首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1726篇
  免费   43篇
  国内免费   5篇
化学   1066篇
晶体学   10篇
力学   24篇
数学   233篇
物理学   441篇
  2022年   13篇
  2021年   16篇
  2020年   21篇
  2019年   21篇
  2016年   25篇
  2015年   27篇
  2014年   27篇
  2013年   76篇
  2012年   79篇
  2011年   91篇
  2010年   61篇
  2009年   36篇
  2008年   73篇
  2007年   84篇
  2006年   78篇
  2005年   68篇
  2004年   95篇
  2003年   55篇
  2002年   55篇
  2001年   48篇
  2000年   51篇
  1999年   26篇
  1998年   28篇
  1997年   18篇
  1996年   21篇
  1995年   23篇
  1994年   29篇
  1993年   45篇
  1992年   35篇
  1991年   27篇
  1990年   18篇
  1989年   26篇
  1988年   23篇
  1987年   9篇
  1986年   18篇
  1985年   23篇
  1984年   18篇
  1983年   14篇
  1982年   18篇
  1981年   15篇
  1980年   13篇
  1979年   17篇
  1978年   21篇
  1977年   14篇
  1976年   25篇
  1975年   16篇
  1974年   10篇
  1973年   11篇
  1972年   10篇
  1971年   10篇
排序方式: 共有1774条查询结果,搜索用时 0 毫秒
51.
To date, both quantum theory and Einstein’s theory of general relativity have passed every experimental test in their respective regimes. Nevertheless, almost since their inception, there has been debate surrounding whether they should be unified, and by now, there exists strong theoretical arguments pointing to the necessity of quantising the gravitational field. In recent years, a number of experiments have been proposed which, if successful, should give insight into features at the Planck scale. Here, we review some of the motivations, from the perspective of semi-classical arguments, to expect new physical effects at the overlap of quantum theory and general relativity. We conclude with a short introduction to some of the proposals being made to facilitate empirical verification.  相似文献   
52.

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   
53.
Statistical control charts are presented for the evaluation of time series radiation counter data from flow cells used for monitoring of low levels of 99TcO4 in environmental solutions. Control chart methods consisted of the 3-sigma (3σ) chart, the cumulative sum (CUSUM) chart, and the exponentially weighted moving average (EWMA) chart. Each method involves a control limit based on the detector background which constitutes the detection limit. Both the CUSUM and EWMA charts are suitable to detect and estimate sample concentration requiring less solution volume than when using a 3σ control chart. Data presented here indicate that the overall accuracy and precision of the CUSUM method is the best.  相似文献   
54.
55.
A recent controversy regarding the proper assignment of two closely spaced bands in the S1 ← S0 electronic transition of trans-p-coumaric acid (pCA) has been addressed by recording their spectra at full rotational resolution. The results show unambiguously that the carrier of these two bands is p-vinylphenol (pVP), a thermal decomposition product of pCA. The two bands belong to two conformers of pVP; trans-pVP at 33,207.3 cm−1 and cis-pVP at 33,211.8 cm−1.  相似文献   
56.
Application of a triple-pulse waveform is described for the anodic detection of methanol, ethanol, and ethylene glycol. The execution of the waveform incorporates the cleaning and reactivation of the platinum electrode, by alternate anodic and cathodic polarization, with measurement of the faradaic signal for the analyte at the reduced electrode surface. Some results for formic acid are also presented. The waveform is completed within approximately 2 s and the faradaic signal exhibits no decay with time as would be the case for amperometric detection at a constant applied potential. Calibration curves made by plotting —1/I vs. 1/C are linear. This is consistent with a reaction mechanism in which the analyte is adsorbed prior to anodic detection. The technique is applicable for detection in chromatographic and flow-injection systems.  相似文献   
57.
