全文获取类型
收费全文 | 397篇 |
免费 | 17篇 |
国内免费 | 3篇 |
专业分类
化学 | 303篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 21篇 |
物理学 | 81篇 |
出版年
2024年 | 2篇 |
2023年 | 5篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 16篇 |
2019年 | 19篇 |
2018年 | 7篇 |
2017年 | 18篇 |
2016年 | 10篇 |
2015年 | 22篇 |
2014年 | 11篇 |
2013年 | 35篇 |
2012年 | 37篇 |
2011年 | 32篇 |
2010年 | 26篇 |
2009年 | 19篇 |
2008年 | 21篇 |
2007年 | 21篇 |
2006年 | 19篇 |
2005年 | 13篇 |
2004年 | 14篇 |
2003年 | 7篇 |
2002年 | 8篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1992年 | 2篇 |
1990年 | 5篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有417条查询结果,搜索用时 15 毫秒
31.
Four new neutral copper-azido polymers [Cu(6)(N(3))(12)(aem)(2)](n)(1), [Cu(6)(N(3))(12)(dmeen)(2)(H(2)O)(2)](n) (2), [Cu(6)(N(3))(12)(N,N'-dmen)(2)](n) (3), and [Cu(6)(N(3))(12)(hmpz)(2)](n) (4) [aem = 4-(2-aminoethyl)morpholine; dmeen = N,N-dimethyl-N'-ethylethylenediamine; N,N'-dmen = N,N'-dimethylethylenediamine and hmpz = homopiperazine] have been synthesized by using 0.33 mol equiv of the chelating diamine ligands with Cu(NO(3))(2)·3H(2)O/CuCl(2)·2H(2)O and an excess of NaN(3). Single crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu(II)(6) building blocks. But the overall structures of these complexes vary widely in dimensionality. While 1 is three-dimensional (3D) in nature, 2 and 3 have a two-dimensional (2D) arrangement (with different connectivity) and 4 has a one-dimensional (1D) structure. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all the four complexes. The experimental susceptibility data have been analyzed by some theoretical model equations. 相似文献
32.
Sandip R. Sabale D. V. Jadhav B. S. Mohite 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(2):273-278
A simple and efficient column chromatographic method has been developed for the sequential separation of U(VI), Th(IV) and
Ce(III) using poly[dibenzo-18-crown-6] as stationary phase and l-arginine as a counter ion. The different elution patterns with various eluting agents were observed for individual element.
The capacity of poly[dibenzo-18-crown-6] for U(VI), Th(IV) and for Ce(III) was found to be 0.96, 0.86 and 1.49 (±0.01) mmol/g
of crown polymer, respectively. The method is efficient to separate the elements in multicomponent mixtures and has good recovery.
The method is extended to determine the U(VI), Th(IV) and Ce(III) from monazite sand. The method is simple, rapid and selective
having good reproducibility (~±2%). 相似文献
33.
Dr. N. Kodiah Beyeh Dr. Fangfang Pan Dr. Sandip Bhowmik Toni Mäkelä Prof. Robin H. A. Ras Acad. Prof. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1355-1361
N‐Alkyl ammonium resorcinarene salts (NARYs, Y=triflate, picrate, nitrate, trifluoroacetates and NARBr) as tetravalent receptors, are shown to have a strong affinity for chlorides. The high affinity for chlorides was confirmed from a multitude of exchange experiments in solution (NMR and UV/Vis), gas phase (mass spectrometry), and solid‐state (X‐ray crystallography). A new tetra‐iodide resorcinarene salt (NARI) was isolated and fully characterized from exchange experiments in the solid‐state. Competition experiments with a known monovalent bis‐urea receptor ( 5 ) with strong affinity for chloride, reveals these receptors to have a much higher affinity for the first two chlorides, a similar affinity as 5 for the third chloride, and lower affinity for the fourth chloride. The receptors affinity toward chloride follows the trend K1?K2?K3≈ 5 >K4, with Ka=5011 m ?1 for 5 in 9:1 CDCl3/[D6]DMSO. 相似文献
34.
