全文获取类型
收费全文 | 701篇 |
免费 | 16篇 |
国内免费 | 2篇 |
专业分类
化学 | 403篇 |
晶体学 | 13篇 |
力学 | 24篇 |
数学 | 142篇 |
物理学 | 137篇 |
出版年
2023年 | 6篇 |
2022年 | 10篇 |
2021年 | 14篇 |
2020年 | 22篇 |
2019年 | 28篇 |
2018年 | 24篇 |
2017年 | 17篇 |
2016年 | 46篇 |
2015年 | 20篇 |
2014年 | 30篇 |
2013年 | 113篇 |
2012年 | 48篇 |
2011年 | 63篇 |
2010年 | 55篇 |
2009年 | 39篇 |
2008年 | 37篇 |
2007年 | 37篇 |
2006年 | 21篇 |
2005年 | 13篇 |
2004年 | 13篇 |
2003年 | 10篇 |
2002年 | 18篇 |
2001年 | 7篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有719条查询结果,搜索用时 0 毫秒
31.
Precision PEGylated Polymers Obtained by Sequence‐Controlled Copolymerization and Postpolymerization Modification 下载免费PDF全文
Sansanee Srichan Dr. Hatice Mutlu Dr. Nezha Badi Dr. Jean‐François Lutz 《Angewandte Chemie (International ed. in English)》2014,53(35):9231-9235
Copolymers containing water‐soluble poly(ethylene glycol) (PEG) side chains and precisely controlled functional microstructures were synthesized by sequence‐controlled copolymerization of donor and acceptor comonomers, that is, styrene derivatives and N‐substituted maleimides. Two routes were compared for the preparation of these structures: a) the direct use of a PEG–styrene macromonomer as a donor comonomer, and b) the use of an alkyne‐functionalized styrenic comonomer, which was PEGylated by copper‐catalyzed alkyne–azide cycloaddition after polymerization. The latter method was found to be the most versatile and enabled the synthesis of high‐precision copolymers. For example, PEGylated copolymers containing precisely positioned fluorescent (e.g. pyrene), switchable (e.g. azobenzene), and reactive functionalities (e.g. an activated ester) were prepared. 相似文献
32.
Two novel bidentate Schiff base ligands, 2-(2-hydroxy-3,5-dichloro/diboromo) benzaldehyde-[4-(3-methyl-3-mesitylcyclobutyl)-1,3-thiazol-2-yl]hydrazone,
L1H, L2H and their transition metal complexes are reported. The new ligands and their complexes have been characterized by elemental
analyses, ΛM, infrared, u.v.–vis, 1H- and 13C-n.m.r. spectroscopy, and magnetic susceptibility measurements. The thermal properties of all complexes have been investigated
by TG technique. The complexes contain two monoanionic, bidentate NO ligands. It was found that all the complexes are mononuclear.
Antimicrobial activities of the ligands and their complexes have been tested against five different microorganisms, and some
of the complexes were found to be active against some of the microorganisms studied. 相似文献
33.
Two new Schiff base ligands (L1, L2) have been prepared from the reaction of 2,6-diacetylpyridine and 2-pyridinecarboxyaldehyde with 4-amino-2,3-dimethyl-1-phenyl-3-pyrozolin-5-on,
and their Co(II), Cu(II), Ni(II), Mn(II), and Cr(III) metal complexes have also been prepared. The complexes are formed by
coordination of N and O atoms of the ligands. Their structures were characterized by physico-chemical and spectroscopic methods.
The analytical data shows that the metal to ligand ratio in the Schiff base complexes is 1:2. The Schiff base ligands and
all complexes were evaluated for their in vitro antibacterial and antifungal activities by the disc diffusion method. In addition,
the genotoxic properties of the ligands were studied. 相似文献
34.
A new method for the extraction of both anions and cations is proposed using electro-synthesized polypyrrole (PPy) and overoxidized sulfonated polypyrrole film (OSPPy). In situ anion (chloride, nitrate, sulfate) and cation (calcium, magnesium) uptake and release were examined under controlled potential conditions for prospective applications in electrochemically controlled solid-phase extraction (EC-SPE). The PPy film was used as an anode (anion-exchanger) and OSPPy film was used as a cathode (cation-exchanger) material and reverse order of the electrodes were investigated in EC-SPE. This new cell arrangement containing two ion exchanger polymer electrodes was developed to provide in situ removal of both anions and cations from aqueous solution. Simple preparation of the film coatings on a platinum plate was possible using a constant potential method. Applied positive and negative potentials facilitated the in situ extraction and desorption of ions, respectively. Both anions and cations were desorbed into sample aliquot and were determined by ion chromatography (IC). The method was validated using a standard reference material and tested for the determination of the ions in real water samples. 相似文献
35.
