全文获取类型
收费全文 | 2438篇 |
免费 | 130篇 |
国内免费 | 4篇 |
专业分类
化学 | 2140篇 |
晶体学 | 5篇 |
力学 | 27篇 |
数学 | 228篇 |
物理学 | 172篇 |
出版年
2024年 | 3篇 |
2023年 | 26篇 |
2022年 | 116篇 |
2021年 | 128篇 |
2020年 | 61篇 |
2019年 | 66篇 |
2018年 | 54篇 |
2017年 | 40篇 |
2016年 | 114篇 |
2015年 | 83篇 |
2014年 | 110篇 |
2013年 | 141篇 |
2012年 | 155篇 |
2011年 | 220篇 |
2010年 | 113篇 |
2009年 | 116篇 |
2008年 | 174篇 |
2007年 | 159篇 |
2006年 | 139篇 |
2005年 | 127篇 |
2004年 | 96篇 |
2003年 | 81篇 |
2002年 | 63篇 |
2001年 | 26篇 |
2000年 | 11篇 |
1999年 | 16篇 |
1998年 | 17篇 |
1997年 | 12篇 |
1996年 | 14篇 |
1995年 | 16篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 10篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1972年 | 2篇 |
1933年 | 2篇 |
排序方式: 共有2572条查询结果,搜索用时 15 毫秒
31.
Alvarez-Bercedo P Bond AD Haigh R Hopkins AD Lawson GT McPartlin M Moncrieff D Mosquera ME Rawson JM Woods AD Wright DS 《Chemical communications (Cambridge, England)》2003,(11):1288-1289
The reaction of CyPHNa with Sn(NMe2)2 in the presence of PMDETA (= (Me2NCH2CH2)2NMe) gives the title compound [(Sn(mu-PCy))3(Na x PMDETA)2] (1), containing an electron-deficient [(Sn(mu-PCy))]3(2-) dianion with a novel two-electron, three centre (2e-3c) bonding arrangement. 相似文献
32.
Jerzy Lisowski Marta Paluch Tadeusz Lis 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):123-129
The template condensation of (R)-2,2′-diamino-1,1′-binaphthyl and 2,6-diformylpyridine leads to lanthanide(III) complexes of the new chiral hexaaza macrocycle L that adopts highly twisted conformation in [LnL](NO3)3 complexes. The complexes have been characterised by ESI MS spectrometry and NMR spectroscopy. The analogous N2O4 chiral crown ether L2 that has the same carbon skeleton as L does not exhibit tendency to bind lanthanide(III) ions. The X-ray crystal structure of L2 exhibit squeezed conformation of the macrocycle and spatial disposition of donor atoms that does not predispose it for coordination of lanthanide(III) ions. 相似文献
33.
A new and highly stereoselective palladium-catalyzed synthesis is reported, based on two subsequent insertions of the bicyclo[2.2.1]heptene system into an aryl or vinylpalladium bond, formed in situ from aryl or vinyl bromides. 相似文献
34.
A new sensitive and selective preconcentration-fluorimetric method for determination of terazosin based on its native fluorescence was developed. The analyte, initially present in aqueous matrix, was treated with an extractive non-ionic surfactant solution and separated by the clouding phenomenon. The optimum analytical conditions for terazosin assay were established. Under these conditions, linear calibration curves were obtained over the range of 1 × 10−5 to 7.0 μg mL−1 with detection and quantification limits of 1.11 × 10−5 and 3.7 × 10−5 μg mL−1, respectively. Additionally, the binding constant (KB) for the terazosin-PONPE 7.5 system was determined given a value of 1028 L mol−1. The developed coupled methodology, which thoroughly satisfies the typical requirements for pharmaceutical control processes, was proved to be appropriate for monitoring terazosin in actual pharmaceutical formulations and biological fluid sample. The results were validated by recovery test and by comparison with other reported methods, being highly satisfactory. 相似文献
35.
