全文获取类型
收费全文 | 3958篇 |
免费 | 188篇 |
国内免费 | 2篇 |
专业分类
化学 | 3259篇 |
晶体学 | 23篇 |
力学 | 40篇 |
数学 | 486篇 |
物理学 | 340篇 |
出版年
2024年 | 4篇 |
2023年 | 48篇 |
2022年 | 32篇 |
2021年 | 59篇 |
2020年 | 72篇 |
2019年 | 79篇 |
2018年 | 88篇 |
2017年 | 85篇 |
2016年 | 169篇 |
2015年 | 165篇 |
2014年 | 152篇 |
2013年 | 248篇 |
2012年 | 319篇 |
2011年 | 351篇 |
2010年 | 199篇 |
2009年 | 154篇 |
2008年 | 297篇 |
2007年 | 295篇 |
2006年 | 264篇 |
2005年 | 220篇 |
2004年 | 158篇 |
2003年 | 172篇 |
2002年 | 122篇 |
2001年 | 44篇 |
2000年 | 32篇 |
1999年 | 25篇 |
1998年 | 13篇 |
1997年 | 27篇 |
1996年 | 40篇 |
1995年 | 14篇 |
1994年 | 14篇 |
1993年 | 15篇 |
1992年 | 17篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 15篇 |
1984年 | 15篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 10篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1974年 | 5篇 |
1973年 | 7篇 |
排序方式: 共有4148条查询结果,搜索用时 15 毫秒
31.
32.
33.
Garcia EM Sanchez MD Tonetto G Volpe MA 《Journal of colloid and interface science》2005,292(1):179-185
The preparation of different samples of vanadia supported on ultrastable zeolite (VO(x)/USY) is discussed. The samples were prepared in order to obtain highly dispersed V-species, avoiding the formation of crystalline vanadia and the destruction of the zeolite framework. Two methods were employed for preparing VO(x)/USY samples: an organic route using V(AcAc)3 and an inorganic route using NH4VO3. The characterization of the samples was performed with XRD, TPR, NH3-TPD, and N2 isotherms. From these results it is concluded that when VO(x) is supported on the surface of USY from acidic aqueous solution of ammonium metavanadate, the destruction of the zeolite framework is accomplished. For higher pH values in the impregnating solution, undesired V2O5 is formed on the USY surface. On the other hand, VO(x)/USY prepared from the organic precursor shows no destruction of the USY structure. In addition, highly dispersed VO(x) are formed, though for relatively high V loadings (6%) an obstruction of the zeolite windows takes place. The samples are tested as catalysts for gas phase dehydrogenation of n-butane to olefins. The catalysts prepared from NH4VO3 are almost inactive for the reaction. On the other hand, both samples prepared from V(AcAc)3 present initial conversion levels in the 8-12% range. However, the selectivity depends on the V loading, the catalysts with 6% loading being the most selective (75%). The catalytic patterns of the samples (activity and selectivity) are in agreement with the physicochemical features of the VO(x)/USY surface. 相似文献
34.
Casas JS Castaño MV García-Tasende MS Rodríguez-Castellón E Sánchez A Sanjuán LM Sordo J 《Dalton transactions (Cambridge, England : 2003)》2004,(13):2019-2026
Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature. 相似文献
35.
Sánchez-Moreno MJ Gómez-Coca RB Fernández-Botello A Ochocki J Kotynski A Griesser R Sigel H 《Organic & biomolecular chemistry》2003,1(10):1819-1826
The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided. 相似文献
36.
Functionalized keto-enamines 6 were obtained by nucleophilic addition of enol ethers to the imine moiety of 2-azadienes derived from dehydroaspartic esters 4. Reactions of 2-azadiene 4c containing three electron-withdrawing substituents (CO(2)R) with enol ethers 5 in the presence of lithium perchlorate led to the formation of tetrahydropyridine derivatives 7 in a regio- and stereoselective fashion. 2H-[1,3]-oxazines 10 and pyridine derivatives 12 and 13 were obtained by heterocycloaddition reactions of electron-poor azadienes 4d-g containing two electron-withdrawing substituents (4-O(2)N-C(6)H(4), CO(2)R) in positions 1 and 4 with carbonyl derivatives (ethyl glyoxalate 9a and diethyl ketomalonate 9b) and the electron-deficient olefin tetracyanoethylene 11. 相似文献
37.