In this study, first, a series of chalcone compounds S1–S6 were synthesized from various acetophenone derivatives (acetophenone, p-methyl acetophenone, and p-methoxy acetophenone) and aromatic aldehyde derivatives (benzaldehyde, p-methyl benzaldehyde, and p-methoxy benzaldehyde) by the Claisen–Schmidt condensation reaction. These S1–S6 compounds were then used in the preparation of 4,5-dihydropyrazol-1-yl derivatives S7–S15. Finally, four new compounds S16–S19 were synthesized from compound (S7, S8, S9, and S12) and 2,4-dinitrophenylhydrazine. Therefore, three known and ten new heterocyclic compounds were synthesized and completely characterized using 1H NMR, 13C NMR, IR, and elemental analysis. 相似文献
36.
Furo[3,2‐c]pyran‐4‐ones, which possess a natural‐product skeleton, are synthesized via a simple, one‐pot, three‐component reaction of furan‐2,3‐diones with dialkyl acetylenedicarboxylates and Ph3P. 相似文献
37.
The Zn(II) complex, dichloro[N-hydroxy-1,1-di(2-pyridinyl)methanimine]zinc(II), was synthesized from the reaction between ZnCl2 and di-2-pyridylketone oxime. The structural and spectral characterizations were performed by using single crystal X-ray diffraction, FT-IR, Laser-Raman, NMR and UV–Vis spectroscopic techniques. To support experimental evidences, computational results were obtained with the DFT/B3LYP method using the 6-311++G(d,p)+LanL2DZ mixed basis set. Theoretical analyses of some structural and spectroscopic results of effects of intermolecular Cl···H interactions in the crystal packing of the Zn(II) complex were investigated with the mentioned computational level. The non-bonding interactions in the experimental crystal packing of the complex were examined by Hirshfeld surface analysis. The HOMO and LUMO analyses were used for investigation of electronic transitions obtained with UV–Vis spectroscopy. NBO analyses were used to investigate the hyperconjugation interactions between donor and acceptor groups, coordination environment, electronic configuration and electron numbers of the Zn(II) metal ion and the natural atomic charges of the complex. The nucleophilic and electrophilic reactive sites of the complex were studied by MEP surface analysis. The static polarizabilities (α) and static hyperpolarizabilities (β) were analyzed theoretically to characterize NLO profile of the complex. The interaction with A-DNA (PDB ID: 1ZF6) of the Zn(II) complex was investigated with a molecular docking study. 相似文献
38.
Hasan Kırmızıbekmez Yiğit İnan Rengin Reis Hande Sipahi Ahmet C. Gören Erdem Yeşilada 《Natural product research》2019,33(17):2541-2544
Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls. 相似文献
39.
New epoxy resins were prepared from hydroxyl substituted Schiff base monomers in two steps. The first step is based on the synthesis of hydroxyl substituted Schiff base monomers via condensation reaction. The second step includes the reaction between Schiff base monomers with epichlorohydrine (EPC) to obtain epoxy resins. The structures of resulting compounds were confirmed by FTIR and 1H-NMR. TG-DTA and DSC measurements were made for thermal characterizations of the compounds. Chemical resistances of the cured epoxy-amine systems in acidic, alkaline and organic solvents were determined for coating applications. HCl (aqueous solution, 10%), NaOH (aqueous solution, 10%), DMSO, DMF, N-methylpyrrolidone, ethanol, THF and acetone were used for corrosion tests. Chemical resistance data show that the synthesized resins have good chemical resistance against various acid, alkaline and common organic solvents. 相似文献
40.
Tekin H Ozaydin-Ince G Tsinman T Gleason KK Langer R Khademhosseini A Demirel MC 《Langmuir : the ACS journal of surfaces and colloids》2011,27(9):5671-5679
Given its biocompatibility, elasticity, and gas permeability, poly(dimethylsiloxane) (PDMS) is widely used to fabricate microgrooves and microfluidic devices for three-dimensional (3D) cell culture studies. However, conformal coating of complex PDMS devices prepared by standard microfabrication techniques with desired chemical functionality is challenging. This study describes the conformal coating of PDMS microgrooves with poly(N-isopropylacrylamide) (PNIPAAm) by using initiated chemical vapor deposition (iCVD). These microgrooves guided the formation of tissue constructs from NIH-3T3 fibroblasts that could be retrieved by the temperature-dependent swelling property and hydrophilicity change of the PNIPAAm. The thickness of swollen PNIPAAm films at 24 °C was approximately 3 times greater than at 37 °C. Furthermore, PNIPAAm-coated microgroove surfaces exhibit increased hydrophilicity at 24 °C (contact angle θ = 30° ± 2) compared to 37 °C (θ = 50° ± 1). Thus PNIPAAm film on the microgrooves exhibits responsive swelling with higher hydrophilicity at room temperature, which could be used to retrieve tissue constructs. The resulting tissue constructs were the same size as the grooves and could be used as modules in tissue fabrication. Given its ability to form and retrieve cell aggregates and its integration with standard microfabrication, PNIPAAm-coated PDMS templates may become useful for 3D cell culture applications in tissue engineering and drug discovery. 相似文献