全文获取类型
收费全文 | 1676篇 |
免费 | 53篇 |
国内免费 | 19篇 |
专业分类
化学 | 1073篇 |
晶体学 | 36篇 |
力学 | 87篇 |
数学 | 187篇 |
物理学 | 365篇 |
出版年
2024年 | 12篇 |
2023年 | 9篇 |
2022年 | 80篇 |
2021年 | 88篇 |
2020年 | 55篇 |
2019年 | 69篇 |
2018年 | 49篇 |
2017年 | 30篇 |
2016年 | 68篇 |
2015年 | 51篇 |
2014年 | 58篇 |
2013年 | 122篇 |
2012年 | 84篇 |
2011年 | 112篇 |
2010年 | 60篇 |
2009年 | 64篇 |
2008年 | 52篇 |
2007年 | 72篇 |
2006年 | 56篇 |
2005年 | 49篇 |
2004年 | 30篇 |
2003年 | 28篇 |
2002年 | 35篇 |
2001年 | 15篇 |
2000年 | 21篇 |
1999年 | 15篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 11篇 |
1995年 | 8篇 |
1994年 | 15篇 |
1993年 | 18篇 |
1992年 | 17篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 16篇 |
1987年 | 15篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 15篇 |
1983年 | 8篇 |
1982年 | 13篇 |
1981年 | 15篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1977年 | 9篇 |
1976年 | 12篇 |
1975年 | 10篇 |
1967年 | 7篇 |
排序方式: 共有1748条查询结果,搜索用时 11 毫秒
51.
Sang Soo Shin Diane M. Armao Monty Shah Young Hoon Kim Chang Hee Lee Tara Rubinas Lauren M. Brubaker Richard C. Semelka 《Magnetic resonance imaging》2010
Purpose
To evaluate the clinical outcomes of conservative management by observation with MRI of patients with branch-duct intraductal papillary mucinous neoplasms (BD-IPMNs).Materials and Methods
Twenty-three consecutive patients, who were followed up by MRI with magnetic resonance cholangiopancreatography (MRCP) over a period of more than 9 months after initial MRI examinations, were enrolled in this study. On MRI, number of lesions, the maximum diameter of BD-IPMNs, lesion location, the presence of associated dilatation of main pancreatic duct (MPD), the presence of enhancing mural nodules within the lesion and the presence of interval change were retrospectively reviewed on initial and follow-up MR images in consensus by two radiologists. All patients were evaluated to search for evidence of malignant progression of disease.Results
The follow-up period ranged from 10 to 96 months (mean, 37 months). On initial MRI with MRCP, a total of 39 lesions were found in 23 patients. The maximum diameter of BD-IPMNs ranged between 6 and 32 mm, with a mean of 12 mm. Thirty-four lesions (87%) of 19 patients remained unchanged in the maximum diameter. Five lesions (13%) of four patients showed an increase in the maximum diameter. Enhancing mural nodules were not found in any individual, neither on the initial MRI study nor on the follow-up studies. There was no patient who had evidence of local aggressive growth of tumor or evidence of metastases to distant sites.Conclusion
Our study suggests that branch-duct IPMNs without enhancing mural nodules are essentially benign and should be managed nonoperatively through observation by MRI. 相似文献52.
We have studied the magnetic and transport properties of Fe doped La0.65A0.35Mn0.95Fe0.05O3 (A = Ca, Sr, Pb, Ba) manganites. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition (TC) except the Pb doped sample which is insulating and ferromagnetic (FM) in the entire temperature range. The magnetization and TC are decreased by decreasing the cation size on La site. The transition temperature and magnetic moment at 77 K is a maximum for Sr doped sample and is decreasing if we increase or decrease the cation size from Sr size. The maximum value of TC and magnetic moment for Sr based sample is most likely due to the closer ionic sizes of La and Sr as compared to the other dopants (Ca, Pb, and Ba). We observed a spin freezing type effect in the Pb doped sample below 120 K in resistivity, ac susceptibility and in magnetization. This suggests that the AFM interactions introduced by the Fe are most effective in the Pb doped composition leading to increased competition between the FM and AFM interactions. This FM and AFM interaction generates some degree of frustration leading to the appearance of spin glass like phase whose typical magnetic behavior is studied for small ion when the metallic like behavior is lost. 相似文献
53.
A novel approach is presented for interpreting and potentially predicting values of the isothermal, isobaric transfer free energy, entropy, and enthalpy (Deltamicrotr2, Deltastr2, and Deltahtr2) for a solute between water and water-cosolvent mixtures. The approach explicitly accounts for volumetric properties of the solvent and solute (the equation of state, EoS) and casts the overall transfer process as a thermodynamic cycle with two stages: (1) isothermal solvent exchange from pure water to the cosolvent composition of interest at fixed mass density; (2) isothermal expansion or compression at the final solvent composition to recover the pressure of the initial state. Using molecular simulations with methane as the solute, the analysis is illustrated over a wide range of cosolvent concentrations for sorbitol-, ethanol-, and methanol-water binary mixtures. The EoS contribution semiquantitatively or quantitatively captures Deltamicrotr2, Deltastr2, and Deltahtr2 in almost all cases tested, highlighting the importance of considering the effects of changes in solvent density on the overall transfer process. The results also indicate that apolar solvation at these length scales is dominated by the work of cavity formation across a range of cosolvent species and concentrations. 相似文献
54.
