全文获取类型
收费全文 | 44537篇 |
免费 | 1438篇 |
国内免费 | 293篇 |
专业分类
化学 | 30097篇 |
晶体学 | 364篇 |
力学 | 1036篇 |
综合类 | 1篇 |
数学 | 7576篇 |
物理学 | 7194篇 |
出版年
2022年 | 275篇 |
2021年 | 537篇 |
2020年 | 729篇 |
2019年 | 722篇 |
2018年 | 532篇 |
2017年 | 488篇 |
2016年 | 1110篇 |
2015年 | 982篇 |
2014年 | 1166篇 |
2013年 | 2262篇 |
2012年 | 2525篇 |
2011年 | 2886篇 |
2010年 | 1639篇 |
2009年 | 1444篇 |
2008年 | 2644篇 |
2007年 | 2436篇 |
2006年 | 2449篇 |
2005年 | 2272篇 |
2004年 | 2013篇 |
2003年 | 1648篇 |
2002年 | 1602篇 |
2001年 | 671篇 |
2000年 | 647篇 |
1999年 | 552篇 |
1998年 | 511篇 |
1997年 | 546篇 |
1996年 | 609篇 |
1995年 | 433篇 |
1994年 | 491篇 |
1993年 | 485篇 |
1992年 | 455篇 |
1991年 | 435篇 |
1990年 | 360篇 |
1989年 | 329篇 |
1988年 | 341篇 |
1987年 | 400篇 |
1986年 | 328篇 |
1985年 | 572篇 |
1984年 | 515篇 |
1983年 | 424篇 |
1982年 | 507篇 |
1981年 | 450篇 |
1980年 | 455篇 |
1979年 | 406篇 |
1978年 | 388篇 |
1977年 | 377篇 |
1976年 | 347篇 |
1975年 | 344篇 |
1974年 | 286篇 |
1973年 | 245篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
941.
Goldsmith JI Hudson WR Lowry MS Anderson TH Bernhard S 《Journal of the American Chemical Society》2005,127(20):7502-7510
The catalytic process of photoinduced hydrogen generation via the reduction of water has been investigated. The use of parallel synthetic techniques has facilitated the synthesis of a 32 member library of heteroleptic iridium complexes that was screened, using high-throughput photophysical techniques, to identify six potential photosensitizers for use in catalytic photoinduced hydrogen production. A Pd/Ni thin film hydrogen selective sensor allowed for rapid quantification of hydrogen produced via illumination of aqueous systems of the photosensitizer, tris(2,2'-dipyridyl)dichlorocobalt ([Co(bpy)(3)]Cl(2)), and triethanolamine (a sacrificial reductant) with ultra-bright light emitting diodes (LEDs). The use of an 8-well parallel photoreactor expedited the investigation of the hydrogen evolution process and facilitated mechanistic studies. All six compounds investigated produced considerably more hydrogen than commonly utilized photosensitizers and had relative quantum efficiencies of hydrogen production up to 37 times greater than that of Ru(bpy)(3)(2+). 相似文献
942.
Haiges R Vij A Boatz JA Schneider S Schroer T Gerken M Christe KO 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):508-517
The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects. 相似文献
943.
Maziarz EP Liu XM Quinn ET Lai YC Ammon DM Grobe GL 《Journal of the American Society for Mass Spectrometry》2002,13(2):170-176
In this study the prepolymer alpha,omega-bis(4-hydroxybutyl) poly(dimethylsiloxane), used in the formulation of oxygen permeable films, is evaluated by gel permeation chromatography (GPC) combined with matrix assisted laser desorption ionization (MALDI) time of flight (TOF) mass spectrometry (MS). Two unexpected mass distributions are observed in the mass spectra. Reaction schemes for the formation of these distributions are proposed. A solution phase trimethylsilane end group modification was performed on the prepolymer to determine whether the unexpected mass distributions occur as impurities from synthesis or as artifacts from the MS process. Evaluation of the TMS modified prepolymer indicates the unexpected mass distributions indeed occur as impurities from the synthetic procedure. Average molecular weight values are determined by traditional GPC, direct MALDI-TOF MS, and GPC-MALDI-TOF MS methods and the results are compared. 相似文献
944.
The molecular structures of tricyclohexane, norbornane, quadricyclane, and cubane were completely refined by standard ab initio force relaxation on the 4-21G level. The results can be used as a basis to interpret some contradictory experimental reports found in the literature and to establish some hitherto unobserved structural trends involving the C? C and C? H bond distances of the cases studied. Group Delta;E values for C? (H)3(C), C? (H)2(C)2, and C? (H)(C)3 (Benson's notation) derived from the total energies of the completely relaxed 4-21G geometries of a number of unstrained hydrocarbons are also listed. The values are used to estimate the strain energies of the systems studied and of the optimized 4-21G geometries of cyclopropane, cyclobutane, cyclohexane, and bicyclo (2.1.0)pentane. Cooperative effects in the strain energies are discussed. 相似文献
945.
S.K. Agarwal R.P. Rastogi H. Van Koningsveld K. Goubitz G.J. Olthof 《Tetrahedron》1980,36(10):1435-1438
A novel natural product, microphyllone, has been isolated from Ehretia microphylla2 together with baurenol and ursolic acid. Spectroscopic techniques, derivative formation and finally X-ray diffraction have been utilized in the structure elucidation of microphyllone. The structure appears to be 4a, 5, 8,8a - tetrahydro -11,14- dihydroxy-7-methyl-4a-(3-methyl-2-butenyl)-5, 8a-o-benzeno-1, 4-naphthoquinone. 相似文献
946.
