全文获取类型
收费全文 | 1968篇 |
免费 | 169篇 |
国内免费 | 166篇 |
专业分类
化学 | 1074篇 |
晶体学 | 16篇 |
力学 | 21篇 |
综合类 | 13篇 |
数学 | 899篇 |
物理学 | 280篇 |
出版年
2024年 | 4篇 |
2023年 | 15篇 |
2022年 | 31篇 |
2021年 | 41篇 |
2020年 | 56篇 |
2019年 | 67篇 |
2018年 | 57篇 |
2017年 | 62篇 |
2016年 | 55篇 |
2015年 | 44篇 |
2014年 | 72篇 |
2013年 | 373篇 |
2012年 | 78篇 |
2011年 | 71篇 |
2010年 | 54篇 |
2009年 | 75篇 |
2008年 | 71篇 |
2007年 | 87篇 |
2006年 | 79篇 |
2005年 | 58篇 |
2004年 | 53篇 |
2003年 | 58篇 |
2002年 | 329篇 |
2001年 | 66篇 |
2000年 | 48篇 |
1999年 | 41篇 |
1998年 | 38篇 |
1997年 | 24篇 |
1996年 | 30篇 |
1995年 | 23篇 |
1994年 | 13篇 |
1993年 | 13篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 4篇 |
1983年 | 14篇 |
1982年 | 22篇 |
1981年 | 18篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有2303条查询结果,搜索用时 31 毫秒
71.
The increasing application of positron emission tomography (PET) in nuclear medicine has stimulated the extensive development of a multitude of novel and versatile techniques to introduce fluorine-18, especially for the radiolabelling of biologically or pharmacologically active molecules. Taking into consideration that the introduction of fluorine-18 (t1/2=109.8 min) mostly proceeds under harsh conditions, radiolabelling of such molecules represents a challenge and is of enormous interest. Ideally, it should proceed in a regioselective manner under mild physiological conditions, in an acceptable time span, with high yields and high specific activities. Special attention has been drawn to 2-fluoroethyl and 3-fluoropropyl groups, which are often the active sites of radiofluorinated compounds. Precursors containing an ammonium leaving group – such as a strained azetidinium or aziridinium moiety – can help to overcome these obstacles leading to a convenient and mild introduction of [18F]fluoride with high radiochemical yields. 相似文献
72.
Peng Sun Zihan Xia Zhongfang Li Ziwei Fan Fengqi He Qiang Liu Xiaoyan Yin 《Materials Today Chemistry》2022
A high-temperature proton exchange membrane with high proton conductivity over a wide humidity range still remains a challenge. PBI dendrimer containing triazine rings (TPBI) was synthesized to approach this aim considering its high content of hygroscopic terminal groups and of larger free volume. A novel proton conductor previously synthesized (zirconium 3-sulfopropyl phosphonate, ZrSP) was doped due to its good proton conductivity over a wide humidity range. TPBI was post-crosslinked with a tetrafunctional epoxy resin (N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, TGDDM) to enhance the mechanical stability at low cross-linking degrees, which allowed high doping levels of ZrSP, and thus, high conductivity. The prepared membranes (TPBI-TGDDM/ZrSP) showed good thermal stability, high proton conductivity over wide humidity range, and good dimensional stability. At suitable degrees of branching, TPBI-TGDDM/ZrSP exhibited superior mechanical property, oxidative stability, methanol barrier property, and membrane selectivity than its linear analog (mPBI-TGDDM/ZrSP). As ZrSP instead of PA was applied as the proton conductor, TPBI-TGDDM/ZrSP showed good durability of proton conductivity, especially in comparison with TPBI-TGDDM/PA, which highly retarded decline in conductivity caused by PA leaking. The proton conductivity at 180 °C of TPBI(20)-TGDDM(10)/ZrSP(50) achieved 142, 84.2 and 23.6 mS cm?1 at 100%, 50%, and 0 RH, respectively. 相似文献
73.
Dr. Joffrey Pijeat Léo Chaussy Roxanne Simoës Dr. Jacopo Isopi Prof. Dr. Jean-Sébastien Lauret Prof. Dr. Francesco Paolucci Prof. Dr. Massimo Marcaccio Dr. Stéphane Campidelli 《ChemistryOpen》2021,10(10):997-1003
The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the β-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin. 相似文献
74.
Jolanta Pyteraf Witold Jamrz Mateusz Kurek Joanna Szafraniec-Szczsny Daniel Kramarczyk Karolina Jurkiewicz Justyna Knapik-Kowalczuk Jacek Tarasiuk Sebastian Wroski Marian Paluch Renata Jachowicz 《Molecules (Basel, Switzerland)》2021,26(11)
The flexibility of dose and dosage forms makes 3D printing a very interesting tool for personalized medicine, with fused deposition modeling being the most promising and intensively developed method. In our research, we analyzed how various types of disintegrants and drug loading in poly(vinyl alcohol)-based filaments affect their mechanical properties and printability. We also assessed the effect of drug dosage and tablet spatial structure on the dissolution profiles. Given that the development of a method that allows the production of dosage forms with different properties from a single drug-loaded filament is desirable, we developed a method of printing ketoprofen tablets with different dose and dissolution profiles from a single feedstock filament. We optimized the filament preparation by hot-melt extrusion and characterized them. Then, we printed single, bi-, and tri-layer tablets varying with dose, infill density, internal structure, and composition. We analyzed the reproducibility of a spatial structure, phase, and degree of molecular order of ketoprofen in the tablets, and the dissolution profiles. We have printed tablets with immediate- and sustained-release characteristics using one drug-loaded filament, which demonstrates that a single filament can serve as a versatile source for the manufacturing of tablets exhibiting various release characteristics. 相似文献
75.
