全文获取类型
收费全文 | 1345篇 |
免费 | 34篇 |
国内免费 | 4篇 |
专业分类
化学 | 955篇 |
晶体学 | 19篇 |
力学 | 21篇 |
数学 | 90篇 |
物理学 | 298篇 |
出版年
2022年 | 8篇 |
2021年 | 8篇 |
2020年 | 16篇 |
2019年 | 15篇 |
2018年 | 10篇 |
2017年 | 10篇 |
2016年 | 12篇 |
2015年 | 17篇 |
2014年 | 34篇 |
2013年 | 49篇 |
2012年 | 79篇 |
2011年 | 75篇 |
2010年 | 32篇 |
2009年 | 38篇 |
2008年 | 87篇 |
2007年 | 72篇 |
2006年 | 69篇 |
2005年 | 58篇 |
2004年 | 64篇 |
2003年 | 51篇 |
2002年 | 70篇 |
2001年 | 41篇 |
2000年 | 18篇 |
1999年 | 15篇 |
1998年 | 18篇 |
1997年 | 13篇 |
1996年 | 20篇 |
1995年 | 20篇 |
1994年 | 15篇 |
1993年 | 18篇 |
1992年 | 25篇 |
1991年 | 20篇 |
1990年 | 11篇 |
1989年 | 13篇 |
1988年 | 13篇 |
1987年 | 16篇 |
1986年 | 17篇 |
1985年 | 21篇 |
1984年 | 21篇 |
1983年 | 15篇 |
1982年 | 18篇 |
1981年 | 14篇 |
1980年 | 10篇 |
1979年 | 18篇 |
1978年 | 17篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1975年 | 13篇 |
1974年 | 12篇 |
1973年 | 15篇 |
排序方式: 共有1383条查询结果,搜索用时 171 毫秒
81.
Dr. Yoshikazu Ito Dr. Yoichi Tanabe Dr. H.‐J. Qiu Dr. Katsuaki Sugawara Dr. Satoshi Heguri Dr. Ngoc Han Tu Dr. Khuong Kim Huynh Dr. Takeshi Fujita Prof. Takashi Takahashi Prof. Katsumi Tanigaki Prof. Mingwei Chen 《Angewandte Chemie (International ed. in English)》2014,53(19):4822-4826
We report three‐dimensional (3D) nanoporous graphene with preserved 2D electronic properties, tunable pore sizes, and high electron mobility for electronic applications. The complex 3D network comprised of interconnected graphene retains a 2D coherent electron system of massless Dirac fermions. The transport properties of the nanoporous graphene show a semiconducting behavior and strong pore‐size dependence, together with unique angular independence. The free‐standing, large‐scale nanoporous graphene with 2D electronic properties and high electron mobility holds great promise for practical applications in 3D electronic devices. 相似文献
82.
Rational Design and Identification of a Non‐Peptidic Aggregation Inhibitor of Amyloid‐β Based on a Pharmacophore Motif Obtained from cyclo[‐Lys‐Leu‐Val‐Phe‐Phe‐]
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Tadamasa Arai Takushi Araya Dr. Daisuke Sasaki Dr. Atsuhiko Taniguchi Dr. Takeshi Sato Dr. Youhei Sohma Prof. Motomu Kanai 《Angewandte Chemie (International ed. in English)》2014,53(31):8236-8239
Inhibition of pathogenic protein aggregation may be an important and straightforward therapeutic strategy for curing amyloid diseases. Small‐molecule aggregation inhibitors of Alzheimer’s amyloid‐β (Aβ) are extremely scarce, however, and are mainly restricted to dye‐ and polyphenol‐type compounds that lack drug‐likeness. Based on the structure‐activity relationship of cyclic Aβ16–20 (cyclo‐[KLVFF]), we identified unique pharmacophore motifs comprising side‐chains of Leu2, Val3, Phe4, and Phe5 residues without involvement of the backbone amide bonds to inhibit Aβ aggregation. This finding allowed us to design non‐peptidic, small‐molecule aggregation inhibitors that possess potent activity. These molecules are the first successful non‐peptidic, small‐molecule aggregation inhibitors of amyloids based on rational molecular design. 相似文献
83.
We investigated the fluorescent properties, including the excited-state intermolecular proton transfer, of urea derivatives comprising a coumarin ring, which is a widely used fluorophore. We prepared two different coumarin–urea derivatives, 6CU and 7CU, which bear a urea-based substituent at the 6 and 7 positions of a coumarin ring, respectively. In the presence of the acetate ion, 7CU showed additional tautomer fluorescence emission with respect to 6CU, indicating that tautomer formation depends on the positions of the urea-based substituent on the coumarin ring. Thus, the resonance structures of urea derivatives might play an important role in the behavior of dual fluorescence, which is an important phenomenon applicable to photochemical anion sensing. Moreover, in order to further improve the fluorescence properties of the mentioned derivatives, a CF3 group was introduced in a phenyl ring opposite to a coumarin ring. The fluorescence quantum yield of 7CUCF3 thus synthesized was 65 times as large as that of 7CU, an observation that renders 7CUCF3 a suitable anion sensor candidate. The results of this study will contribute to the development of new molecular designs for highly fluorescent sensing. 相似文献
84.
