全文获取类型
收费全文 | 875篇 |
免费 | 17篇 |
国内免费 | 4篇 |
专业分类
化学 | 663篇 |
晶体学 | 8篇 |
力学 | 6篇 |
数学 | 72篇 |
物理学 | 147篇 |
出版年
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 10篇 |
2018年 | 11篇 |
2017年 | 10篇 |
2016年 | 15篇 |
2015年 | 6篇 |
2014年 | 9篇 |
2013年 | 28篇 |
2012年 | 26篇 |
2011年 | 34篇 |
2010年 | 25篇 |
2009年 | 33篇 |
2008年 | 65篇 |
2007年 | 45篇 |
2006年 | 47篇 |
2005年 | 52篇 |
2004年 | 48篇 |
2003年 | 45篇 |
2002年 | 41篇 |
2001年 | 14篇 |
2000年 | 22篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 15篇 |
1996年 | 16篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 9篇 |
1992年 | 10篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 29篇 |
1983年 | 8篇 |
1982年 | 17篇 |
1981年 | 15篇 |
1980年 | 11篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1969年 | 4篇 |
1968年 | 6篇 |
1967年 | 4篇 |
排序方式: 共有896条查询结果,搜索用时 90 毫秒
851.
A novel selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography-olfactometry/mass spectrometry with preparative fraction collection (selectable (1)D/(2)D GC-O/MS with PFC) system was developed. The main advantages of this system are the simple and fast selection of (1)D GC-O/MS or (2)D GC-O/MS or (1)D GC-PFC or (2)D GC-PFC operation with a mouse click (without any instrumental set-up change), and total transfer of enriched compounds with thermal desorption (TD) on the same system for identification with (2)D GC-O/MS analysis. Recovery of PFC enrichment with 20 injection cycles of 15 model compounds at 500pg each (e.g. alcohol, aldehyde, ester, lactone, and phenol) was very good with recoveries in the range of 98-116%. The feasibility and benefit of the proposed system was demonstrated with an identification of off-flavor compounds (e.g. 2,4,6-trichloroanisole (TCA), 2-isobutyl-3-methoxypyrazine (IBMP), and geosmin) in spiked wine at odor perception threshold level (5-50ngL(-1)). After parallel stir bar sorptive extraction (SBSE) for 20 aliquots of a sample and subsequent PFC enrichment for the odor-active fractions from the 20 stir bars, three off-flavor compounds were clearly resolved and detected with TD-(2)D GC-O/MS in scan mode. The good efficiency of SBSE-PFC enrichment in the range of 71-78% shows that all analytical steps, e.g. SBSE, TD, (1)D/(2)D GC-O/MS, and PFC, are quantitative and identification of off-flavor compounds at ngL(-1) level in wine is possible. 相似文献
852.
This paper analyzes strategic store openings in a situation in which firms can open multiple stores depending on the financial constraints of the firm. Specifically, given any upper limit of the number of store openings that two potentially symmetric firms can open, they sequentially determine the number of store openings, including their locations, to maximize their profits. As a result of our analysis in a microeconomic framework, we show that the equilibrium strategy can be wholly classified into only two following opposite strategies according to the level of their financial constraints involved. When firms can afford to invest significant amounts of money in the market, the leader chooses “segmentation strategy,” in which a part of the market can be monopolized by opening a chain of multiple stores and deterring the follower’s entry. In contrast, when the leader has a severe financial constraint so that it can only monopolize less than half of the market, the leader chooses “minimum differentiation strategy,” where firms open each of their stores at exactly the same point as the rival’s. Under this strategy, the leader necessarily captures just half of the market. Furthermore, we show that regardless of potential symmetry between firms, both first and second mover advantages in terms of profit can occur in the equilibrium. 相似文献
853.
By exploiting a case regarded as trivial, this paper presents global active noise control using a parametric beam focusing source (PBFS). As with a dipole model, one is used for a primary sound source and the other for a control sound source, the control effect for minimizing a total acoustic power depends on the distance between the two. When the distance becomes zero, the total acoustic power becomes null, hence nothing less than a trivial case. Because of the constraints in practice, there exist difficulties in placing a control source close enough to a primary source. However, by projecting a sound beam of a parametric array loudspeaker onto the target sound source (primary source), a virtual sound source may be created on the target sound source, thereby enabling the collocation of the sources. In order to further ensure feasibility of the trivial case, a PBFS is then introduced in an effort to meet the size of the two sources. Reflected sound wave of the PBFS, which is tantamount to the virtual sound source output, aims to suppress the primary sound. Finally, a numerical analysis as well as an experiment is conducted, verifying the validity of the proposed methodology. 相似文献
854.
This paper presents the wave filtering method for a rectangular panel, which is necessary for a feedforward wave control system, and clarifies its validity in the control system. Firstly, a wave solution of a rectangular panel is derived to describe the wave dynamics of the structure. This is followed by the derivation of the wave filtering equations that indicates the structure of the filter. It is found that the proposed wave filter consists of a modal filter, a rearrangement filter and a wave decomposition filter. Then, from the viewpoint of numerical simulations, the characteristics of the wave propagation in a rectangular panel as well as the accuracy of the wave fitter are verified. For the evaluation of the filter accuracy, the condition number is used as a performance index. Finally, an experiment on the adaptive feedforward control system using the wave filter is carried out, demonstrating that the reflected wave absorbing control enables the inactivation of vibration modes. 相似文献
855.
