全文获取类型
收费全文 | 8664篇 |
免费 | 203篇 |
国内免费 | 62篇 |
专业分类
化学 | 5820篇 |
晶体学 | 84篇 |
力学 | 260篇 |
综合类 | 1篇 |
数学 | 1324篇 |
物理学 | 1440篇 |
出版年
2022年 | 82篇 |
2021年 | 83篇 |
2020年 | 156篇 |
2019年 | 112篇 |
2018年 | 85篇 |
2017年 | 95篇 |
2016年 | 190篇 |
2015年 | 153篇 |
2014年 | 197篇 |
2013年 | 397篇 |
2012年 | 457篇 |
2011年 | 560篇 |
2010年 | 282篇 |
2009年 | 226篇 |
2008年 | 495篇 |
2007年 | 456篇 |
2006年 | 446篇 |
2005年 | 450篇 |
2004年 | 432篇 |
2003年 | 285篇 |
2002年 | 310篇 |
2001年 | 90篇 |
2000年 | 85篇 |
1999年 | 66篇 |
1998年 | 79篇 |
1997年 | 99篇 |
1996年 | 139篇 |
1995年 | 85篇 |
1994年 | 69篇 |
1993年 | 96篇 |
1992年 | 68篇 |
1991年 | 81篇 |
1990年 | 82篇 |
1989年 | 59篇 |
1988年 | 75篇 |
1987年 | 63篇 |
1986年 | 57篇 |
1985年 | 113篇 |
1984年 | 131篇 |
1983年 | 93篇 |
1982年 | 114篇 |
1981年 | 108篇 |
1980年 | 95篇 |
1979年 | 84篇 |
1978年 | 111篇 |
1977年 | 94篇 |
1976年 | 82篇 |
1975年 | 71篇 |
1974年 | 71篇 |
1973年 | 60篇 |
排序方式: 共有8929条查询结果,搜索用时 0 毫秒
911.
Torrent-Sucarrat M Ruiz-Lopez MF Martins-Costa M Francisco JS Anglada JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(18):5076-5085
We have investigated the HO(2) adsorption and acid dissociation process on the surface of (H(2)O)(20) and (H(2)O)(21) clusters by using quantum-chemistry calculations. Our results show that the radical forms a stable hydrogen-bond complex on the cluster. The HO(2) acid dissociation is more favorable in the case of the (H(2)O)(21) cluster, for which the inner water molecule plays a crucial role. In fact, acid dissociation of HO(2) is found to occur in two steps. The first step involves H(2) O autoionization in the cluster, and the second one involves the proton transfer from the HO(2) radical to the hydroxide anion. The presence of the HO(2) radicals on the surface of the cluster facilitates water autoionization in the cluster. 相似文献
912.
Raja DS Paramaguru G Bhuvanesh NS Reibenspies JH Renganathan R Natarajan K 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4548-4559
Four 2-oxo-1,2-dihydroquinoline-3-carbaldehyde N-substituted thiosemicarbazone ligands (H(2)-OQtsc-R, where R = H, Me, Et or Ph) and their corresponding new copper(II) complexes [CuCl(2)(H(2)-OQtsc-H)]·2H(2)O (1), [CuCl(2)(H(2)-OQtsc-Me)]·2H(2)O (2), [CuCl(2)(H(2)-OQtsc-Et)(CH(3)OH)]Cl (3) and [CuCl(H-OQtsc-Ph)]·CH(3)OH (4) have been synthesized in order to correlate the effect of terminal N-substitution on coordination behaviour, structure and biological activity. Single crystal X-ray diffraction studies revealed that the complexes 1, 2 and 3 have square pyramidal geometry around the central metal ion. In the complexes 1 and 2, the copper ion is coordinated by the ligand with ONS donor atoms, one chloride ion in apical position and the other chloride in the basal plane. Complex 3 consists of [CuCl(2)(H(2)-OQtsc-Et)(CH(3)OH)](+) cation and a chloride as counter ion. The copper ion is coordinated by the ligand with ONS donor atoms and by one chloride ion in the basal plane. One methanol molecule is bonded through its neutral oxygen in the apical position. Complex 4 is square planar with the ligand coordinating through uni-negative tridentate ONS(-) and by one chloride ion in the basal plane. The binding of complexes with lysozyme protein was carried out by fluorescence spectroscopy. Investigations of antioxidation properties showed that all the copper(II) complexes have strong radical scavenging properties. The cytotoxicity of the complexes 3 and 4 against NIH 3T3 and HeLa cell lines showed that synergy between the metal and ligands results in a significant enhancement in the cell death with IC(50) of ~10-40 μM. A size dependence of substitution at terminal N in the thiosemicarbazones on the biological activities of the complexes has been observed. 相似文献
913.