Bhattacharya S Nayak SK Chattopadhyay S Ghosh K Banerjee M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(5):1257-1262
To improve the selectivity ratio of C70 over C60, a new designer molecule, viz., 3-fluoromesotetraphenylporphyrin (1) has been reported in the present investigations. Fluorescence studies reveal that the Q-absorption band of 1 gets sufficient quenching effect upon addition of both C60 and C70. Binding constants (K) of the C60/1 and C70/1 complexes are estimated to be 580 and 10,800 dm3 mol(-1), respectively. Thus, K(C70)/K(C60) is approximately 19 which is very large and even comparable with other macrocyclic host molecules like calix[5]arene, azacalix[m]arene[n]pyridine, cyclotriveratrylenophane and calixarene bisporphyrin. 1H NMR chemical shift measurements show that the -NH- proton of 1 suffers more shifts in presence of C70 compared to C60. This finding also offers a good support in favor of high K value for C70/1 complex as well as large selectivity ratio of C70 over C60. 相似文献
35.
Ghosh K Semwal A Nayak SK Banerjee SB Banerjee M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,66(4-5):1122-1125
[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital. 相似文献
36.
Sandip Halder Theodor Schneller Rainer Waser Florian Thomas 《Journal of Sol-Gel Science and Technology》2007,41(3):203-207
Nickel thin films have been sputtered on standard Si/SiO2 substrates with TiO2 as an adhesive layer. The thermal stability of these substrates was analyzed. SEM images show an increase in grain size with
annealing temperature. They were found to be stable till 800°C, beyond which the nickel layer disintegrated. These substrates
were used for deposition of BaTiO3 and (Ba,Sr)TiO3 dielectric thin films under a reducing atmosphere. The dielectric thin films were processed with various pyrolysis and annealing
temperatures in order to optimize the dielectric properties. Increased pyrolysis temperatures showed an increase in the grain
size. Results on these nickelised substrates were finally compared with dielectric films deposited on platinized silicon substrates
under identical conditions but crystallized in an oxygen atmosphere. 相似文献
37.
Sandip?HalderEmail author Theodor?Schneller Rainer?Waser 《Journal of Sol-Gel Science and Technology》2005,33(3):299-306
A new chemical solution deposition (CSD) route for the fabrication of Ba0.7Sr0.3TiO3 (BST) thin films has been developed which completely prevents the formation of an intermediate oxo-carbonate phase. The latter has been reported previously by several authors to be responsible for increased crystallization temperatures. Barium and strontium diaminoethoxides were synthesized starting from pure barium and strontium metal and aminoethanol. These alkoxides were found to be readily soluble in a wide range of solvents and thus were excellent candidates for the CSD process. To prepare a stable precursor solution the aminoalkoxides were dissolved in 2-butoxyethanol and then used for the deposition of BST thin films. We conclude that the minimum crystallization temperature of 600C to be independent of the formation of the oxo-carbonate phase. DTA-TGA were performed on the precursors and their solutions to study their decomposition behaviour. All films annealed at different temperatures were physically characterized by XRD, IR, and SEM. The films prepared by this route at 650C were found to have high dielectric constant and the leakage currents were comparable to BST films prepared by normal carboxylate based routes at 750C. 相似文献
38.
Premamoy Ghosh Samir Biswas Utpal Niyogi 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):1053-1063
Photopolymerization of methyl methacrylate (MMA) in visible light was studied at 40°C using Rhodamine 6G—Benzoyl peroxide combination as photoinitiator. The photopolymerization proceeds by a free radical mechanism and the radical generation process occurs by an initial complexation reaction between the initiator components. Kinetic data indicated a lower-order dependence of Rp on initiator concentrations (initiator exponent < 0.5). Initiator-dependent chain termination was significant along with the bimolecular mode of chain termination. 相似文献
39.