Rosseto R Bibak N DeOcampo R Shah T Gabrielian A Hajdu J 《The Journal of organic chemistry》2007,72(5):1691-1698
A new stereoselective synthesis of lysophosphatidylcholines is reported. The synthesis is based upon (1) the use of 3-p-toluenesulfonyl-sn-glycerol to provide the stereocenter for construction of the optically active lysophospholipid molecule, (2) tetrahydropyranylation of the secondary alcohol function to achieve orthogonal protection of the sn-2- and sn-3-glycerol positions, and (3) elaboration of the phosphodiester headgroup using a 2-chloro-1,3,2-dioxaphospholane/trimethylamine sequence. In the course of developing the synthesis it has been discovered that methoxyacetate displacement of the sn-3-p-toluenesulfonate yields a reactive methoxyacetyl ester, which in turn can be selectively cleaved with methanol/tert-butylamine, while the ester group at the sn-1-position remains unaffected. The sequence has been shown to be suitable for preparation of spectroscopically labeled lysophosphatidylcholines. One of these compounds was readily converted to a double-labeled mixed-chain phosphatidylcholine applicable for real-time fluorescence resonance energy transfer (FRET) assay of lipolytic enzymes. In addition, the work led to new synthetic strategies based on chemoselective manipulation of the tosyl group in the presence of other base-labile groups such as FMOC derivatives that are often used for the protection of amino and hydroxyl groups in syntheses. 相似文献
55.
Muhammad I. Khan Abad Khan Zafar Iqbal Lateef Ahmad Yasar Shah 《Chromatographia》2010,71(7-8):577-586
A versatile isocratic reversed-phase liquid chromatographic/ultraviolet–visible detection method for simultaneous determination of all-trans-retinol and α-tocopherol in human serum was developed and validated after optimization of various chromatographic conditions and other experimental parameters. Analytes were separated on a Kromasil 100 RP18 (150 × 4.6 mm, 5 μm) analytical column protected by a Perkin Elmer RP18 (30 × 4.6 mm, 10 μm) guard cartridge. The mobile phase, methanol–water (96:04 v/v) was pumped at a flow rate of 2.2 mL min?1 and the column eluents were monitored at the wavelength of 292 nm using retinyl acetate (1.0 μg mL?1) as the internal standard for both analytes. Sample preparation was based on protein precipitation and stabilization with 2,6-bis(1,1-dimethylethyl)-4-methylphenol/ethanol and a two step extraction process using n-hexane followed by dichloromethane as extraction solvents. Sample size was kept 20 μL and separation of analytes was achieved in less than 7 min. The present method demonstrated acceptable values for specificity/selectivity, linearity within the expected concentration range, recovery, precision, sensitivity, stability of solutions, robustness, and system suitability specifications and tests. The method was used for monitoring all-trans-retinol and α-tocopherol concentrations in human serum samples and could also be applied to other sample matrices such as brain slices and cosmetic products if attention is paid to the extraction procedure. 相似文献
56.
Köhler A Khan AL Wilson JS Dosche C Al-Suti MK Shah HH Khan MS 《The Journal of chemical physics》2012,136(9):094905
The intrinsic non-radiative decay (internal conversion) from the triplet excited state in phosphorescent dyes can be described by a multi-phonon emission process. Since non-radiative decay of triplet excitons can be a significant process in organic light-emitting diodes, a detailed understanding of this decay mechanism is important if the overall device efficiency is to be controlled. We compare a deuterated Pt(II)-containing phenylene ethynylene with its non-deuterated counterpart in order to investigate which phonon modes control to the non-radiative decay path. We observe that deuteration does not decrease the non-radiative decay rate. A Franck-Condon analysis of the phosphorescence spectra shows that the electronic excitation is coupled strongly to the breathing mode of the phenyl ring and the C≡C carbon stretching modes, while high-energy C-H or C-D stretching modes play an insignificant role. We, therefore, associate the internal conversion process with the carbon-carbon stretching vibrations. 相似文献
57.
58.
The mixed-ligand complexes formed by copper(II) with an amino-acid (valine, threonine, isoleucine, aspartic acid, glutamic acid, lysine) and malonic acid have been investigated polarographically and their stability constants determined. The complexes are less stable than the corresponding complexes with oxalic acid instead of malonic, but also exhibit less disproportionation into the simple complexes, because the simple oxalate complexes are more stable than the malonate complexes. 相似文献
59.
Vivek B. Shah Gregory S. Orf Sean Reisch Lucas B. Harrington Mindy Prado Robert E. Blankenship Pratim Biswas 《Analytical and bioanalytical chemistry》2012,404(8):2329-2338
Photosynthetic organisms have light-harvesting complexes that absorb and transfer energy efficiently to reaction centers. Light-harvesting complexes (LHCs) have received increased attention in order to understand the natural photosynthetic process and also to utilize their unique properties in fabricating efficient artificial and bio-hybrid devices to capture solar energy. In this work, LHCs with different architectures, sizes, and absorption spectra, such as chlorosomes, Fenna–Matthews–Olson (FMO) protein, LH2 complex, and phycobilisome have been characterized by an electrospray-scanning mobility particle-sizer system (ES-SMPS). The size measured by ES-SMPS for FMO, chlorosomes, LH2, and phycobilisome were 6.4, 23.3, 9.5, and 33.4?nm, respectively. These size measurements were compared with values measured by dynamic light scattering and those reported in the literature. These complexes were deposited onto a transparent substrate by electrospray deposition. Absorption and fluorescence spectra of the deposited LHCs were measured. It was observed that the LHCs have light absorption and fluorescence spectra similar to that in solution, demonstrating the viability of the process. 相似文献
60.