Structure of colloid silica determined by viscosity measurements 总被引:3,自引:0,他引:3
The viscosity of nanosized colloid silica suspensions, used as binders in the investment casting, was determined as a function of their weight fraction reaching 52%. A new capillary viscometer was used whose construction eliminated sedimentation effects. The experiments have been carried out at fixed pH 10.0 and controlled ionic strength. It was found that for a low silica concentration range (weight fraction below 5%) the suspension viscosity increased more rapidly than the Einstein theory predicts. This anomalous behavior could not be explained in terms of the primary electroviscous effect predicted to be a few orders of magnitude smaller as observed. This discrepancy was accounted for by postulating a fuzzy, gel-like structure of colloid silicas used in our experiments. Hence, the apparent hydrodynamic radius of silica particles in aqueous suspensions was found to be larger than the primary particle size in accordance with previous observations. Based on this postulate, an apparent density of the silica sols was found to be 1.32-1.37 g/cm(3) instead of 2.2-2.32 g/cm(3) as determined from the suspension dilution method. This behavior was interpreted in terms of the core/shell model with high shell porosity, reaching 85%. Similarly, for higher concentration ranges, silica viscosity increased more rapidly with increased sol concentration than predicted by the Batchelor model derived for hard particles. The deviation was attributed to the secondary electroviscous effect stemming from the electrostatic interactions among silica particles in sheared suspensions. This effect has quantitatively been interpreted in terms of Russel's theory. On the other hand, for the high concentration range the experimental results were well accounted for by the Dougherty-Krieger model. By exploiting our experimental findings a sensitive method of determining the structure and apparent density of silica sols in aqueous media was proposed. 相似文献
36.
A previously described pyrolysis device with a movable reaction zone was used in the present work for thermal degradation of cured novolac and resol resins. After the pyrolysis the usual major components were identified, as well as relatively low-volatile aromatic compounds which were revealed after their separation in a capillary chromatographic column. Among the latter components, for both types of cured resins, xanthene and its methyl derivatives were found. The isomers of bis(hydroxyphenyl)methane were found in considerable quantities only in the case of partially cured novolac resins which contained any linear sequences in their structure. 相似文献
37.
38.
Regina Y. Moriya Adilson R. Gonçalves Marta C. T. Duarte 《Applied biochemistry and biotechnology》2005,121(1-3):171-181
Organosolv (ethanol/water and acetosolv) pulps were treated with Bacillus pumilus xylanase for 4, 8, and 12 h and compared with commercial Cartazyme HS xylanase-treated pulps. Treatment of ethanol/water pulps with B. pumilus xylanase increased viscosity by 40% in 8 h of treatment compared with pulps treated without enzyme. However, acetosolv pulps treated with B. pumilus xylanase lost viscosity. Ethanol/water pulps treated with Cartazyme had a viscosity of 18.5 cP in 4 h of treatment. In the acetosolv pulps treated with commercial enzyme, the loss of viscosity was 20% compared with pulps treated without enzyme. Ethanol/water pulps treated with B. pumilus and Cartazyme had similar effects: a 44% reduction in kappa number for pulps treated with enzyme followed by alkaline extraction compared with pulps treated with alkaline extraction. In acetosolv pulps treated with B. pumilus, the kappa number was from 12 to 18, compared with pulps treated without enzyme, which had a 40% reduction in 4 and 12 h and a 60% reduction in 8 h. Cartazyme-treated acetosolv pulps had a kappa number of 14 in 4 and 8 h of treatment. For 12 h of treatment, the kappa number was 8. Fourier transform infrared spectra of the pulps showed that enzyme-treated pulps had changes in the 1000 cm?1 absorption owing to a C-O bond present in esters. Using principal component analysis, it is possible to differentiate the unbleached pulps and enzyme-treated pulps. 相似文献
39.
The suitability of the differential thermal and thermogravimetric techniques for the determination of compositions of solid and soft drug formulations has been studied. A total of 117 pharmaceutical preparations have been examined, including powders, dusting powders, capsules, granulates, tablets, tablets for sucking, effervescent tablets, dragees, suppositories and ointments. Both techniques have been shown to be applicable for identification of pharmaceutical preparations. A specification has been made of thermal processes which can be employed for assaying the main components of the preparations. A rough estimate of the relative errors has been given.