A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2′:6′,2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI–TOF mass spectrometry, UV–Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311–577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications. 相似文献
85.
水滑石类化合物 (LDH) 的层板金属阳离子组成具有可调变性,通过将具有变价特性的过渡金属定量引入 LDH 层板,经热处理后可以得到具有高比表面积和层板金属原子级分散的混合金属氧化物,后者可广泛用作催化剂载体.如三元Mg-Al-Fe 类水滑石材料在光催化、H2S 选择性氧化和乙苯脱氢等反应中表现出较好的活性.Ir 催化剂在α,β-不饱和醛加氢反应中具有较好的活性,Fe 修饰 Ir 催化剂可提高不饱和醇选择性,但有关 Fe 的作用以及 Fe 与活性组分 Ir 间的相互作用本质还不是很清楚.本文以类水滑石材料 Mg3Al1–xFex为载体,采用等体积浸渍法制备了 Ir 催化剂,并用于肉桂醛加氢反应,通过考察 Fe的加入对 Ir 电子和几何结构的影响揭示了 Fe 的加入对活性和选择性的影响规律.结果表明,当 x 从 0 (Ir/Mg3Al) 增加到 1 (Ir/Mg3Fe) 时,肉桂醛加氢的反应速率在 x = 0.25 时达到最大值,肉桂醇选择性从 44.9% 增加到 80.3%,且不随肉桂醛转化率的增加而改变.透射电镜结果表明,Ir 纳米粒子的粒径随着 x 的增加未发生明显变化,均为 1.7±0.2 nm.H2程序升温还原结果发现 Ir 可以促进 Fe3+的还原且两者之间存在相互作用.X射线光电子能谱结果表明,Fe 的掺杂没有改变催化剂表面Ir0和 Ir4+含量的比值,但当 Fe 含量增加时,Fe2+2p3/2向高结合能方向偏移,且 Ir04f7/2向低结合能方向偏移,说明电子从 Fe2+转移到 Ir,形成了富电子的 Ir 物种和缺电子的 Fe 物种.富电子的 Ir 物种有利于肉桂醛分子中的 C=O 键在其表面吸附,并且和 Ir 相邻的 Fen+物种可以作为亲电位点吸附肉桂醛分子中氧,从而极化和活化 C=O 键,因而催化剂活性和选择性增大.采用吸附 CO 红外光谱表征了催化剂表面的几何结构,2058–2069 cm-1处出现了 CO 吸附峰,归属于 Ir0表面 CO 的线性吸附,高波数 2069 cm-1的吸附峰归属于 CO 在高配位 Ir 位点 (平台) 的吸附,低波数 2058 cm-1的吸附峰归属于 CO 在低配位Ir 位点 (台阶、角、楞) 的吸附.随着 Fe 含量的增加,CO 吸附峰蓝移 11 cm-1,表明 Fe 的加入改变了催化剂表面 Ir 的几何结构,低配位 Ir 位点减少,高配位 Ir 位点增多.高配位 Ir 位点 (平台) 有利于肉桂醛分子中 C=O 键的吸附,从而提高了肉桂醇的选择性.总之,Fe 的加入虽然没有明显改变 Ir 纳米粒子的粒径,但却改变了其电子和几何结构,从而提高了催化剂活性和选择性. 相似文献
86.
87.
88.
89.
Suzuki T Arai K Goto H Hanano M Watanabe J Tomono K 《Chemical & pharmaceutical bulletin》2002,50(6):741-743
Nifedipine-containing calcium phosphate cement (CPC) was prepared, and nifedipine (NF) release from this preparation was evaluated by the shaking method (SK), Japanese Pharmacopoeia XIV (JPXIV) paddle method (PD), and JPXIV flow-through cell method (FT). The release of NF from the CPC preparation continued for 7 d or longer by all these methods. This suggests that the release of NF can be controlled by preparing NF-containing CPC. The release pattern of NF from CPC in these tests was found to follow the Higuchi equation. However, the Higuchi constant differed among the three dissolution tests, probably because the apparent tortuosity of capillary system (tau) varied. 相似文献
90.
Okada K Nagashima T Kameshima Y Yasumori A 《Journal of colloid and interface science》2002,248(1):111-115
The effect of crystallite size on the thermal phase change and porous properties of boehmite was investigated using boehmites with crystallite sizes of 2.9 to 24.4 nm and boehmite gels prepared by precipitation and hydrothermal methods. The dehydroxylation temperature of boehmite increases, its phase transition temperature from gamma- to theta-Al(2)O(3) decreases and the theta- to alpha-Al(2)O(3) transition temperature increases as the crystallite size of the boehmite increases. Boehmite with a crystallite size of approximately 5 nm shows the highest specific surface area and greatest thermal stability. This boehmite contains pores of about 2-3 nm radius, suggested to be responsible for the superior porous properties and thermal stability. 相似文献