourmacr;2(1)c, Z = 2, with a = 26.295(10) ? and c = 12.342(7) ?. The structure shows a random occupation of the metal site by Mn(III) and Mn(II) ions in 3/4 and 1/4 ratios, respectively. 4 crystallizes in the triclinic system, space group P&onemacr;, Z = 1, with a = 7.066(7) ?, b = 11.844(1) ?, c = 14.292(5) ?, alpha = 105.64(2) degrees, beta = 97.67(5) degrees, and gamma = 102.13(3) degrees. The structure consists of Mn(III)Cu(II)Mn(III) trinuclear species, with Cu-O-Mn bridges involving oxygen atoms of the oxamato groups already linked to the metal atom. The magnetic properties of compounds 1-4 have been investigated and quantitatively interpreted. For 3, this magnetic investigation has been performed on a single crystal, which allows us to determine unambiguously the sign of the axial zero-field splitting parameter for the Mn(III) ion. The potentialities of these new molecular bricks have been discussed. 相似文献
95.
Rancan F Wiehe A Nöbel M Senge MO Omari SA Böhm F John M Röder B 《Journal of photochemistry and photobiology. B, Biology》2005,78(1):17-28
The search for new efficient sensitizers for photodynamic therapy (PDT) points to improve photophysical properties like absorption in the red region and singlet oxygen quantum yield as well as to control the localization of the sensitizer within the tumour cell. Depending on their physicochemical properties and their uptake mechanism, sensitizers can reach different intracellular concentrations and localize in different subcellular compartments. Moreover, the preferential localization of a sensitizer in target organelles, like mitochondria or lysosomes, could determine the cell death mechanism after PDT. This study aimed to investigate the influence of substitutions on dihydroxychlorins with regard to intracellular uptake, subcellular localization and cell death pathway. Moreover, the effect of a liposome-based delivery system was tested. The intracellular uptake was found to be strictly dependent on the sensitizer molecular structure and the means of its delivery. The most polar sensitizer in this study (compound 3) had, depending on incubation time, an intracellular concentration 2-8 times higher than the unsubstituted chlorin 1. All investigated photosensitizers localize predominantly in lysosomes but after longer incubation times weak fluorescence intensity was also detected in mitochondria and Golgi apparatus. The cell death pathway was found to be influenced by the sensitizer intracellular concentration and the applied light doses. In general, the increasing amphiphilicity of the sensitizer molecules is correlated with an increased sensitizer uptake and an increased rate of necrotic cells after irradiation. 相似文献
96.
Khalid Mohammed Khan Ghulam Murtaza MaharviSafdar Hayat Zia-UllahM. Iqbal Choudhary Atta-ur-Rahman 《Tetrahedron》2003,59(29):5549-5554
Treatment of aromatic carboxylic acids and substituted toluenes with a mixture of sodium bromate and sodium hydrogen sulfite in a two-phase system gave the corresponding esters in good yield. The intermediate α-brominated toluene was formed by the in situ generated hypobromous acid. The α-bromotoluene underwent an intermolecular nucleophilic substitution reaction with aromatic carboxylic acids present in the reaction mixture to afford the corresponding esters. 相似文献
97.
A method using solid-phase extraction (SPE) has been developed for analysis of mepivacaine in human serum. A procedure for isolation of mepivacaine and lidocaine (internal standard) from human serum by use of Chromosorb 104 (acrylonitrile–divinylbenzene polymer) as extraction adsorbent is described in detail. Analysis was performed by gas chromatography on an HP-INNOWax (cross-linked PEG) capillary column, with flame ionization detection, after splitless injection. Relative standard deviations ranged between 3.6 and 4.4 for a serum mepivacaine concentration of 0.5 g mL–1 and between 4.7 and 5.9 for a concentration of 1 g mL–1. Recoveries were approximately 95%. The method was applied in a stomatological clinic to healthy volunteers to whom anesthesia with mepivacaine was administered. 相似文献
98.