Zusammenfassung Die Eignung der differentialthermoanalytischen und thermogravimetrischen Methoden zur Bestimmung der Zusammensetzung fester und weicher ArzeneiprÄparate wurde studiert. Eine Gesamtzahl von 117 pharmazeutischen PrÄparaten, einschliesslich Pulver, Streupulver, Kapseln, Granulate, Tabletten, Saugtabletten, Brausetabletten, Dragees, Suppositorien und Salben wurde untersucht. Beide Methoden erwiesen sich als anwendbar zur Identifizierung pharmazeutischer PrÄparate. Eine Spezifizierung der zur Bestimmung der Hauptkomponenten der PrÄparate geeigneten thermischen Prozesse wurde durchgeführt. Eine grobe SchÄtzung der relativen Fehler wurde gegeben.
Résumé On a étudié l'utilité des techniques ATD et TG pour déterminer la composition des préparations pharmaceutiques solides et molles. On a soumis à l'examen un total de 117 préparations pharmaceutiques comprenant des poudres, des talcs, des capsules, des granulats, des tablettes, des tablettes à sucer, des tablettes effervescentes, des dragées, des suppositoires et des onguents. Les deux techniques se sont montrées applicables à l'identification des préparations pharmaceutiques. On a effectué une spécification des processus thermiques qui se prÊtent au dosage des composants essentiels des préparations. On a donné une évaluation approximative des erreurs relatives.
- - . 117 , , - , , , , , , , . , - . , . - .相似文献
40.
Morales D Pérez J Riera L Riera V Miguel D Mosquera ME García-Granda S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4132-4143
Reactions of the complex [MoCl(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1) (phen=1,10-phenanthroline) with potassium arylamides were used to synthesize the amido complexes [Mo(N(R)Ar)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (R=H, Ar=Ph, 2 a; R=H, Ar=p-tolyl, 2 b; R=Me, Ar=Ph; 2 c). For 2 b the Mo-N(amido) bond length (2.105(4) A) is consistent with it being a single bond, with which the metal attains an 18-electron configuration. The reaction of 2 b with HOTf affords the amino complex [Mo(eta(3)-C(3)H(4)-Me-2)(NH(2)(p-tol))(CO)(2)(phen)]OTf (3-OTf). Treatment of 3-OTf with nBuLi or KN(SiMe(3))(2) regenerates 2 b. The new amido complexes react with CS(2), arylisothiocyanates and maleic anhydride. A single product corresponding to the formal insertion of the electrophile into the Mo-N(amido) bond is obtained in each case. For maleic anhydride, ring opening accompanied the formation of the insertion product. The reaction of 2 b with maleimide affords [Mo(eta(3)-C(3)H(4)-Me-2)[NC(O)CH=CHC(O)](CO)(2)(phen)] (7), which results from simple acid-base metathesis. The reaction of 2 b with (p-tol)NCO affords [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(eta(2)-MoO(4))] (8), which corresponds to oxidation of one third of the metal atoms to Mo(VI). Complex 8 was also obtained in the reactions of 2 b with CO(2) or the lactide 3,6-dimethyl-1,4-dioxane-2,5-dione. The structures of the compounds 2 b, 3-OTf, [Mo(eta(3)-C(3)H(4)-Me-2)[SC(S)(N(H)Ph)](CO)(2)(phen)] (4), [Mo(eta(3)-C(3)H(4)-Me-2)[SC(N(p-tol))(NH(p-tol))](CO)(2)(phen)] (5 a), and [Mo(eta(3)-C(3)H(4)-Me-2)[OC(O)CH=CHC(O)(NH(p-tol))](CO)(2)(phen)] (6), 7, and 8 (both the free complex and its N,N'-di(p-tolyl)urea adduct) were determined by X-ray diffraction. 相似文献