Seghezzo L Trupiano AP Liberal V Todd PG Figueroa ME Gutiérrez MA Da Silva Wilches AC Iribarnegaray M Guerra RG Arena A Cuevas CM Zeeman G Lettinga G 《Applied biochemistry and biotechnology》2003,109(1-3):167-180
A pilot-scale sewage treatment system consisting of two upflow anaerobic sludge bed (UASB) reactors followed by five waste stabilization ponds (WSPs) in series was studied under subtropical conditions. The first UASB reactor started up in only 1 mo (stable operation, high chemical oxygen demand [COD] removal efficiency, low volatile fatty acids concentration in the effluent, alkalinity ratio above 0.7, biogas production above 0.1 Nm3/kg of CODremoved). Removal efficiencies up to 90% were obtained in the anaerobic steps at a hydraulic retention time of 6 + 4 h (80% removal in the first step). Fecal coliform removal in the whole system was 99.9999% (99.94% in anaerobic steps and 99.98% in WSPs). COD balances over UASB reactors are provided. A minimum set of data necessary to build COD balances is proposed. Intermittent sludge washout was detected in the reactors with the COD balances. Sludge washout from single-step UASB reactors should be monitored and minimized in order to ensure constant compliance with discharge standards, especially when no posttreatment is provided. The system combined high COD and fecal coliform removal efficiency with an extremely low effluent concentration, complying with discharge standards, and making it an attractive option for sewage treatment in subtropical regions. 相似文献
38.
Mikkelsen LM Hernáiz MJ Martín-Pastor M Skrydstrup T Jiménez-Barbero J 《Journal of the American Chemical Society》2002,124(50):14940-14951
The conformational properties of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man in solution have been carefully analyzed by a combination of NMR spectroscopy and time-averaged restrained molecular dynamics. It has been found that both the alpha-1,3- and the alpha-1,6-glycosidic linkages show a major conformational averaging. Unusual Phi ca. 60 degrees orientations for both Phi torsion angles are found. Moreover, a major conformational distinction between the natural compound and the glycomimetic affects to the behavior of the omega(16) torsion angle around the alpha-1 --> 6-linkage. Despite this increased flexibility, the C-glycosyl analogue is recognized by three mannose binding lectins, as shown by NMR (line broadening, TR-NOE, and STD) and surface plasmon resonance (SPR) methods. Moreover, a process of conformational selection takes place, so that these lectins probably bind the glycomimetic similarly to the way they recognize the natural analogue. Depending upon the architecture and extension of the binding site of the lectin, loss or gain of binding affinity with respect to the natural analogue is found. 相似文献
39.
Aurora González-Portal F. Bermejo-Martínez C. Baluja-Santos María Cristina Diez-Rodríguez 《Microchemical Journal》1985,31(3):368-374
A new method for the Spectrophotometric determination of bismuth using N-(2-acetamido)iminodiacetic acid as complexometric agent is proposed. The complex is formed in a wide pH range, 5.5–7.5, and has a maximum absorption at 265 nm. Beer's law is obeyed in the interval 3.8–17.9 μg of bismuth(III)/ml, with a minimum photometric error of 2.3. The molar absorptivity is 9.1 × 103 liters/cm mol. The stoichiometry of the reaction takes place in the metal-to-ligand ratio 1:2. The interferences produced by the more common ions are studied. The method has been successfully applied to the determination of bismuth in pharmaceutical formulations. 相似文献
40.
Gutiérrez MC Sleegers A Simpson HD Alphand V Furstoss R 《Organic & biomolecular chemistry》2003,1(20):3500-3506
The first fluorogenic assay allowing for detection of microbial enzymes able to perform Baeyer-Villiger oxidation is described. This is based on the use of 4-oxopentyl umbelliferyl ether 1 as a fluorogenic substrate. When Baeyer-Villigerases active against this test ketone are present in the selected whole cells, 1 is transformed into 3-hydroxypropyl umbelliferyl ether 3, which, in a subsequent step, releases the fluorescent product umbelliferone. Different microorganisms, known to be endowed with Baeyer-Villigerase activity, were assayed. 相似文献