全文获取类型
收费全文 | 9889篇 |
免费 | 1333篇 |
国内免费 | 2061篇 |
专业分类
化学 | 10503篇 |
晶体学 | 118篇 |
力学 | 416篇 |
综合类 | 83篇 |
数学 | 59篇 |
物理学 | 2104篇 |
出版年
2024年 | 21篇 |
2023年 | 150篇 |
2022年 | 325篇 |
2021年 | 487篇 |
2020年 | 747篇 |
2019年 | 557篇 |
2018年 | 373篇 |
2017年 | 449篇 |
2016年 | 477篇 |
2015年 | 484篇 |
2014年 | 505篇 |
2013年 | 911篇 |
2012年 | 683篇 |
2011年 | 531篇 |
2010年 | 412篇 |
2009年 | 500篇 |
2008年 | 508篇 |
2007年 | 527篇 |
2006年 | 547篇 |
2005年 | 491篇 |
2004年 | 520篇 |
2003年 | 437篇 |
2002年 | 407篇 |
2001年 | 270篇 |
2000年 | 242篇 |
1999年 | 169篇 |
1998年 | 151篇 |
1997年 | 167篇 |
1996年 | 158篇 |
1995年 | 192篇 |
1994年 | 152篇 |
1993年 | 146篇 |
1992年 | 125篇 |
1991年 | 77篇 |
1990年 | 61篇 |
1989年 | 50篇 |
1988年 | 48篇 |
1987年 | 47篇 |
1986年 | 25篇 |
1985年 | 25篇 |
1984年 | 19篇 |
1983年 | 12篇 |
1982年 | 18篇 |
1981年 | 19篇 |
1980年 | 17篇 |
1979年 | 13篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 8篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Effects of graded porous structure on local strain distribution under compression in silicone rubber
Keijiro Yoshimura Kazunori Nakano Takeshi Nishiwaki Yuki Iwama Masanobu Murata 《Journal of Polymer Science.Polymer Physics》2019,57(16):1033-1042
Silicone rubber samples with gradually changing pore sizes within the range of 70–610 μm are produced using an improved spacer method. The samples are scanned using an X‐ray computed tomography to evaluate their graded structure as compared to uniform rubber. A compressive test reveals that graded porous silicone rubber has characteristic stress–strain curves whose slope changes within a specific strain range depending on the porous structure. Analysis results of local strain based on a digital image correlation of the graded porous silicone rubber under compression demonstrate that the characteristic stress–strain properties are caused by shifts in the main deformation region in the graded structure. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1033–1042 相似文献
72.
Three multinuclear Cu (II), Zn (II) and Cd (II) complexes, [Cu2(L)(μ‐OAc)]·CHCl2 ( 1 ), [Zn2(L)(μ‐OAc)(H2O)]·3CHCl3 ( 2 ) and [{Cd2(L)(OAc)(CH3CH2OH)}2]·2CH3CH2OH ( 3 ) with a single‐armed salamo‐like dioxime ligand H3L have been synthesized, and characterized by FT‐IR, UV–vis, X‐ray crystallography and Hirshfeld surfaces analyses. The ligand H3L has a linear structure and C‐H···π interactions between the two molecules. The complex 1 is a dinuclear Cu (II) complex, Cu1 and Cu2 are all five‐coordinate possessing distorted square pyramidal geometries. The complex 2 also forms a dinuclear Zn (II) structure, and Zn1 and Zn2 are all five‐coordinate bearing distorted trigonal bipyramidal geometries. The complex 3 is a symmetrical tetranuclear Cd (II) complex, and Cd1 is a hexa‐coordinate having octahedral configuration and Cd2 is hepta‐coordinate with a pentagonal bipyramidal geometry, and it has π···π interactions inside the molecule. In addition, fluorescence properties of the ligand and its complexes 1 – 3 have also been discussed. 相似文献
73.
Viko Ladelta George Zapsas Yves Gnanou Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2450-2456
New tricrystalline triblock terpolymers, polyethylene‐block‐poly(ε‐caprolactone)‐block‐poly(L‐lactide) (PE‐b‐PCL‐b‐PLLA), were synthesized by ROP of ε‐caprolactone (CL) and L‐lactide (LLA) from linear ω‐hydroxyl polyethylene (PE‐OH) macroinitiators. The linear PE‐OH macroinitiators were prepared by C1 polymerization of methylsulfoxonium methylide (polyhomologation). Tin(II) 2‐ethylhexanoate was used as the catalyst for the sequential ROP of CL and LLA in one‐pot polymerization at 85 °C in toluene (PE‐OH macroinitiators are soluble in toluene at 80 °C). 1H NMR spectra confirmed the formation of PE‐b‐PCL‐b‐PLLA triblock terpolymers through the appearance of the characteristic proton peaks of each block. GPC traces showed the increase in the number average molecular weight from PE‐OH macroinitiator to PE‐b‐PCL, and PE‐b‐PCL‐b‐PLLA corroborating the successful synthesis. The existence of three crystalline blocks was proved by DSC and XRD spectroscopy. © 2019 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2450–2456 相似文献
74.
Alisson J. Santana Denis A. Turchetti Cristiano Zanlorenzi Jos C. R. Santos Edson Laureto Adilson J. A. De Oliveira Leni Akcelrud 《Journal of Polymer Science.Polymer Physics》2019,57(6):304-311
Poly[9,9′‐dihexylfluorene‐2,7‐diyl)‐6,6″‐(2,2′:6′,2″‐terpyridine)] (LaPPS75) and its complexes with neodymium were synthesized and characterized. Magnetic measurements showed that the noncomplexed polymer presented a ferromagnetic contribution due to the formation of π stacking, and that in absence of those, the ferromagnetic behavior is suppressed. The pristine polymer, the complexed one and a low‐molecular‐weight model compound with the same structure of the complexed site in the parent polymer were studied. The observed behavior found is presented and discussed, the most important finding was that when a conjugated chain is used as a host for the metallic ion, an amplification of four times for the magnetization is achieved, using the same metallic content for complexed polymer and model compound for comparison. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 304–311 相似文献
75.
