全文获取类型
收费全文 | 12474篇 |
免费 | 651篇 |
国内免费 | 138篇 |
专业分类
化学 | 8855篇 |
晶体学 | 116篇 |
力学 | 573篇 |
综合类 | 3篇 |
数学 | 1553篇 |
物理学 | 2163篇 |
出版年
2024年 | 26篇 |
2023年 | 106篇 |
2022年 | 557篇 |
2021年 | 496篇 |
2020年 | 415篇 |
2019年 | 527篇 |
2018年 | 509篇 |
2017年 | 419篇 |
2016年 | 712篇 |
2015年 | 489篇 |
2014年 | 651篇 |
2013年 | 1219篇 |
2012年 | 946篇 |
2011年 | 887篇 |
2010年 | 649篇 |
2009年 | 542篇 |
2008年 | 607篇 |
2007年 | 566篇 |
2006年 | 409篇 |
2005年 | 392篇 |
2004年 | 265篇 |
2003年 | 249篇 |
2002年 | 211篇 |
2001年 | 131篇 |
2000年 | 89篇 |
1999年 | 93篇 |
1998年 | 54篇 |
1997年 | 68篇 |
1996年 | 62篇 |
1995年 | 46篇 |
1994年 | 51篇 |
1993年 | 27篇 |
1992年 | 42篇 |
1991年 | 40篇 |
1990年 | 41篇 |
1989年 | 38篇 |
1988年 | 41篇 |
1987年 | 44篇 |
1986年 | 35篇 |
1985年 | 47篇 |
1984年 | 55篇 |
1983年 | 29篇 |
1982年 | 31篇 |
1981年 | 31篇 |
1980年 | 40篇 |
1979年 | 29篇 |
1978年 | 30篇 |
1977年 | 19篇 |
1976年 | 22篇 |
1974年 | 18篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
191.
Effects of cetyltrimethylammonium bromide (CTABr) micelles on second-order rate constants (k(n)(obs)) for nucleophilic reactions of amines (piperidine and n-butylamine) with ionized phenyl salicylate (PS(-)) reveal a nonlinear decrease with the increase in [D(n)] (where [D(n)] = [CTABr](T) - cmc) at a constant [NaBr] and 35 degrees C. The observed data, at a constant [NaBr], fit reasonably well to a pseudophase model of micelles, and such a data fit gives kinetic parameters such as CTABr micellar binding canstant (K(S)) of PS(-). The effect of [NaBr] upon K(S) is explained with the empirical relationship K(S) = K(S)(0)/(1 + psi[NaBr]), where psi is an empirical parameter. 相似文献
192.
The many fold aromatic ketones 2a‐d are versatile compounds for the synthesis of the many fold 1,2,3‐selenadiazole aromatic derivatives 5a‐d . The preparation starts with the reaction between the many fold bromomethylene benzene derivatives 1a‐d and 4‐hydroxyacetophenone, which are transformed through the reaction with semicarbazide hydrochloride or ethylhydrazine carboxylate into the corresponding semicarbazones derivatives 3a‐d or hydrazones 4a‐d . The reaction with selenium dioxide leads to regiospecific ring closure of semicarbazones or hydrazones to give the many fold 1,2,3‐selenadiazole aromatic derivatives in high yield. 相似文献
193.
Tetra- and pentapeptides of α-methylalanine give with PCl5, SOCl2 etc. intermediates which, with or without loss of amino adds, lead to bi- and tricyclic products containing imidazole and piperazine rings through different routes. 相似文献
194.
Syed Laik Ali 《Analytical and bioanalytical chemistry》1972,262(4):278-282
The different aspects of Vitamin D3 determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D3 in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D3 on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D3 zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination. 相似文献
195.
The new 10 μg l−1 arsenic standard in drinking water has been a spur to the search for reliable routine analytical methods with a limit of detection at the μg l−1 level. These methods also need to be easy to handle due to the routine analyses that are required in drinking water monitoring. Graphite furnace atomic absorption spectrometry (GFAAS) meets these requirements, but the limit of detection is generally too high except for methods using a pre-concentration or separation step. The use of a high-intensity boosted discharge hollow-cathode lamp decreases the baseline noise level and therefore allows a lower limit of detection. The temperature program, chemical matrix modifier and thermal stabilizer additives were optimized for total inorganic arsenic determination with GFAAS, without preliminary treatment. The optimal furnace program was validated with a proprietary software. The limit of detection was 0.26 μg As l−1 for a sample volume of 16 μl corresponding to 4.2 pg As. This attractive technique is rapid as 20 samples can be analysed per hour. This method was validated with arsenic reference solutions. Its applicability was verified with artificial and natural groundwaters. Recoveries from 91 to 105% with relative standard deviation <5% can be easily achieved. The effect of interfering anions and cations commonly found in groundwater was studied. Only phosphates and silicates (respectively at 4 and 20 mg l−1) lead to significant interferences in the determination of total inorganic arsenic at 4 μg l−1. 相似文献
196.