János Osán Szabina Török Bálint Alföldy Anita Alsecz Gerald Falkenberg Soo Yeun Baik René Van Grieken 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007
The rivers in the Hungarian Upper Tisza Region are frequently polluted mainly due to mining activities in the catchment area. At the beginning of 2000, two major mining accidents occurred in the Romanian part of the catchment area due to the failure of a tailings dam releasing huge amounts of cyanide and heavy metals to the rivers. Surface sediment as well as water samples were collected at six sites in the years 2000–2003, from the northeast-Hungarian section of the Tisza, Szamos and Túr rivers. The sediment pollution of the rivers was compared based on measurements of bulk material and selected single particles, in order to relate the observed compositions and chemical states of metals to the possible sources and weathering of pollution. Non-destructive X-ray analytical methods were applied in order to obtain different kinds of information from the same samples or particles. In order to identify the pollution sources, their magnitude and fate, complementary analyses were carried out. Heterogeneous particulate samples were analyzed from a large geographical territory and a 4-year time period. Individual particles were analyzed only from the “hot” samples that showed elevated concentrations of heavy metals. Particles that were classified as anthropogenic were finally analyzed to identify trace concentrations and chemical states of heavy metals. 相似文献
947.
Luzgin MV Stepanov AG Arzumanov SS Rogov VA Parmon VN Wang W Hunger M Freude D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):457-465
By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5. 相似文献
948.
Covalent and noncovalent chemistries that are selective to single-walled carbon nanotubes of a particular electronic type have become increasingly important for electronic structure separation and on-chip modification of nanoelectronic devices. By monitoring transient Raman spectroscopy and photoluminescence (PL) during a reaction with 4-chlorobenzene diazonium in aqueous solution, evidence for a characteristic two-step mechanism with two distinct time constants is uncovered. A long-lived intermediate selectively and noncovalently binds and partially dopes the nanotube surface (tau = 2.4 min). A slower, covalent reaction is tracked using the time-dependent increase in the disorder mode in Raman (tau = 73 min). The transient Raman and PL data are well described using a series of two first-order reactions. The covalent bonding step can be deactivated by changing the structure of the surfactant adsorbed phase, further supporting the mechanism. 相似文献
949.
Atomic charges and delocalization indexes (DIs) for a series of carbonyl compounds comprising dimethyl ketone, acetaldehyde, acetic acid, methyl acetate, acetamide, methyl vinyl ketone, divinyl ketone, and benzoic acid were studied using two different atomic partitionings: the QTAIM and the Hirshfeld (stockholder) scheme. The resonance model, traditionally employed to explain the reactivity of these compounds, is not in line with the total atomic charges and DIs calculated by both methodologies. However, the resonance model is supported to some extent by the pi charges and pi DIs calculated by both schemes, but the calculated values indicate that the pi population delocalizes only to a small degree. Although the absolute values of QTAIM and stockholder atomic charges are significantly different, the pi charges and the values of the DIs show similar trends for all the atoms and molecules of this study; this is especially the case for the pi DIs. A study of the electron density on the level of a single MO performed for CO, H2CO, F2CO, and H2CS reveals that the differences in the atomic sigma charges computed with both partitionings can be traced back to their different treatment of interatomic regions. 相似文献
950.
Five acidic calix[4]arenes with carboxylic or sulfonic groups at either the upper or lower rim of the cavity and one resorc[4]arene were investigated to separate three thioxanthenes (flupentixol, clopenthixol, chlorprothixene) and a dibenz[b,e]oxepin derivative (doxepin) with cis-/trans-isomerism by nonaqueous capillary electrophoresis (NACE). Partial filling of the capillary with the UV-absorbing selectors led to a low detection limit and an advantageous signal-to-noise ratio (S/N). A sufficient electrophoretic mobility of the calixarenes towards the anode was necessary to outweigh the oppositely directed electroosmotic flow (EOF). This depended from the functional groups, the dissociation and the hydrodynamic radius of the cyclophanes. In contrast, the resorcinarene was useable only by addition of sodium dodecyl sulfate (SDS) because only the complex of the two selectors had an anodic apparent electrophoretic mobility. p-Sulfonyl-calix[4]arene (ss-a1) was the most capable selector for all E/Z-isomers with maximal alpha-values ranging from 1.056 for doxepin to 1.224 for chlorprothixene. This was due to the sufficient migration in reversed direction to the EOF even at low pH* values of 3.0. Otherwise, electrostatic as well as hydrophobic interactions with the positively charged isomers seem to contribute to a superior recognition. Increasing the concentration up to 15 mM ss-a1 and using acidic media (pH* 5.0) led to high separation efficiency. Changing the organic solvent provides a powerful tool to improve selectivity with N,N-dimethylformamide-methanol (DMF-MeOH)-mixtures for thioxanthenes. Further electrophoretic parameters were optimized, such as the concentration of the electrolytes, the addition of SDS, the kind of electrolytes and the voltage. Distinct differences in selectivities were found between the derivatives with thioxanthene and dibenzo[b,e]oxepin ring system, respectively. Further, the different basic side chain was responsible for the different selectivity at higher pH* values. In contrast, the substitution at position 2 of the thioxanthenes played a secondary role. Based on the studies of single parameters a method for a simultaneous separation of the four pairs of isomers within 13 min was developed. 相似文献