全文获取类型
收费全文 | 33459篇 |
免费 | 1310篇 |
国内免费 | 162篇 |
专业分类
化学 | 23080篇 |
晶体学 | 262篇 |
力学 | 640篇 |
综合类 | 7篇 |
数学 | 4542篇 |
物理学 | 6400篇 |
出版年
2023年 | 285篇 |
2022年 | 244篇 |
2021年 | 418篇 |
2020年 | 565篇 |
2019年 | 566篇 |
2018年 | 738篇 |
2017年 | 664篇 |
2016年 | 1280篇 |
2015年 | 1069篇 |
2014年 | 1068篇 |
2013年 | 2157篇 |
2012年 | 2425篇 |
2011年 | 2578篇 |
2010年 | 1493篇 |
2009年 | 1220篇 |
2008年 | 2153篇 |
2007年 | 2104篇 |
2006年 | 1870篇 |
2005年 | 1656篇 |
2004年 | 1346篇 |
2003年 | 1018篇 |
2002年 | 926篇 |
2001年 | 687篇 |
2000年 | 598篇 |
1999年 | 452篇 |
1998年 | 326篇 |
1997年 | 251篇 |
1996年 | 383篇 |
1995年 | 239篇 |
1994年 | 235篇 |
1993年 | 293篇 |
1992年 | 265篇 |
1991年 | 174篇 |
1990年 | 165篇 |
1989年 | 136篇 |
1988年 | 140篇 |
1987年 | 140篇 |
1986年 | 124篇 |
1985年 | 189篇 |
1984年 | 160篇 |
1983年 | 129篇 |
1982年 | 119篇 |
1981年 | 108篇 |
1980年 | 79篇 |
1979年 | 109篇 |
1978年 | 98篇 |
1977年 | 96篇 |
1976年 | 89篇 |
1975年 | 85篇 |
1973年 | 93篇 |
排序方式: 共有10000条查询结果,搜索用时 17 毫秒
101.
The global optimization basin-hopping (BH) method has been used to locate the global minima (GM) of Mg(n)F(2n) (n=1-30) clusters using a Born-Mayer-type potential. Some of the GM were particularly difficult to find, requiring more than 1.5 x 10(4) BH steps. We have found that both the binding energy per MgF2 unit and the effective volume of the GM isomers increase almost linearly with n, and that cluster symmetry decreases with cluster size. The data derived from the BH runs reveal a growing density of local minima just above the GM as n increases. Despite this, the attraction basin around each GM is relatively large, since after all their atomic coordinates are randomly displaced by values as high as 2.0 bohrs, the perturbed structures, upon reoptimization, relax back to the GM in more than 50% of the cases (except for n=10 and 11). The relative stabilities derived from energy second differences suggest that n=8,10,13,15, and 20 are probably the magic numbers for these systems. Mass spectrum experiments would be very useful to clarify this issue. 相似文献
102.
Fernández-Varela R Suárez-Rodríguez D Gómez-Carracedo MP Andrade JM Fernández E Muniategui S Prada D 《Talanta》2005,68(1):116-125
The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation. 相似文献
103.
The principle of tandem on-line continuous separation techniques as an alternative means of introducing samples into plasmas was applied to the development of a sensitive, selective and convenient method for the determination of arsenic by inductively coupled plasma atomic emission spectrometry (ICP-AES). Arsenic is continuously extracted as AsI3 into xylene from the sample dissolved in 0.1 M potassium iodide solution in 7.2 M hydrochloric acid. The xylene phase (containing the analyte) is continuously mixed on-line with NaBH4 in dimethylformamide and acetic acid solutions. Arsine is thus continuously generated directly from the organic phase and is separated in a gas—liquid separation device which prevents most of the xylene phase vapour from reaching the ICP. The system was optimized for the continuous extraction of AsI3, the direct generation of arsine from xylene and the final ICP determination of arsenic. Finally, the tandem on-line continuous separation ICP detection system was applied to the determination of arsenic in real samples (white metal, cast iron, cupro-nickel and orchard leaves standard materials). Very good agreement between the experimental results and the certified values was obtained. 相似文献
104.
The indications of a Clark-type electrochemical sensor with a polyethylene foil used as a membrane are noticeably changed if vapours of chlorine derivatives of methane (CCl4, CHCl3, CH2Cl2) are present in the atmosphere examined and the sensor has been calibrated in an atmosphere from which those vapours were absent. The sensitivity of the sensor increases and tends to deviate from linearity. The increase is more profound, when the number of chlorine atoms within a molecule of the vapour increases, the partial pressure of the vapour increases and the temperature of the atmosphere examined decreases. If the vapours affect the membrane for a long time, the response time decreases. If the membrane is freshly subjected to the influence of the vapours, a longer period of time is needed to reach a stable indication corresponding to the partial pressure of oxygen actually observed. 相似文献
105.
