全文获取类型
收费全文 | 4468篇 |
免费 | 154篇 |
国内免费 | 19篇 |
专业分类
化学 | 3252篇 |
晶体学 | 36篇 |
力学 | 90篇 |
数学 | 601篇 |
物理学 | 662篇 |
出版年
2024年 | 4篇 |
2023年 | 29篇 |
2022年 | 83篇 |
2021年 | 112篇 |
2020年 | 78篇 |
2019年 | 69篇 |
2018年 | 62篇 |
2017年 | 65篇 |
2016年 | 165篇 |
2015年 | 109篇 |
2014年 | 124篇 |
2013年 | 267篇 |
2012年 | 340篇 |
2011年 | 370篇 |
2010年 | 201篇 |
2009年 | 154篇 |
2008年 | 317篇 |
2007年 | 295篇 |
2006年 | 246篇 |
2005年 | 288篇 |
2004年 | 215篇 |
2003年 | 187篇 |
2002年 | 157篇 |
2001年 | 57篇 |
2000年 | 53篇 |
1999年 | 32篇 |
1998年 | 41篇 |
1997年 | 30篇 |
1996年 | 66篇 |
1995年 | 27篇 |
1994年 | 30篇 |
1993年 | 39篇 |
1992年 | 21篇 |
1991年 | 29篇 |
1990年 | 35篇 |
1989年 | 24篇 |
1988年 | 25篇 |
1987年 | 29篇 |
1986年 | 15篇 |
1985年 | 28篇 |
1984年 | 19篇 |
1983年 | 12篇 |
1982年 | 17篇 |
1981年 | 11篇 |
1980年 | 13篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1974年 | 6篇 |
排序方式: 共有4641条查询结果,搜索用时 0 毫秒
141.
Figuerola A Ribas J Llunell M Casanova D Maestro M Alvarez S Diaz C 《Inorganic chemistry》2005,44(20):6939-6948
The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions. 相似文献
142.
A simple and fast analytical procedure has been developed for the determination of As, Sb, Se, Te and Bi in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS). Samples were treated with aqua regia for 10 min in an ultrasound water bath and pre-reduced with KBr for total Se and Te determination or with KI and ascorbic acid for total As and Sb, the determination of Bi being possible in all with or without pre-reduction. Slurries of samples, in the presence of antifoam A, were treated with NaBH4 in HCl medium to obtain the corresponding hydrides, and AFS measurements were processed in front of external calibrations prepared and measured in the same way as samples. Results obtained by the developed procedure compare well with those found after microwave-assisted complete digestion of samples. The proposed method is simple and fast, and only 1 ml of milk is needed. The values obtained for detection limit are 2.5, 1.6, 3, 6 and 7 ng l−1 for As, Sb, Se, Te and Bi respectively in the diluted samples, with average relative standard deviation values of 3.8, 3.1, 1.9, 6.4 and 1.2% for three independent analysis of a series of commercially available samples of different origin. Data found in Spanish market samples varied from 3.2±0.3 to 11.3±0.2 ng g−1 As, from 3.1±0.2 to 11.6±0.4 ng g−1 Sb, from 10.7±0.5 to 25.5±0.4 ng g−1 Se, from 0.9±0.2 to 9.4±0.6 ng g−1 Te and from 11.5±0.1 to 27.7±0.4 ng g−1 Bi. 相似文献
143.
Miguel F. Braa Jos M. Castellano Maria L. Lpez Rodriguez Magdalena Glvez Manuel R. Amil Enrique Rubio 《Journal of heterocyclic chemistry》1987,24(2):369-371
Hydrolysis of N,N'-diacyl-1,2-di(4-pyridyl)ethylenediamines 1 in aqueous sulfuric acid gave the corresponding imidazolines 3. 1,2-Di-(4-pyridyl)ethylenediamine 2 was prepared in 61 % yield by treating N,N'-di-t-butyl-oxycarbonyl-1,2-di(4-pyridyl)ethylenediamine 4 with trifluoroacetic acid or in 94% yield by the hydrolysis under basic conditions of N,N'-diphthaloylglycyl-1,2-di(4-pyridy)ethylenediamine 13. 相似文献
144.