The spectroscopic, electronic, and DNA-binding characteristics of two novel ruthenium complexes based on the dialkynyl ligands 2,3-bis(phenylethynyl)-1,4,8,9-tetraaza-triphenylene (bptt, 1) and 2,3-bis(4-tert-butyl-phenylethynyl)-1,4,8,9-tetraaza-triphenylene (tbptt, 2) have been investigated. Electronic structure calculations of bptt reveal that the frontier molecular orbitals are localized on the pyrazine-dialkynyl portion of the free ligand, a property that is reflected in a red shift of the lowest energy electronic transition (1: λ(max) = 393 nm) upon substitution at the terminal phenyl groups (2: λ(max) = 398 nm). Upon coordination to ruthenium, the low-energy ligand-centered transitions of 1 and 2 are retained, and metal-to-ligand charge transfer transitions (MLCT) centered at λ(max) = 450 nm are observed for [Ru(phen)(2)bptt](2+)(3) and [Ru(phen)(2)tbptt](2+)(4). The photophysical characteristics of 3 and 4 in ethanol closely parallel those observed for [Ru(bpy)(3)](2+) and [Ru(phen)(3)](2+), indicating that the MLCT excited state is primarily localized within the [Ru(phen)(3)](2+) manifold of 3 and 4, and is only sparingly affected by the extended conjugation of the bptt framework. In an aqueous environment, 3 and 4 possess notably small luminescence quantum yields (3: ?(H(2)O) = 0.005, 4: ?(H(2)O) = 0.011) and biexponential decay kinetics (3: τ(1) = 40 ns, τ(2) = 230 ns; 4: τ(1) ~ 26 ns, τ(2) = 150 ns). Addition of CT-DNA to an aqueous solution of 3 causes a significant increase in the luminescence quantum yield (?(DNA) = 0.045), while the quantum yield of 4 is relatively unaffected (?(DNA) = 0.013). The differential behavior demonstrates that tert-butyl substitution on the terminal phenyl groups inhibits the ability of 4 to intercalate with DNA. Such changes in intrinsic luminescence demonstrate that 3 binds to DNA via intercalation (K(b) = 3.3 × 10(4) M(-1)). The origin of this light switch behavior involves two competing (3)MLCT states similar to that of the extensively studied light switch molecule [Ru(phen)(2)dppz](2+). The solvent- and temperature-dependence of the luminescence of 3 reveal that the extended ligand aromaticity lowers the energy of the (3)ππ* excited state into competition with the emitting (3)MLCT state. Interconversion between these two states plays a significant role in the observed photophysics and is responsible for the dual emission in aqueous environments.  相似文献   
58.
Dickie DA  Coker EN  Kemp RA 《Inorganic chemistry》2011,50(22):11288-11290
The P,P-chelated stannylene [(i-Pr(2)P)(2)N](2)Sn takes up 2 equiv of carbon dioxide (CO(2)) to form an unusual product in which CO(2) binds to the Sn and P atoms, thus forming a six-membered ring complex. Gentle heating of the solid product releases CO(2), indicating that CO(2) is bound as an adduct to the main-group complex. The groups bound to the CO(2) fragment are not particularly sterically crowded or highly acidic, thus indicating that "frustrated" Lewis acid-base pairs are not required in the binding of CO(2) to main-group elements.  相似文献   
59.
The determination of seven arsenic species in seafood was performed using ion exchange chromatography on an IonPac AS7 column with inductively coupled plasma mass spectrometry detection after microwave assisted extraction. The effect of five parameters on arsenic extraction recoveries was evaluated in certified reference materials. The recoveries of total arsenic and of arsenic species with the two best extraction media (100% H2O and 80% aqueous MeOH) were generally similar in the five seafood certified reference materials considered. However, because MeOH co-elutes with arsenite, which would result in a positively biased arsenite concentration, the 100% H2O extraction conditions were selected for validation of the method. Figures of merit (linearity, LOQs (0.019-0.075 mg As kg−1), specificity, trueness (with recoveries between 82% (As(III)) and 104% (As(V) based on spikes or certified concentrations), repeatability (3-14%), and intermediate precision reproducibility (9-16%) of the proposed method were satisfactory for the determination of arsenite, monomethylarsonic acid, dimethylarsinic acid, arsenate, arsenobetaine and arsenocholine in fish and shellfish. The performance criteria for trimethylarsine oxide, however, were less satisfactory. The method was then applied to 65 different seafood samples. Arsenobetaine was the main species in all samples. The percentage of inorganic arsenic varied between 0.4-15.8% in shellfish and 0.5-1.9% at the utmost in fish. The main advantage of this method that uses only H2O as an extractant and nitric acid as gradient eluent is its great compatibility with the long-term stability of both IEC separation and ICP-MS detection.  相似文献   
60.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号