全文获取类型
收费全文 | 7013篇 |
免费 | 808篇 |
国内免费 | 600篇 |
专业分类
化学 | 5232篇 |
晶体学 | 542篇 |
力学 | 106篇 |
综合类 | 29篇 |
数学 | 72篇 |
物理学 | 2440篇 |
出版年
2024年 | 11篇 |
2023年 | 56篇 |
2022年 | 115篇 |
2021年 | 150篇 |
2020年 | 223篇 |
2019年 | 188篇 |
2018年 | 211篇 |
2017年 | 226篇 |
2016年 | 411篇 |
2015年 | 265篇 |
2014年 | 306篇 |
2013年 | 1009篇 |
2012年 | 335篇 |
2011年 | 327篇 |
2010年 | 312篇 |
2009年 | 370篇 |
2008年 | 364篇 |
2007年 | 471篇 |
2006年 | 387篇 |
2005年 | 359篇 |
2004年 | 305篇 |
2003年 | 271篇 |
2002年 | 235篇 |
2001年 | 189篇 |
2000年 | 173篇 |
1999年 | 177篇 |
1998年 | 154篇 |
1997年 | 83篇 |
1996年 | 107篇 |
1995年 | 88篇 |
1994年 | 95篇 |
1993年 | 71篇 |
1992年 | 53篇 |
1991年 | 35篇 |
1990年 | 44篇 |
1989年 | 22篇 |
1988年 | 37篇 |
1987年 | 23篇 |
1986年 | 20篇 |
1985年 | 16篇 |
1984年 | 25篇 |
1983年 | 12篇 |
1982年 | 18篇 |
1981年 | 12篇 |
1980年 | 11篇 |
1979年 | 13篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1975年 | 8篇 |
1973年 | 9篇 |
排序方式: 共有8421条查询结果,搜索用时 349 毫秒
1.
The effects of PEA on the γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy(OM), infrared spectroscopy(IR) and scanning electron microscopy(SEM). The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within the γ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF. 相似文献
2.
Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ismael Gracia Beatriz Feringán Prof. José Luis Serrano Dr. Roberto Termine Dr. Attilio Golemme Dr. Ana Omenat Prof. Joaquín Barberá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(3):1359-1369
The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role. 相似文献
3.
Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Yuya Domoto Dr. Eric Busseron Prof. Dr. Mounir Maaloum Dr. Emilie Moulin Prof. Dr. Nicolas Giuseppone 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1938-1948
We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by 1H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases. 相似文献
4.
Renny Mathew Karolina A. Uchman Lydia Gkoura Chris J. Pickard Maria Baias 《Magnetic resonance in chemistry : MRC》2020,58(11):1018-1025
A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated 1H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs. 相似文献
5.
Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis
Dr. Damien Dambournet Dr. Karena W Chapman Dr. Mathieu Duttine Dr. Olaf Borkiewicz Dr. Peter J Chupas Dr. Henri Groult 《ChemistryOpen》2015,4(4):443-447
The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties. 相似文献
6.
Thomas Marmin Prof. Yves L. Dory 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6707-6711
Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C3-symmetric rings incorporating conjugated alkenes and dienes. All three C3-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals. 相似文献
7.
Denis Kudryavtsev Anastasia Isaeva Daria Barkova Ekaterina Spirova Renata Mukhutdinova Igor Kasheverov Victor Tsetlin 《Molecules (Basel, Switzerland)》2021,26(5)
Slow-channel congenital myasthenic syndromes (SCCMSs) are rare genetic diseases caused by mutations in muscle nicotinic acetylcholine receptor (nAChR) subunits. Most of the known SCCMS-associated mutations localize at the transmembrane region near the ion pore. Only two SCCMS point mutations are at the extracellular domains near the acetylcholine binding site, α1(G153S) being one of them. In this work, a combination of molecular dynamics, targeted mutagenesis, fluorescent Ca2+ imaging and patch-clamp electrophysiology has been applied to G153S mutant muscle nAChR to investigate the role of hydrogen bonds formed by Ser 153 with C-loop residues near the acetylcholine-binding site. Introduction of L199T mutation to the C-loop in the vicinity of Ser 153 changed hydrogen bonds distribution, decreased acetylcholine potency (EC50 2607 vs. 146 nM) of the double mutant and decay kinetics of acetylcholine-evoked cytoplasmic Ca2+ rise (τ 14.2 ± 0.3 vs. 34.0 ± 0.4 s). These results shed light on molecular mechanisms of nAChR activation-desensitization and on the involvement of such mechanisms in channelopathy genesis. 相似文献
8.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
9.
Dr. Si-Yong Qin Yan Jiang Dr. Han Sun Han Liu Prof. Ai-Qing Zhang Prof. Xinxiang Lei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17245-17251
Residual dipolar coupling (RDC), a robust anisotropic NMR parameter for structural elucidation of organic molecules, is only accessible in an anisotropic environment. Herein, we introduce a novel alignment medium based on the molecular self-assembly of oligopeptide amphiphile (OPA). This medium is compatible with different intermediate and polar solvent systems, such as CD3OD, [D6]DMSO, and D2O. The preparation of the OPA-based medium is simple and rapid, while only very weak background signals were observed from OPAs. Furthermore, we show that the purity of OPA has only a minor influence on the quality of the RDC data. These advantages allow RDC measurements of organic molecules with different polarities and solubilities with high efficiency and accuracy. 相似文献
10.
In this work, the beam splitter with two input ports and two output ports in two-dimensional photonic crystals is studied through the finite-difference time-domain method. The beam splitter consists of two orthogonally cross line defects. The diameter of the two diagonal air holes at the intersection of the two line defects was modified. The input light can be identically divided into the two output ports. The beam splitters can be applied in the photonic crystal Mach-Zehnder interferometers or photonic crystal optical switches. 相似文献