Reaction of benzotriazol‐1‐yl acetone 1 with phenyl isothiocyanate followed with α‐chloroacetone or ethyl‐α‐chloroacetate afforded 2‐anilinothiophenes 3 or 4 , respectively. Treatment of 3 with malononitrile at different reaction conditions afforded 6 or 7 . Reaction of 1 with CS2 in DMF and phenacylbromide afforded S‐alkylated thiophene 10 . Reactions of the latter compound with different active methylene nitriles afforded thienylthiopyridine derivatives 14 and 15 . Condensation of 10 with hydrazine hydrate afforded hydrazon derivative 16 . Reaction of thiophene 17 with formamide in DMF afforded 19 which converted to N‐thienylpyrimidine 20 when treated with malononitrile. The structure of the newly synthesized compounds has been established on the basis of their analytical and spectral data. The compounds were also investigated for antibacterial and antifungal activities. 相似文献
197.
Onur ahin Orhan Büyükgüngr Dursun Ali Kse Hacali Necefoglu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):m510-m512
The title compound, [Cu(C7H5O3)2(C6H6N2O)2(H2O)2], is a two‐dimensional hydrogen‐bonded supramolecular complex. The CuII ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridine N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R22(4), R22(8) and R22(15) rings which lead to one‐dimensional polymeric chains. An extensive two‐dimensional network of N—H...O and O—H...O hydrogen bonds and C—H...π interactions are responsible for crystal stabilization. 相似文献
198.
A series of new platinum(II) and platinum(IV) complexes of the type [PtII(HMI)2X] (where HMI=hexamethyleneimine, X=dichloro, sulfato, 1,1-cyclobutanedicarboxylato [CBDCA], oxalato, methylmalonato, or tatronato) and [PtIV(HMI)2Y2Cl2] (where Y=hydroxo, acetato, or chloro) were synthesized and characterized by infrared (IR) spectroscopy, 13C and 195Pt nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Among the complexes synthesized, [PtII(hexamethyleneimine)2(1,1-cyclobutanedicarboxylato)]·H2O was examined by single-crystal X-ray diffraction. The slightly distorted square planar coordination environment of the platinum metal includes the amino group of the hexamethyleneimine (HMI) molecule and the oxygen atoms of the carboxylato ligand. The cyclobutanedicarboxylic acid (CBDCA) molecule adopts six-member chelating rings with platinum. Hydrogen bonding plays an important part in holding the crystal lattice together. 相似文献
199.
Ali Raza Hala A. Hejazi Sami Ullah Khan M. Ijaz Khan Kamel Smida Iskander Tlili 《印度化学会志》2022,99(7):100568
In this investigation, a mixed convective nanoparticles fluid flow over an inclined plate is deliberated. The effects of slip boundary wall and magnetic field are also considered. The dimensionless governing system for the considered problem is attained by implementing recent definitions of fractional derivatives (FD). The generalized solution is obtained through the Laplace Transformation Scheme (LTS) for the momentum and thermal expressions. To improve the novelty and to demonstrate some more physical perception of the stated research work, some remarkable special cases of velocity distribution through CF and AB-fractional derivative concept are addressed, whose daily life implication is well known in the existing literature. Moreover, to evaluate the physical interest of the stated problem, the outcomes of the obtained system graphical illustrations are made by utilizing MATHEMATICA. As a result, we concluded that the aluminium oxide nanoparticles show more decaying behavior as compared to titanium oxide nanoparticles for temperature and velocity profile. Furthermore, both fields i.e., momentum and thermal distributions are increased with the help of rising estimations parameter. Current results report novel applications in enhancement of heat transfer, thermal engineering, chemical processes, engineering and electronics devices, solar systems, extrusion processes, fission reactions etc. 相似文献
200.
Richard G. Brereton Ali Rahmani Yi-zeng Liang Olav M. Kvalheim 《Photochemistry and photobiology》1994,59(1):99-110
Abstract –The products of chlorophyll allomerization in methanol were isolated and analyzed by open column sucrose chromatography, liquid chromatography mass spectrometry (LCMS) and DAD-HPLC (diode-array high-performance liquid chromatography). Four main bands were found with molecular ions of (a) 908, (b) 938, (c) 938 and (d) 938, consistent with the structures (a) 132 -hydroxy-chlorophyll a (II), (b) and (c) Mg(II)-31 ,32 -didehydro-151 -hydroxy-151 -methoxy-rhodochlorin-15 acetic acid δ-lactone 152 -methyl 173 -phytyl ester and its epimer (III) and (d) Mg(II)-31 ,32 -didehydro-rhodochlorin-15-glyoxylic acid 131 ,152 -dimethyl 173 -phytyl ester (IV), evidence enhanced by UV/visible spectroscopy, chromatographic coelutions and chemometrics. Chlorophyll a was degraded both in the dark and light, under O2 and N2 . DAD-HPLC of the resultant degradation mixtures were analyzed using the chemometric heuristic-evolving latent projection method for resolution. Ultraviolet/visible spectra of II and III are reproducibly extracted from the mixtures after a short degradation time, whereas III and IV are the dominant compounds after longer degradation times. Changes in relative elution order of IV using open column chromatography and reverse-phase HPLC are established. A possible allomerization pathway is proposed. 相似文献