全文获取类型
收费全文 | 35705篇 |
免费 | 2351篇 |
国内免费 | 1754篇 |
专业分类
化学 | 21476篇 |
晶体学 | 528篇 |
力学 | 726篇 |
综合类 | 615篇 |
数学 | 6592篇 |
物理学 | 9873篇 |
出版年
2023年 | 227篇 |
2022年 | 373篇 |
2021年 | 1264篇 |
2020年 | 754篇 |
2019年 | 832篇 |
2018年 | 627篇 |
2017年 | 671篇 |
2016年 | 958篇 |
2015年 | 925篇 |
2014年 | 1167篇 |
2013年 | 2535篇 |
2012年 | 1345篇 |
2011年 | 1556篇 |
2010年 | 1463篇 |
2009年 | 1936篇 |
2008年 | 2011篇 |
2007年 | 2232篇 |
2006年 | 1666篇 |
2005年 | 1063篇 |
2004年 | 977篇 |
2003年 | 1047篇 |
2002年 | 3514篇 |
2001年 | 1227篇 |
2000年 | 730篇 |
1999年 | 534篇 |
1998年 | 534篇 |
1997年 | 361篇 |
1996年 | 457篇 |
1995年 | 401篇 |
1994年 | 413篇 |
1993年 | 454篇 |
1992年 | 447篇 |
1991年 | 292篇 |
1990年 | 261篇 |
1989年 | 204篇 |
1988年 | 242篇 |
1987年 | 197篇 |
1986年 | 214篇 |
1985年 | 320篇 |
1984年 | 243篇 |
1983年 | 145篇 |
1982年 | 299篇 |
1981年 | 469篇 |
1980年 | 431篇 |
1979年 | 471篇 |
1978年 | 371篇 |
1977年 | 282篇 |
1976年 | 239篇 |
1974年 | 77篇 |
1973年 | 156篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
91.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
92.
A greener and efficient method for the synthesis of ynones and 1,3-diynes using copper oxide nanoparticles (CuONPs) doped reduced graphene oxide (CuO@rGO) catalyst under palladium, ligand and solvent free conditions have been developed. The catalyst was subsequently utilized for the synthesis of biologically active 1,5-benzodiazepines in one pot via sequential addition of acyl chlorides, terminal alkynes and o-phenylenediamines. The methodology initially involves in situ formation of ynones which react with o-phenylenediamines in presence of ethanol to afford a wide variety of benzodiazepines. Mild reaction conditions, good to an excellent yield of the products, cheap and recyclable catalyst make this methodology environmentally benign and sustainable. 相似文献
93.
Metal closures with a polymer-based sealing for beer bottles have been known since the late nineteen-sixties. However, to what extent which parameter of the polymer sealing gasket plays a role in closure performance to keep the beer quality to a highest level possible is not fully understood. For this purpose three thermoplastic elastomer (TPE) liners were investigated by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectrometry, dynamical mechanical analysis (DMA), scanning electron microscopy (SEM) and surface roughness in order to understand the effect of relative humidity (RH) and carbon dioxide (CO2) on their physical and chemical properties as well as their macromolecular structures. The TPEs’ viscoelasticity in the frequency domain under different isothermal conditions was evaluated. RH and CO2 were effective for changes in thermomechanical and surface properties. Liner C was found to have lower seal performance attributed to its relatively higher crystallinity, stiffness, weaker bond structure and rougher surface. Vibrations can lead to seal leakage in Liner B due to its higher damping behavior during production and transportation. Liner A outperforms others due to stabile behavior within the operational temperature range. 相似文献
94.
Suresh P S Ravi Kumar Trivedi Nuggehally R. Srinivas Ramesh Mullangi 《Biomedical chromatography : BMC》2020,34(1):e4742
Quantitation of drugs used for the treatment of chronic lymphocytic leukemia in various biological matrices during both pre-clinical and clinical developments is very important, often in routine therapeutic drug monitoring. The first developed methods for quantitation were traditionally done on LC in combination with either UV or fluorescence detection. However, the emergence of LC with mass spectrometry in tandem in early 1990s has revolutionized the quantitation as it has provided better sensitivity and selectivity within a shorter run time; therefore it has become the choice of method for the analysis of various drugs. In this article, an overview of various bioanalytical methods (HPLC or LC–MS/MS) for the quantification of drugs for the treatment of chronic lymphocytic leukemia, along with applicability of these methods, is given. 相似文献
95.
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
96.
Yuto Kurasaki Yasuhito Suzuki Akikazu Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2020,58(7):923-931
We carried out the thermal curing of the copolymers of N-allylmaleimide (AMI) and 2-ethylhexyl acrylate (2EHA) using 1,3,4,6-tetra(2-mercaproethyl)glycoluril ( G1 ), 1,3,4,6-tetra(3-mercaptopropyl)glycoluril ( G2 ), 1,3,4,6-tetraallylglycoluril ( G3 ), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3-mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (Tg) and the maximum temperature of thermal decomposition (Tmax) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap-shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 923–931 相似文献
97.