The first stereoselective syntheses of the naturally occurring, ,β-unsaturated lactone hyptolide 1 and of its nonnatural epimer at C-6 are described. Ethyl l-lactate was the chiral starting material. Key steps of these syntheses were a Brown's asymmetric allylation, a Carreira's asymmetric ethynylation and a ring closing metathesis. 相似文献
145.
In this work, different extracts from the microalga Spirulina platensis are obtained using pressurized liquid extraction (PLE) and four different solvents (hexane, light petroleum, ethanol and water). Different extraction temperatures (115 and 170 degrees C) were tested using extraction times ranging from 9 to 15 min. The antioxidant activity of the different extracts is determined by means of an in vitro assay using a free radical method. Moreover, a new and fast method is developed using micellar electrokinetic chromatography with diode array detection (MEKC-DAD) to provide a preliminary analysis on the composition of the extracts. This combined application (i.e., in vitro assays plus MEKC-DAD) allowed the fast characterization of the extracts based on their antioxidant activity and the UV-vis spectra of the different compounds found in the extracts. To our knowledge, this work shows for the first time the great possibilities of the combined use of PLE-in vitro assay-MEKC-DAD to investigate natural sources of antioxidants. 相似文献
146.
Cuesta L Gerbino DC Hevia E Morales D Navarro Clemente ME Pérez J Riera L Riera V Miguel D del Río I García-Granda S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1765-1777
The hydroxo compounds [Re(OH)(CO)(3)(N-N)] (N-N=bipy, 2 a; Me(2)-bipy, 2 b) were prepared in a biphasic H(2)O/CH(2)Cl(2) medium by reaction of [Re(OTf)(CO)(3)(N-N)] with KOH. In contrast, when anhydrous CH(2)Cl(2) was used, the binuclear hydroxo-bridged compound [[Re(CO)(3)(bipy)](2)(mu-OH)]OTf (3-OTf) was obtained. Compound [Re(OH)(CO)(3)(Me(2)-bipy)] (2 b) reacted with phenyl acetate or vinyl acetate to afford [Re(OAc)(CO)(3)(Me(2)-bipy)] (4) and phenol or acetaldehyde, respectively. The reactions of [Mo(OH)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1), 2 a, and 2 b toward several unsaturated organic electrophiles were studied. The reaction of 1 with (p-tolyl)isocyanate afforded an adduct of N,N'-di(p-tolyl)urea and the carbonato-bridged compound [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(mu-eta(1)(O),eta(1)(O)-CO(3))] (5). In contrast, the reaction of 2 a with phenylisocyanate afforded [Re(OC(O)NHPh)(CO)(3)(bipy)] (6); this results from formal PhNCO insertion into the O-H bond. On the other hand, compounds [Mo[SC(O)NH(p-tolyl)](eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (7), [Re[SC(O)NH(p-tolyl)](CO)(3)(Me(2)-bipy)] (8 a), and [Re[SC(O)NHEt](CO)(3)(Me(2)-bipy)] (8 b) were obtained by reaction of 1 or 2 b with the corresponding alkyl or aryl isothiocyanates. In those cases, RNCS was inserted into the M-O bond. The reactions of 1, 2 a, and 2 b with dimethylacetylenedicarboxylate (DMAD) gave the complexes [Mo[C(OH)-C(CO(2)Me)C(CO(2)Me)-O](eta(3)-C(3)H(4)-Me-2)(CO)(phen)] (9) and [Re[C(OH)C(CO(2)Me)C(CO(2)Me)O](CO)(2)(N-N)] (N-N=bipy, 10 a; Me(2)-bipy, 10 b). The molecules of these compounds contain five-membered metallacycles that are the result of coupling between the hydroxo ligand, DMAD, and one of the CO ligands. The new compounds were characterized by a combination of IR and NMR spectroscopy, and for [[Re(CO)(3)(bipy)(2)(mu-OH)]BF(4) (3-BF(4)), 4, 5, 6, 7, 8 b, 9, and 10 b, also by means of single-crystal X-ray diffraction. 相似文献
147.