E. B. Tarabukina E. I. Fatullaev A. P. Filippov K. A. Abzaeva 《International Journal of Polymer Analysis and Characterization》2019,24(1):10-17
Metal complexes of polyacrylic acid containing Li, Li, and Cu, or Li and Zn have been studied in saline aqueous solutions using molecular hydrodynamics and light scattering methods. Intrinsic viscosities, weight-average molar masses, hydrodynamic radii, and radii of gyration were obtained. It was shown that the macromolecules of polymetalloacrylates containing divalent metals form small and large supramolecular structures, their dimensions, and composition being dependent on the ionic strength of the solution. 相似文献
76.
Heavy metal ions are harmful to aquatic life and humans owing to their high toxicity and non‐biodegradability, so their removal from wastewater is an important task. Therefore, this work focuses on designing suitable, simple and economical nanosensors to detect and remove these metal ions with high selectivity and sensitivity. Based on this idea, different types of mesoporous materials such as hexagonal SBA‐15, cubic SBA‐16 and spherical MCM‐41, their chloro‐functionalized derivatives, as well as 4‐(4‐nitro‐phenylazo)‐naphthalen‐1‐ol (NPAN) azo dye have been synthesized, with the aim of designing some optical nanosensors for metal ions sensing applications. The mentioned azo dye has been anchored into the chloro‐functionalized mesoporous materials. The designed nanosensors were characterized using scanning and transmission electron microscopy as well as Fourier transform infrared and UV–visible spectral analysis, nitrogen adsorption–desorption isotherms, low‐angle X‐ray diffraction and thermogravimetric analyses. Their optical sensing to various toxic metal ions such as Cd (II), Hg (II), Mn (II), Fe (II), Zn (II) and Pb (II) at different values of pH (1.1, 4.9, 7 and 12) was investigated. The optimization of experimental conditions, including the effect of pH and metal ion concentration, was examined. The experimental results showed that the solution pH had a major impact on metal ion detection. The optical nanosensors respond well to the tested metal ions, as reflected by the enhancement in both absorption and emission spectra upon adding different concentrations of the metal salts and were fully reversible on adding ethylene diamine tetra acetic acid or citric acid to the formed complexes. High values of the binding constants for the designed nanosensors were observed at pHs 7 and 12, confirming the strong chelation of different metals to the nanosensor at these pHs. Also, high binding constants and sensitivity were observed for NPAN‐MCM‐41 as a nanosensor to detect the different metal ions. From the obtained results, we succeeded in transforming the harmful azo dye into an environmentally friendly form via designing of the optical nanosensors used to detect toxic metal ions in wastewater with high sensitivity. 相似文献
77.
Vidya Rani Chandrasekhar Kesavan Mookkandi Palsamy Ravi Lokesh Daniel Thangadurai T. Indra Gandhi N. Rajesh Jegathalaprathaban Rajagopal Gurusamy 《应用有机金属化学》2019,33(3)
Three new metal complexes [Cu(L)2] (1), [Co(L)2] (2) and [Zn(L)2] (3) have been prepared by the reaction of hydrated salts of metal (II) acetate with new Schiff base ligand HL, [2‐((4‐(dimethylamino)phenylimino)methyl)‐4,6‐di‐t‐butylphenol] and characterized by different physico‐chemical analyses such as elemental analysis, single XRD, 1H NMR, FTIR and UV–Vis spectroscopic techniques. Their biomolecular docking, antimicrobial and cytotoxicity studies have also been demonstrated. The proposed structure of Schiff base ligand HL and complex 2 are confirmed by Single crystal X‐ray crystallography study. This analysis revealed that metal (II) complexes remain in distorted tetrahedral coordination environments. The electronic properties such as HOMO and LUMO energies are carried out by gaseous phase DFT/B3LYP calculations using Gaussian 09 program. Complex 1 showed a good binding propensity to the DNA and HSA, during the assessment of docking studies. Schiff base ligand HL and its metal (II) complexes, 1–3 screened for their in vitro antimicrobial activities using the disc diffusion method against selected microbes. Complex 1 shows higher antimicrobial activity than complexes 2, 3 and Schiff base ligand HL. According to the results obtained from the cytotoxic studies, Schiff base ligand HL and its metal (II) complexes 1–3 have better cytotoxicity against MCF‐7 cell lines with potency higher than the currently used chemotherapeutic agent cyclophosphamide. 相似文献
78.
Anshu Dandia Dinesh Kumar Mahawar Ruchi Sharma Ranveer Singh Badgoti Kuldeep S. Rathore Vijay Parewa 《应用有机金属化学》2019,33(11)
Graphene oxide (GO)‐catalyzed selective synthesis of amides via CSp3–H activation of methylarenes and consequent C–N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co‐oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal‐free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform‐infrared, UV–Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over‐oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles. 相似文献
79.
Y. T. Angel Wong Vinicius Martins Dr. Bryan E. G. Lucier Prof. Dr. Yining Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(8):1848-1853
Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development. 相似文献
80.
Dr. Ritesh Haldar Kamal Batra Stefan Michael Marschner Dr. Agnieszka B. Kuc Dr. Stefan Zahn Prof. Dr. Roland A. Fischer Prof. Dr. Stefan Bräse Prof. Dr. Thomas Heine Prof. Dr. Christof Wöll 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7847-7851
In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties. 相似文献