Yu-Yi Zhang De-Shan Zhang Tian Li Dr. Mohamedally Kurmoo Prof. Dr. Ming-Hua Zeng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):721-728
Dehydration of (S,S)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethane-1,2-diol (H4L) to (Z)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethenol) (H3L′) was found to be metal-assisted, occurs under solvothermal conditions (H2O/CH3OH), and leads to [MnII4(H3L)4Cl2]Cl2 ⋅ 5 H2O ⋅ 5 CH3OH ( Mn4L4 ) and [MnII4(H2L′)6(μ3-OH)]Cl ⋅ 4 CH3OH ⋅ H2O ( Mn4L′6 ), respectively. Their structures were determined by single-crystal XRD. Extensive ESI-MS studies on solutions and solids of the reaction led to the proposal consisting of an initial stepwise assembly of Mn4L4 from the reactants via [MnL] and [Mn2L2] below 80 °C, and then disassembly to [MnL] and [MnL2] followed by ligand modification before reassembly to Mn4L′6 via [MnL′], [MnL′2], and [Mn2L′3] with increasing solvothermal temperature up to 140 °C. Identification of intermediates [Mn4LxL′6−x] (x=5, 4, 3, 2, 1) in the process further suggested an assembly/disassembly/in situ reaction/reassembly transformation mechanism. These results not only reveal that multiple phase transformations are possible even though they were not realized in the crystalline state, but also help to better understand the complex transformation process between coordination clusters during “black-box” reactions. 相似文献
98.
Dr. Luca Fornasari Dr. Anna Olejniczak Dr. Federica Rossi Dr. Simone d'Agostino Prof. Michele R. Chierotti Prof. Roberto Gobetto Prof. Andrzej Katrusiak Prof. Dario Braga 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):5061-5069
The structures and solid-state dynamics of the supramolecular salts of the general formula [(12-crown-4)2 ⋅ DABCOH2](X)2 (where DABCO=1,4-diazabicyclo[2.2.2]octane, X=BF4, ClO4) have been investigated as a function of temperature (from 100 to 360 K) and pressure (up to 3.4 GPa), through the combination of variable-temperature and variable-pressure XRD techniques and variable-temperature solid-state NMR spectroscopy. The two salts are isomorphous and crystallize in the enantiomeric space groups P3221 and P3121. All building blocks composing the supramolecular complex display dynamic processes at ambient temperature and pressure. It has been demonstrated that the motion of the crown ethers is maintained on lowering the temperature (down to 100 K) or on increasing the pressure (up to 1.5 GPa) thanks to the correlation between neighboring molecules, which mesh and rotate in a concerted manner similar to spiral gears. Above 1.55 GPa, a collapse-type transition to a lower-symmetry ordered structure, not attainable at a temperature of 100 K, takes place, proving, thus, that the pressure acts as the means to couple and decouple the gears. The relationship between temperature and pressure effects on molecular motion in the solid state has also been discussed. 相似文献
99.
Dr. Beatriz Feringán Jesús Cerdá Dr. Beatriz Diosdado Dr. Juan Aragó Prof. Dr. Enrique Ortí Dr. Raquel Giménez Dr. Teresa Sierra 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15313-15322
The ability of a star-shaped tris(triazolyl)triazine derivative to hierarchically build supramolecular chiral columnar organizations through the formation of H-bonded complexes with benzoic acids was studied from a theoretical and experimental point of view. The combined study has been done at three different levels including the study of the structure of the triazine core, the association with benzoic acids in stoichiometry 1:3, and the assembly of 1:3 complexes in helical aggregates. Although the star-shaped triazine core crystallizes in a non-C3 conformation, the C3-symmetric conformation is theoretically predicted to be more stable and gives rise to a favorable C3 supramolecular 1:3 complex upon the interaction with three benzoic acids in their voids. In addition, calculations at different levels (DFT, PM7, and MM3) for the 1:3 host-guest complex predict the formation of large stable columnar helical aggregates stabilized by the compact packing of the interstitial acids by π–π and CH⋅⋅⋅π interactions. The acids restrict the movement of the the star-shaped triazine cores along the stacking axis causing a template effect in the self-assembly of the complex. Theoretical predictions correlate with experimental results, since the interaction with achiral or chiral 3,4,5-(4-alkoxybenzyloxy)benzoic acids gives rise to supramolecular complexes that organize in bulk hexagonal columnar mesophases stable at room temperature with intracolumnar order. The existence of supramolecular chirality in the mesophase was determined for complexes formed by acids derived from (S)-2-octanol. Chiral aggregation was also evidenced for complexes formed in dodecane. 相似文献
100.
Wenbin Guo Dr. Nathalie Daro Dr. Sébastien Pillet Dr. Mathieu Marchivie Dr. El-Eulmi Bendeif Dr. Elodie Tailleur Dr. Kittipong Chainok Dominique Denux Dr. Guillaume Chastanet Prof. Philippe Guionneau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12927-12930
The current craze for research around the spin crossover phenomenon can be justified to some extent by the mechanical properties due to the decrease of volume associated with the transition of the metal ion from the HS state to the LS state. As demonstrated here, the molecular complex [Fe(PM-pBrA)2(NCS)2] exhibits, on the contrary, an increase of the unit-cell volume from HS to LS. This counter-intuitive and unprecedented behavior that concerns both the thermal and the photoexcited spin conversions is revealed by a combination of single-crystal and powder X-ray diffraction complemented by magnetic measurements. Interestingly, this abnormal volume change appears concomitant with the wide rotation of a phenyl ring which induces a drastic modification, though reversible, of the structural packing within the crystal. In addition, the light-induced HS state obtained through the Light-Induced Excited Spin-State Trapping shows a remarkably high relaxation temperature, namely T(LIESST), of 109 K, one of the highest so far reported. The above set of quite unusual characteristics opens up new fields of possibilities within the development of spin crossover materials. 相似文献