Nobuo Sakairi Toshio Yoneta Md. Dalilur Rahman Yoshiharu Ishido 《Journal of carbohydrate chemistry》2013,32(1):51-65
Abstract Hydrazinolyses of hexa-0-benzoyl-tetra-N-benzyloxycarbonyl-and N-ethoxycarbonylkanamycin A were performed and found to be sufficiently regioselective to give the corresponding 2′-hydroxyl derivatives in good yields under controlled conditions. The products were converted into the corresponding 2′-triflates, which were then subjected to nucleophilic substitution reactions with sodium benzenethioxide, sodium benzoate, and sodium azide to give the corresponding d-mannopyranosyl derivatives in good yields. Deprotection of the phenylthio (10) and azido (12) derivatives, and hydrogenolysis, gave 2′-deoxykankmycin A and 2′-epi-kanamycin B, respectively. Moreover, deprotection of the benzoyl compound 11 gave 2′-epi-kanamycin A. 相似文献
856.
Hitoshi Tamiaki Nobuo Kosaka Yusuke Kinoshita 《Research on Chemical Intermediates》2013,39(1):221-232
A cyclic chlorophyll hetero-dyad 1-H2H2, prepared by double ester linking of two structurally different pyropheophorbide-a moieties through 3-CH2OCO-132′ and 172-COOCH2-3′, was metallated with zinc and copper to give mono and di-metallated complexes 1-MH2 or 1-H2M and 1-MM. The metallation proceeded stepwise and regioselectively, with predominant synthesis of one of the two mono-metallated complexes 1-MH2 as intermediate. The di-zinc complex produced, 1-ZnZn, was demetallated exclusively via the same mono-zinc complex 1-ZnH2 as was the major intermediate during metallation. Visible and/or circular dichroism spectra of 1-H2H2, 1-MH2, 1-H2M, and 1-MM (M = Ni, Cu, or Zn) were measured in organic solvents. Intramolecular interaction of chlorin chromophores is discussed and compared with that of the corresponding monomeric species. 相似文献
857.
Polymeric analogs of tetramethylurea were prepared by free-radical polymerization of N,N,N'-trimethyl-N'-p-vinylbenzylurea and copolym-erization of this monomer with styrene. These polymers are soluble in toluene and have the ability to extract alkali metal ions such as lithium, sodium, and potassium. Moreover, these polymers act as phase-transfer catalysts for typical S N 2 reactions, although the monomeric analogs tetramethylurea and N,N,N'-trimethyl-N'-benzylurea do not. A plausible mechanism for these catalytic reactions is proposed. 相似文献
858.
In this paper, we propose a regularized Newton method without line search. The proposed method controls a regularization parameter instead of a step size in order to guarantee the global convergence. We show that the proposed algorithm has the following convergence properties. (a) The proposed algorithm has global convergence under appropriate conditions. (b) It has superlinear rate of convergence under the local error bound condition. (c) An upper bound of the number of iterations required to obtain an approximate solution \(x\) satisfying \(\Vert \nabla f(x) \Vert \le \varepsilon \) is \(O(\varepsilon ^{-2})\) , where \(f\) is the objective function and \(\varepsilon \) is a given positive constant. 相似文献
859.
Luminescence Color Tuning of PtII Complexes and a Kinetic Study of Trimer Formation in the Photoexcited State 下载免费PDF全文
T. Kayano S. Takayasu Dr. K. Sato Prof. K. Shinozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16583-16589
We investigated the luminescence properties and color tuning of [Pt(dpb)Cl] (dpbH=1,3‐di(2‐pyridyl)benzene) and its analogues. An almost blue emission was obtained for the complex [Pt(Fmdpb)CN] (FmdpbH=4‐fluoro‐1,3‐di(4‐methyl‐2‐pyridyl)benzene), modified by the introduction of ?F and ?CH3 groups to the dpb ligand and the substitution of ?Cl by ?CN. As the concentration of the solution was increased, the color of the emission varied from blue to white to orange. The color change resulted from a monomer–excimer equilibrium in the excited state. A broad emission spectrum around 620 nm was clearly detected along with a structured monomer emission around 500 nm. Upon further increases in concentration, another broad peak appeared in the longer wavelength region of the spectrum. We assigned the near‐infrared band to the emission from an excited trimer generated by the reaction of the excimer with the ground‐state monomer. The emission lifetimes of the monomer, dimer, and trimer were evaluated as τM=12.8 μs, τD=2.13 μs, and τT=0.68 μs, respectively, which were sufficiently long to allow association with another PtII complex and dissociation into a lower order aggregate. Based on equilibrium constants determined from a kinetic study, the formation of the excimer and the excited trimer were concluded to be exothermic processes, with ΔG*D=?24.5 kJ mol?1 and ΔG*T=?20.4 kJ mol?1 respectively, at 300 K. 相似文献
860.