提出了三种基于少模光纤的全光纤熔融模式选择耦合器. 根据模式匹配原理采用单模光纤与少模光纤熔融连接方式, 运用耦合模理论及光束传播法模拟分析了模式选择耦合器的结构参数对模式选择及耦合特性的影响, 实现了单模光纤中基模到少模光纤中不同阶模式的转换, 以满足不同的应用需求. 实验上以2× 2熔融光纤耦合器为例, 采用对称和非对称熔融拉锥方式, 分别实现了从基模到LP11, LP21模式的转换. 实验结果表明所得到的LP11, LP21模式在1530–1560 nm的波长带宽范围内均有较高的模式纯净度, 且模式耦合效率高于80%, 与理论模拟结果基本一致. 相似文献
76.
In light of the generator polynomials of constacyclic codes over finite chain rings, the depth spectrum of constacyclic codes can be determined if (n,p)=1. 相似文献
77.
We study electron energies in a double concentric quantum ring with anisotropy in the rims heights in the presence of the external magnetic field applied along the symmetry axis. To this end, we consider a model in which the thickness grows linearly from the axis up to the inner rim with a slope different from one between the inner and the outer rims. The anisotropy in the rims heights originated by the presence in the structure of various valleys we simulate by periodic dependence of the slope on the radial direction. We show that the wave functions of the electron confined in such structure can be found analytically if the slopes in all radial directions are the same, and by using a simple exact diagonalization procedure otherwise. The behavior of the electron energies as functions of the magnetic field, rings radii and rims heights, as well as the number of the valleys and their depths is consistently described with our formalism. The entanglement of the states with different radial and orbital quantum numbers, the period and the amplitude of the Aharonov–Bohm oscillations are very sensible to any variations of the rims heights. 相似文献
78.
Synthesis of Chiral Exocyclic Amines by Asymmetric Hydrogenation of Aromatic Quinolin‐3‐amines 下载免费PDF全文
Xian‐Feng Cai Ran‐Ning Guo Mu‐Wang Chen Lei Shi Prof. Yong‐Gui Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7245-7248
Asymmetric hydrogenation of aromatic quinolin‐3‐amines was successfully developed with up to 94 % enantiomeric excess (ee). Introduction of the phthaloyl moiety to the amino group is crucial to eliminate the inhibition effect caused by the substrate and product, to activate the aromatic ring, and to improve the diastereoselectivity. This new methodology provides direct and facile access to chiral exocyclic amines. Notably, this report is the first on the highly enantioselective hydrogenation of aromatic amines. 相似文献
79.
HOMO Stabilisation in π‐Extended Dibenzotetrathiafulvalene Derivatives for Their Application in Organic Field‐Effect Transistors 下载免费PDF全文
Dr. Yan Geng Dr. Raphael Pfattner Antonio Campos Prof. Wei Wang Dr. Olivier Jeannin Dr. Jürg Hauser Dr. Joaquim Puigdollers Prof. Stefan T. Bromley Prof. Silvio Decurtins Prof. Jaume Veciana Prof. Concepció Rovira Dr. Marta Mas‐Torrent Dr. Shi‐Xia Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16672-16679
Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB‐TTF) central core and a 2,1,3‐chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB‐TTF, have been synthesised as active materials for organic field‐effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron‐withdrawing 2,1,3‐chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution‐processed single‐crystal transistors exhibit high performance with a hole mobility up to 0.04 cm2 V?1 s?1 as well as good ambient stability. 相似文献
80.
Oligotriarylamines with a Pyrene Core: A Multicenter Strategy for Enhancing Radical Cation and Dication Stability and Tuning Spin Distribution 下载免费PDF全文
Hai‐Jing Nie Chang‐Jiang Yao Jiang‐Yang Shao Prof. Dr. Jiannian Yao Prof. Dr. Yu‐Wu Zhong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17454-17465
Monoamine 1 , diamines 2 – 4 , triamine 5 , and tetraamine 6 have been synthesized by substituting dianisylamino groups at the 1‐, 3‐, 6‐, and/or 8‐positions of pyrene. Diamines 2 – 4 differ in the positions of the amine substituents. No pyrene–pyrene interactions are evident in the single‐crystal packing of 3 , 4 , and 6 . With increasing numbers of amine substituents, the first oxidation potential decreases progressively from the mono‐ to the tetraamine. These compounds show intense charge‐transfer (CT) emission in CH2Cl2 at around 530 nm with quantum yields of 48–68 %. Upon stepwise oxidation by electrolysis or chemical oxidation, these compounds were transformed into radical cations 1 ?+– 6 ?+ and dications 2 2+– 6 2+, which feature strong visible and near‐infrared absorptions. Time‐dependent density functional theory studies suggested the presence of localized transitions from the pyrene radical cation and aminium radical cation, intervalence CT, and CT between the pyrene and amine moieties. Spectroscopic studies indicated that these radical cations and dications have good stability. Triamine 5 and tetraamine 6 formed efficient CT complexes with tetracyanoquinodimethane in solution. The results of EPR spectroscopy and density functional theory calculations suggested that the dications 2 2+– 4 2+ have a triplet ground state, whereas 5 2+ and 6 2+ have a singlet ground state. The dication of 1,3‐disubstituted diamine 4 exhibits a strong EPR signal. 相似文献