Farida Larit Khaled M. Elokely Manal A. Nael Samira Benyahia Francisco Len Stephen J. Cutler Mohammed M. Ghoneim 《Molecules (Basel, Switzerland)》2021,26(4)
The in vitro activity of L. donovani (promastigotes, axenic amastigotes and intracellular amastigotes in THP1 cells) and T. brucei, from the fractions obtained from the hydroalcoholic extract of the aerial part of Hypericum afrum and the isolated compounds, has been evaluated. The chloroform, ethyl acetate and n-butanol extracts showed significant antitrypanosomal activity towards T. brucei, with IC50 values of 12.35, 13.53 and 12.93 µg/mL and with IC90 values of 14.94, 19.31 and 18.67 µg/mL, respectively. The phytochemical investigation of the fractions led to the isolation and identification of quercetin (1), myricitrin (2), biapigenin (3), myricetin (4), hyperoside (5), myricetin-3-O-β-d-galactopyranoside (6) and myricetin-3’-O-β-d-glucopyranoside (7). Myricetin-3’-O-β-d-glucopyranoside (7) has been isolated for the first time from this genus. The chemical structures were elucidated by using comprehensive one- and two-dimensional nuclear magnetic resonance (1D and 2D NMR) spectroscopic data, as well as high-resolution electrospray ionization mass spectrometry (HR-ESI–MS). These compounds have also been evaluated for their antiprotozoal activity. Quercetin (1) and myricetin (4) showed noteworthy activity against T. brucei, with IC50 and IC90 values of 7.52 and 5.71 µM, and 9.76 and 7.97 µM, respectively. The T. brucei hexokinase (TbHK1) enzyme was further explored as a potential target of quercetin and myricetin, using molecular modeling studies. This proposed mechanism assists in the exploration of new candidates for novel antitrypanosomal drugs. 相似文献
99.
Molybdenum(VI) oxide, ammonium molybdate and molybdic acid reacted in molten sodium nitrite—potassium nitrite eutectic to form orthomolybdate, nitrogen dioxide and nitric oxide (with nitrate as a secondary product), a more polymerised polymolybdate being formed as an intermediate product. Tungsten(VI) oxide reacted similarly but less rapidly. Molybdenum and tungsten metals reacted to form the orthoxyanion and nitrogen, the latter metal reacting considerably faster and forming smaller amounts of nitric oxide and nitrous oxide. Reaction temperatures and stoichiometries are given and reaction pathways suggested. 相似文献
100.
Mahmoud M. Al Omari Mohammad B. Zughul J. Eric D. Davies Adnan A. Badwan 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):159-164
Ternary complexes exploiting solubility synergism (SSn) between basic drugs and β-cyclodextrin (β-CD) in the presence of an organic hydoxy acid have been reported to provide the pharmaceutical technology with highly soluble ternary complexes, even with the least soluble β-CD. In this work, phase solubility techniques were used to study factors affecting SSn in aqueous solution, which may help in understanding the mechanism involved in ternary complex formation in solution, under equilibrium conditions. The equilibrium solubility of both β-CD and each of 8 structurally unrelated drugs were measured in tandem in the presence of different acid types at low and high pHs, and at different time intervals over a period of 1–40 days. The results indicate that SSn is evident regardless of acid type (organic and inorganic) at low pH, but the extent of SSn is acid type dependant and is limited by the drug salt solubility product constant (pK
sp). Among different drugs, no apparent trend exists between drug salt solubility and the extent of SSn, but lowering drug salt solubility by increasing pH depresses SSn. The results also reveal no apparent trend between the magnitude of the complex formation constant (K
ij) and SSn. For example, drugs of low K
ij values such as astemizole, cisapride and sildenafil do not show any SSn, yet ketotifen and pizotifen, which also have low K
ij values, exhibit substantial SSn. However, the solublizing power of β-CD represented by the slope of phase solubility diagram can be used as a marker for SSn (slopes exceeding 0.4 induce SSn). 相似文献