Pulkkinen S Noguera M Rodríguez-Santiago L Sodupe M Bertran J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(23):4393-4399
The intramolecular proton transfer in cationized glycine and chlorine substituted derivatives with M = Na+, Mg2+, Ni+, Cu+, and Cu2+ has been studied with the three parameter B3LYP density functional method. The coordination of metal cations to the oxygens of the carboxylic group of glycine stabilizes the zwitterionic structure. For all monocations the intramolecular proton transfer occurs readily with small energy barriers (1-2 kcalmol(-1)). For the dication Mg2+ and Cu2+ systems, the zwitterionic structure becomes very stable. However, whereas for Mg2+, the proton transfer process takes place spontaneously, for Cu2+ the reaction occurs with an important energy barrier. The substitution of the hydrogens of the amino group by chlorine atoms decreases the basicity of nitrogen, which destabilizes the zwitterionic structure. For monosubstituted glycine complexed with Na+, the zwitterionic structure still exists as a minimum, but for disubstituted glycine no minimum appears for this structure. In contrast, for Mg2+ complexed to mono- and disubstituted glycine, the zwitterionic structure remains the only minimum, since the enhanced electrostatic interaction with the dication overcomes the destabilizing effect of the chlorine atoms. 相似文献
106.
R. Usón L.A. Oro D. Carmona M.A. Esteruelas C. Foces-Foces F.H. Cano S. García-Blanco A.Vázquez De Miguel 《Journal of organometallic chemistry》1984,273(1):111-128
A new series of cationic areneiridium(I) complexes of formula [Ir(barrelene)(arene)]+ or [Ir(barrelene)(PhNRPh)]+ (R= Ph or H) have been synthesized from neutral iridium complexes of the type [IrY(barrelene)]x (barrelene = Me3TFB, Y = Cl or OMe (x = 2), Y = acac (x = 1); barrelene = TFB, Y = OMe (x = 2), Y = acac (x = 1)). The crystal structures of [Ir(Me3TFB)(1,4-C6H4Me2)]ClO4 and [Ir(TFB)(PhNPh2)]BF4·CH2Cl2 have been determined by X-ray diffraction. They crystallize in the space groups Pbca and Pna21 respectively with lattice constants of 17.6947(11), 15.8072(10), 16.0019(11) Å and 9.8059(2), 20.8097(9), 14.3367(4) Å. Final R factors were 0.063 and 0.042 for the observed data. Both complexes show a staggered arrangement between the arene and the TFB moieties and deviation from planarity of the coordinated arene ligands. In the second complex the IrC and NC distances, the CNC angle, the type of arene puckering, and the spectroscopic data indicate a distortion of the coordinated arene towards a η5-coordinated iminocyclohexadienyl form. 相似文献
107.
M. García-León C. I. Sánchez-Angulo 《Journal of Radioanalytical and Nuclear Chemistry》1987,115(2):377-388
The analysis of99Tc was carried out in filter, peat and rainwater samples. A solvent extraction technique was used to separate Tc from them, where tributylphosphate was the extracting agent. Radiochemical yield was obtained by using99mTc as an internal tracer. A typical value of 60% was found for it. However, problems encountered in its determination are discussed in the text. Additionally, rainwater samples were analyzed for137Cs. This was adsorbed in ammonium phosphomolibdate. Radiochemical yield was obtained by using134Cs as an internal tracer.Work partially supported under Contract CAICYT No. 2849/83. 相似文献
108.
Martínez-Alvarez R Martín N Seoane C Suárez M Pérez R Rodríguez H Kayali N 《Rapid communications in mass spectrometry : RCM》2001,15(10):758-762
The electrospray ionisation (ESI) in negative mode of the pharmacologically significant 3,5-disubstituted tetrahydro-2H-1,3,5-thiadiazin-2-thiones, and their subsequent fragmentations using an ion-trap mass spectrometer, have been investigated. Experiments on sequential product ion fragmentations (MS(n)) were performed in order to elucidate the degradation pathways for these compounds. The data presented show that the fragmentation of the even-electron [M - H](-) ions could proceed through an internal nucleophilic substitution displacement. Decarboxylation and extrusion of carbon disulfide are other fragmentations observed. 相似文献
109.
110.
Peter Rogl Subhash K. Naik Erwin Rudy 《Monatshefte für Chemie / Chemical Monthly》1977,108(5):1189-1211
The system TiC?HfC?WC was investigated by means of melting point, differential thermoanalytical, X-ray diffraction and metallographic techniques on hot pressed and heat treated as well as melted alloy specimens and a complete constitutional diagram from 1500°C through the melting range established. According to the peritectic melting of hexagonal WC both isopleths, TiC?WC as well as HfC?WC show a class II reaction at 2760°C in Ti?W?C and at 2730°C in Hf?W?C. The phase behaviour within the TiC?HfC?WC system is characterized by the presence of a (binary) miscibility gap within TiC?HfC [T c=1780°C, (TiC)0.55(HfC)0.45] which extends into the ternary forming a closed ternary miscibility gap at higher temperatures with an isolated ternary critical point:T c=1800°C, (TiC)0.55(HfC)0.45(WC)0.05. Interaction of the solvus (boundary of the cubic-B 1 monocarbide solid solution) and the ternary miscibility gap was established at 1540°C and (TiC)0.27(HfC)0.41(WC)0.32: Alloys of this composition enter a decomposition reaction on cooling into two isotypic cubic B 1 phases and hexagonal WC. Isothermal sections were calculated assuming regular solutions. 相似文献