Cheng Y Meyers JD Broome AM Kenney ME Basilion JP Burda C 《Journal of the American Chemical Society》2011,133(8):2583-2591
Efficient drug delivery to tumors is of ever-increasing importance. Single-visit diagnosis and treatment sessions are the goal of future theranostics. In this work, a noncovalent PDT cancer drug-gold nanoparticle (Au NP) conjugate system performed a rapid drug release and deep penetration of the drug into tumors within hours. The drug delivery mechanism of the PDT drug through Au NPs into tumors by passive accumulation was investigated via fluorescence imaging, elemental analysis, and histological staining. The pharmacokinetics of the conjugates over a 7-day test period showed rapid drug excretion, as monitored via the fluorescence of the drug in urine. Moreover, the biodistribution of Au NPs in this study period indicated clearance of the NPs from the mice. This study suggests that noncovalent delivery via Au NPs provides an attractive approach for cancer drugs to penetrate deep into the center of tumors. 相似文献
914.
B. Joseph 《Journal of Thermal Analysis and Calorimetry》1993,40(3):1447-1450
The Laboratory of the Government Chemist (LGC) is a focal point for the production, analysis and certification of reference materials. Within the field of thermal analysis the LGC is concerned with the development of purity standards and materials certified for enthalpy of fusion and melting point. For some time the LGC has been concerned with the significant differences in purity data which can be produced by the different manufactures' differential scanning calorimeters. This paper will highlight the initiatives the LGC is undertaking in overcoming this uncertainty in purity measurements through the use of certified thermal standards. 相似文献
915.
916.
Nadine Tachon Farid Jahouh Michel Delmas Joseph H. Banoub 《Rapid communications in mass spectrometry : RCM》2011,25(18):2657-2671
We have identified compounds obtained from the SARA fractions of bitumen by using atmospheric pressure photoionization mass spectrometry and low‐energy collision tandem mass spectrometric analyses with a QqToF‐MS/MS hybrid instrument. The identified compounds were isolated from the maltene saturated oil and the aromatic fractions of the SARA components of a bitumen. The QqToF instrument had sufficient mass resolution to provide accurate molecular weight information and to enhance the tandem mass spectrometry results. The APPI‐QqToF‐MS analysis of the separated compounds showed a series of protonated molecules [M + H]+ and molecular ions [M]+? of the same mass but having different chemical structures, in the maltene saturated oil and the aromatic SARA fractions. These isobaric ions were a molecular ion [M2]+? at m/z 418.2787 and a protonated molecule [M5 + H]+ at m/z 287.1625 in the saturated oil fraction, and molecular ions [M6]+? at m/z 418.1584 and [M7]+? at m/z 287.1285 in the aromatic fraction. The identification of this series of chemical compounds was achieved by performing CID‐MS/MS analyses of the molecular ions [M]+? ([M1]+? at m/z 446. 2980, [M2]+? at m/z 418.2787, [M3]+? at m/z 360.3350 and [M4]+? at m/z 346.2095) in the saturated oil fraction and of the [M5 + H]+ ion at m/z 287.1625 also in the saturated oil fraction. The observed CID‐MS/MS fragmentation differences were explained by proposed different breakdown processes of the precursor ions. The presented tandem mass spectrometric study shows the capability of MS/MS experiments to differentiate between different classes of chemical compounds of the SARA components of bitumen and to explain the reasons for the observed mass spectrometric differences. However, greater mass resolution than that provided by the QqToF‐MS/MS instrument would be required for the analysis of the asphaltene fraction of bitumen. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
917.