Pérez González M Gonzalez Díaz H Molina Ruiz R Cabrera MA Ramos de Armas R 《Journal of chemical information and computer sciences》2003,43(4):1192-1199
A new application of TOPological Sub-structural MOlecular DEsign (TOPS-MODE) was carried out in herbicides using computer-aided molecular design. Two series of compounds, one containing herbicide and the other containing nonherbicide compounds, were processed by a k-Means Cluster Analysis in order to design the training and prediction sets. A linear classification function to discriminate the herbicides from the nonherbicide compounds was developed. The model correctly and clearly classified 88% of active and 94% of inactive compounds in the training set. More specifically, the model showed a good global classification of 91%, i.e., (168 cases out of 185). While in the prediction set, they showed an overall predictability of 91% and 92% for active and inactive compounds, being the global percentage of good classification of 92%. To assess the range of model applicability, a virtual screening of structurally heterogeneous series of herbicidal compounds was carried out. Two hundred eighty-four out of 332 were correctly classified (86%). Furthermore this paper describes a fragment analysis in order to determine the contribution of several fragments toward herbicidal property; also the present of halogens in the selected fragments were analyzed. It seems that the present TOPS-MODE based QSAR is the first alternate general "in silico" technique to experimentation in herbicides discovery. 相似文献
148.
Mohammad Abul‐Haj Miguel Quirs Juan M. Salas 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):934-935
The title compound, [Ni(NCS)2(C5H4N4O)2(H2O)2], crystallizes in the triclinic space group P. The molecular unit contains two neutral molecules of 4,5‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidin‐5‐one (5HtpO) coordinated through the N atom in position 3, two thiocyanate ligands coordinated through their N atoms and two water molecules completing an octahedral environment around the NiII ion, which lies on a centre of inversion. The structure is stabilized by hydrogen bonding. Distances in the coordination sphere are Ni—N3(5HtpO) 2.132 (2), Ni—O(water) 2.085 (2) and Ni—N(thiocyanato) 2.040 (2) Å. 相似文献
149.
Zully A. Benzo Manuelita Velosa Claudio Ceccarelli Miguel Guardia Amparo Salvador 《Fresenius' Journal of Analytical Chemistry》1991,339(4):235-239
Summary The literature on the application of the slurry technique to biological materials is reviewed. It is obvious from the various applications that the most frequently employed atomization method for slurry analysis in biological materials is electrothermal atomization using either graphite tube or platform atomizers. The slurry technique is particularly useful when certified reference materials are not available and when the standard addition method is to be avoided. The literature survey revealed that this technique compares favourably with other methods for the determination of trace metals in biological materials. 相似文献
150.
Francisco Vega Reyes lvaro Rodríguez-Rivas Juan F. Gonzlez-Saavedra Miguel A. Lpez-Castao 《Entropy (Basel, Switzerland)》2022,24(11)
We study an air-fluidized granular monolayer composed of plastic spheres which roll on a metallic grid. The air current is adjusted so that the spheres never lose contact with the grid and so that the dynamics may be regarded as pseudo two dimensional (or two dimensional, if the effects of the sphere rolling are not taken into account). We find two surprising continuous transitions, both of them displaying two coexisting phases. Moreover, in all the cases, we found the coexisting phases display a strong energy non-equipartition. In the first transition, at a weak fluidization, a glass phase coexists with a disordered fluid-like phase. In the second transition, a hexagonal crystal coexists with the fluid phase. We analyze, for these two-phase systems, the specific diffusive properties of each phase, as well as the velocity correlations. Surprisingly, we find a glass phase at a very low packing fraction and for a wide range of granular temperatures. Both phases are also characterized by strong anticorrelated velocities upon a collision. Thus, the dynamics observed for this quasi two-dimensional system unveil phase transitions with peculiar properties, very different from the predicted behavior in well-know theories for their equilibrium counterparts. 相似文献