全文获取类型
收费全文 | 4912篇 |
免费 | 103篇 |
国内免费 | 16篇 |
专业分类
化学 | 3657篇 |
晶体学 | 52篇 |
力学 | 81篇 |
数学 | 229篇 |
物理学 | 1012篇 |
出版年
2022年 | 34篇 |
2021年 | 40篇 |
2020年 | 42篇 |
2019年 | 53篇 |
2018年 | 33篇 |
2017年 | 38篇 |
2016年 | 68篇 |
2015年 | 83篇 |
2014年 | 80篇 |
2013年 | 236篇 |
2012年 | 204篇 |
2011年 | 222篇 |
2010年 | 128篇 |
2009年 | 124篇 |
2008年 | 242篇 |
2007年 | 219篇 |
2006年 | 247篇 |
2005年 | 270篇 |
2004年 | 253篇 |
2003年 | 211篇 |
2002年 | 241篇 |
2001年 | 151篇 |
2000年 | 113篇 |
1999年 | 78篇 |
1998年 | 54篇 |
1997年 | 60篇 |
1996年 | 78篇 |
1995年 | 61篇 |
1994年 | 67篇 |
1993年 | 64篇 |
1992年 | 86篇 |
1991年 | 67篇 |
1990年 | 61篇 |
1989年 | 54篇 |
1988年 | 57篇 |
1987年 | 41篇 |
1986年 | 55篇 |
1985年 | 86篇 |
1984年 | 76篇 |
1983年 | 40篇 |
1982年 | 61篇 |
1981年 | 43篇 |
1980年 | 48篇 |
1979年 | 60篇 |
1978年 | 53篇 |
1977年 | 48篇 |
1976年 | 33篇 |
1975年 | 35篇 |
1974年 | 36篇 |
1973年 | 37篇 |
排序方式: 共有5031条查询结果,搜索用时 10 毫秒
961.
5-O-(4-[125 I]Iodobenzyl)-L-ascorbic acid: electrophilic radioiodination and biodistribution in mice
Kim J Kino T Kato H Yamamoto F Sano K Mukai T Maeda M 《Chemical & pharmaceutical bulletin》2012,60(2):235-240
As a part of our efforts to develop potential imaging agents for ascorbate bioactivity, 5-O-(4-[(125)I]iodobenzyl)-L-ascorbic acid ([(125)I]1) was prepared through a two-step sequence which involved radioiodo-destannylation of a protected tributylstannyl precursor 6, followed by hydrolysis in acidic methanol of the protecting groups in 61% overall radiochemical yield, with a radiochemical purity of over 98% and a specific activity of more than 15.4?GBq/μmol. Tissue distribution of [(125)I]1 in tumor-bearing mice showed signs of distribution profiles similar to the reported results for 6-deoxy-6-[(18)F]fluoro-L-ascorbic (6-(18)FAsA) acid and 6-deoxy-6-[(131)I]iodo-L-ascorbic acid (6-(131)IAsA) but with notable differences in the adrenal glands, in which considerably lower uptake of radioactivity and rapid clearance with time were observed. Pretreatment of mice with a known inhibitor of ascorbate transport, sulfinpyrazone, did not produce any significant change in the adrenal uptake of radioactivity after injection of [(125)I]1 compared to the control, suggesting that uptake in the adrenal glands is independent of the sodium-dependent vitamin C transporter 2 transport mechanism. Introduction of a bulky substituent at C-5 on AsA, such as an iodobenzyloxy group, may not be suitable for the design of analogs that may still be able to maintain characteristic distribution properties in vivo seen with AsA itself. 相似文献
962.
Seki M Tsuruta O Aoyama Y Soejima A Shimada H Nonaka H 《Chemical & pharmaceutical bulletin》2012,60(4):488-498
In investigating potent sodium (Na(+)) channel blockers for the treatment of ischemic stroke, we synthesized a novel series of 3-amino-1-(5-indanyloxy)-2-propanol derivatives and evaluated their inhibitory effects on neuronal Na(+) channels. The 3-amino-1-(5-indanyloxy)-2-propanol derivatives exhibited potent blocking activity for Na(+) channels and a significantly low affinity for dopamine D(2) receptors, which demonstrates a minimal clinical risk for extrapyramidal side effects. In particular, compound 4b, a 3-amino-1-(5-indanyloxy)-2-propanol derivative bearing a benzimidazole moiety, showed desirable neuroprotective activity in a rat transient middle cerebral artery occlusion model. Furthermore, compound 4b displayed a high binding affinity for neurotoxin receptor site 2 of the Na(+) channels, which suggests that 4b would act as a use-dependent Na(+) channel blocker in sustained depolarization during ischemic stroke. 相似文献
963.
The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO-NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the (1)HNO → (1)NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol(-1). For the barrierless decomposition of (1)HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol(-1). For (1)NOH → H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol(-1). On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol(-1) for the isomerization reaction (3)HNO → (3)NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol(-1). Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol(-1) for the dissociation reaction of (3)NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet-triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol(-1) for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to 400 K. Hence, our theoretical findings clearly explain why (1)NOH has not yet been observed experimentally. 相似文献
964.