Al-Hariri LA Reisch A Schlenoff JB 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):3914-3919
Different positive polyelectrolytes having the same charge density, molecular weight, and molecular weight distribution were employed for polyelectrolyte multilayer (PEMU) assembly. The polycations differed only in the heteroatom on which the positive charge resided: poly(vinyl benzyl trimethyl ammonium) chloride, poly(vinyl benzyl trimethyl phosphonium) chloride, and poly(vinyl benzyl dimethyl sulfonium) chloride. While the ammonium repeat unit has been employed on numerous occasions for PEMU assembly, the phosphonium and sulfonium units are relatively neglected. The polyanions, poly(styrene sulfonate), PSS, or poly(acrylic acid), PAA, were typical pH-independent or pH-dependent polymers, respectively. All three polyoniums were quite similar in showing linear layer-by-layer buildup with PSS and exponential growth with PAA, under the conditions employed. Hydration and wettability were also similar between polyoniums. 相似文献
918.
919.
Investigation of the insertion reactivity of the tethered silylalkyl complex (η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)(2)U (1) has led to a series of new reactions for U-C bonds. Elemental sulfur reacts with 1 by inserting two sulfur atoms into each of the U-C bonds to form the bis(tethered alkyl disulfide) complex (η(5):η(2)-C(5)Me(4)SiMe(2)CH(2)S(2))(2)U (2). The bulky substrate N,N'-diisopropylcarbodiimide, (i)PrN═C═N(i)Pr, inserts into only one of the U-C bonds of 1 to produce the mixed-tether complex (η(5)-C(5)Me(4)SiMe(2)CH(2)-κC)U[η(5)-C(5)Me(4)SiMe(2)CH(2)C((i)PrN)(2)-κ(2)N,N'] (3). Carbon monoxide did not exclusively undergo a simple insertion into the U-C bond of 3 but instead formed {μ-[η(5)-C(5)Me(4)SiMe(2)CH(2)C(═N(i)Pr)O-κ(2)O,N]U[OC(C(5)Me(4)SiMe(2)CH(2))CN((i)Pr)-κ(2)O,N](2) (4) in a cascade of reactions that formally includes U-C bond cleavage, C-N bond cleavage of the amidinate ligand, alkyl or silyl migration, U-O, C-C, and C-N bond formations, and CO insertion. The reaction of 3 with isoelectronic tert-butyl isocyanide led to insertion of the substrate into the U-C bond, but with a rearrangement of the amidinate ligand binding mode from κ(2) to κ(1) to form [η(5):η(2)-C(5)Me(4)SiMe(2)CH(2)C(═N(t)Bu)]U[η(5)-C(5)Me(4)SiMe(2)CH(2)C(═N(i)Pr)N((i)Pr)-κN] (5). The product of double insertion of (t)BuN≡C into the U-C bonds of 1, namely [η(5):η(2)-C(5)Me(4)SiMe(2)CH(2)C(═N(t)Bu)](2)U (6), was found to undergo an unusual thermal rearrangement that formally involves C-H bond activation, C-C bond cleavage, and C-C bond coupling to form the first formimidoyl actinide complex, [η(5):η(5):η(3)-(t)BuNC(CH(2)SiMe(2)C(5)Me(4))(CHSiMe(2)C(5)Me(4))]U(η(2)-HC═N(t)Bu) (7). 相似文献
920.
He F Wang W Chen W Xu T Darling SB Strzalka J Liu Y Yu L 《Journal of the American Chemical Society》2011,133(10):3284-3287
A series of semiconducting copolymers (PTAT-x) containing extended π-conjugated tetrathienoanthracene units have been synthesized. It was shown that the extended conjugation system enhanced the π-π stacking in the polymer/PC(61)BM blend films and facilitated the charge transport in heterojunction solar cell devices. After structural fine-tuning, the polymer with bulky 2-butyloctyl side chains (PTAT-3) exhibited a PCE of 5.6% when it was blended with PC(61)BM. 相似文献