The voluminous utilization and application of plate and frame heat exchangers (PFHE) in many industries has accelerated the consumer and designer both to optimize exchanger total cost. Over the last few years, several old and new generation algorithms were employed and exploited to optimize PFHE cost. This study explores the application and performance of three new-generation algorithms Big Bang-Big Crunch (BBBC), Grey Wolf Optimizer (GWO), and Water Evaporation Optimization (WEO) in designing optimally PFHE. Besides, this study also compares the performance of three well-established old generations algorithms namely genetic algorithm (genetics and natural selection), particle swarm optimization (animals behaviour), and differential evolution (population-based) with the above three new algorithms in the optimization of PFHE.Seven design factors are chosen for PFHE optimization: exchanger length on hot and cold sides, height and thickness of fin, length of the fin-strip, fin frequency, and the number of hot side layers. The applicability of the suggested algorithms is assessed using a case study based on published research. Though DE performs the best in this study of design optimization concerning total cost and computational time, the three new-generation meta-heuristic algorithms BBBC, GWO, and WEO also provide the novel scope of application in heat exchanger design optimization and successfully finding the cost of the heat exchanger. According to this study, capital costs increase by 19.5% for BBBC, 24% for GWO, and 7.6% for GWO, but operational costs fall by 9.5% for BBBC and GWO when compared to the best performing algorithm (DE). On the other hand, WEO shows an increase of 32.6% in operational costs. Aside from that, a full analysis of the computing time for each algorithm is also provided. The DE has the quickest run time of 0.09 ?s, while the PSO takes the longest at 33.97 ?s. The rest of the algorithms have nearly identical values. As a result, a good comparison is established in this study, offering an excellent platform for designers and customers to make selections. Additionally, the three new generations algorithms mentioned here were not used earlier for optimization of PFHE and the comparative study illustrates that each of them possesses eat potential for cost optimization and also solving other complex problems. 相似文献
40.
We have performed molecular dynamics simulation studies of the structural, thermodynamic, and dynamical properties of liquid-vapor interfaces of pure and binary Stockmayer fluids of different polarity. The density profiles, the width of the liquid-vapor interface, and the orientational structure of the interfaces are calculated to characterize the structural aspects of the interfaces. Among the thermodynamic properties, we have computed the surface tension and also the free energy of transfer of a charged solute across the liquid-vapor interface for both pure and mixed fluids. Among the dynamical properties of the interfaces, we have calculated the time dependence of the velocity and angular velocity autocorrelation functions, continuous and intermittent survival probabilities, mean square displacements, diffusion coefficients, and also the dipole correlation functions and orientational relaxation times of interfacial solvent molecules. It is found that the width of the interfaces decreases with increase of concentration of the more polar component. The dipole vectors of the interfacial molecules tend to align parallel to the surfaces and this alignment is enhanced with increasing dipole moment of the fluid molecules. Also, the surface tension shows an increasing trend with increase of dipole moment of the molecules. The dynamical properties of the interfaces are found to be different from those of the corresponding bulk liquid phases. In general, the molecules at the interfaces are found to rotate and translate in the parallel direction at a somewhat faster rate than the bulk molecules. Also, on increase of concentration of the more polar component, the diffusion and orientational relaxation of interfacial molecules are found to show a weaker slowing down than those of the bulk molecules, which can be attributed to the preferential presence of the more polar component in the bulk liquid regions. The temporal behavior of the interfacial survival probabilities reveals a decrease of the survival times with increasing polarity, which can be attributed to a corresponding decrease in the interfacial thickness. Results are presented for both continuous and intermittent survival times and the origins of their differences are discussed. The free energy calculations reveal no minimum at the interfaces for adsorption of a charged solute, which shows that the ions would prefer to stay in the interior of the liquid phases, rather than at interfaces, for these model dipolar systems. 相似文献