Atsuyoshi Nakayama Minoru UkitaJun Iyoda Norioki KawasakiNoboru Yamamoto 《Polymer Degradation and Stability》2012,97(1):14-20
Copolyesters of poly(ε-caprolactone) diol and 1,18-octadecane dicarboxylic acid were synthesized by polyaddition. The copolymers have a "mixed" structure of ’polyester-polyethylene’. Characterization was carried out by using 1H and 13C NMR, FT-IR, viscosities, DSC, and GPC. The tensile strength varied from 11.9 to 19.9 MPa, and elongation at break varied from 370 to 660 %, respectively. Biodegradability was evaluated by enzymatic hydrolysis (lipases from Rhizopus arrhizus and Candida cylindracea and an esterase form hog liver) and by soil burial test. Both tests showed that the copolyesters were characterized by enhanced biodegradability. 相似文献
965.
966.
Several dereverberation algorithms have been studied. The sampling frequencies used in conventional studies are typically 8–16 kHz because their main purpose is preprocessing for improving the intelligibility of speech communication and articulation for automatic speech recognition. However, in next-generation communication systems, techniques to analyze and reproduce not only semantic information of sound but also more high-definition components such as spatial information and directivity will be increasingly necessary. To decompose these sound field characteristics with high definition, a dereverberation algorithm that is useful at high sampling frequencies is an important technique to process sound that includes high-frequency spectra such as musical sounds. The LInear-predictive Multichannel Equalization (LIME) algorithm is a promising dereverberation method. Using the LIME algorithm, however, a dereverberation signal cannot be solved at high sampling frequencies when the source signal is colored, such as in the case of speech and sound of musical signals. Because the rank of the correlation matrix calculated from such a colored signal is not full, the characteristic polynomial cannot be calculated precisely. To alleviate this problem, we propose preprocessing of all input signals with filters to whiten their spectra so that this algorithm can function for colored signals at high sampling frequencies. 相似文献
967.
非高斯风压的极值计算方法 总被引:2,自引:0,他引:2
以经典极值理论为基础,发展了一种基于单个标准样本的非高斯风压的极值计算方法. 首先介绍了风洞试验及试验数据处理的基本概况;然后在阐述经典Gumbel极值理论的基础上,根据观察极值的相互独立性推导了短时距下极值分布参数和长时距下极值分布参数的关系式,给出了一种由短时距样本推算长时距下的极值估算方法; 最后基于风洞试验数据,将常用极值估算方法(峰值因子法、改进峰值因子法和Sadek-Simiu法)和该方法的计算结果进行了比较. 得到如下结论:将一个标准长度的非高斯风压时程数据划分成若干等长的子段,可以通过子段的极值分布规律准确地估算出母段的极值期望值,子段的最佳分段长度可以通过自相关分析给出;与常用的极值估算方法相比,该方法更能准确估计非高斯风压的极值. 相似文献
968.
N. Yasuda K. Uchikawa K. Amemiya N. Watanabe H. Takahashi M. Nakazawa M. Yamamoto K. Ogura 《Radiation measurements》2001,34(1-6):45-49
As a frame work of the study for the latent track size measurement using atomic force microscope, we have measured the minute etch pits and the extremely small amount of bulk etch of CR-39 at the beginning of chemical etching, and obtained its growth curves in nanometer dimensions. The pieces of CR-39 were exposed to 6 MeV/nC and Fe ions with normal incidence angle and were etched in 70°C 7 N NaOH solution for 0.5,1,2,3,5 min. The diameters of latent track were estimated to be 17 nm for Fe ions and 8 nm for C ions, respectively. These values are comparable to the experimental data on the average ‘track core diameters’ that have been obtained by various experimental techniques. 相似文献
969.
Naoki Yasuda Shigeyuki Yamamoto Yuji Wada Shozo Yanagida 《Journal of polymer science. Part A, Polymer chemistry》2001,39(24):4196-4205
Photochemical reactions of aromatic azide groups were applied for a novel photosensitive silicone ladder polymer, that is, partially vinyl‐substituted polyphenylsilsesquioxane sensitized with aromatic bisazide compounds as a photocrosslinker. The photocrosslinking reaction in this system was investigated from the viewpoint of the efficiency of the photocrosslinker, that is, the ratio of the photocrosslinker consumed for crosslinking. The numbers of photodecomposed azide groups and crosslinks in the polymer were determined by Fourier transform infrared measurements. At a higher bisazide concentration, the predominant reaction of nitrenes formed as the intermediary radical by the photolysis of azide was a coupling reaction that could not contribute to the gelation of the polymer. The ratio of the bisazide compound consumed for crosslinking showed the highest value at its concentration of 3 wt % and decreased with the addition of a larger amount. The semiempirical molecular orbital calculations were applied to the theoretical analysis of the photoreaction of nitrenes using phenylnitrene as a model structure. The calculation results indicated that the coupling reaction of nitrenes should proceed more easily than the photocrosslinking reaction in N2 atmosphere, and the fact that the oxidation of nitrenes should proceed exclusively in the atmosphere including O2 agreed with the experimental results. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4196–4205, 2001 相似文献
970.
N Asao T Shimada T Shimada Y Yamamoto 《Journal of the American Chemical Society》2001,123(44):10899-10902
Intramolecular trans-vinylsilylation using silicon-tethered alkynylvinylsilanes 3b-c was catalyzed dramatically by Lewis acids such as EtAlCl(2) to give the corresponding six-membered silacycles 4b-c in high yields. The reaction proceeded via an exo-mode cyclization. In addition to the vinylsilylation, the intramolecular trans-arylsilylations using carbon-tethered alkynylarylsilanes 8a-b were also catalyzed by Lewis acids such as HfCl(4) to give six- and seven-membered cyclic (E)-vinylsilanes 9a-b, respectively. The cyclization of silicon-tethered substrates 13a-d afforded five- and six-membered silacycle products 14a-d in low to high yields. All arylsilylation reactions proceeded via an exo-mode fashion exclusively. 相似文献