全文获取类型
收费全文 | 1720篇 |
免费 | 83篇 |
国内免费 | 3篇 |
专业分类
化学 | 1492篇 |
晶体学 | 10篇 |
力学 | 16篇 |
数学 | 62篇 |
物理学 | 226篇 |
出版年
2024年 | 2篇 |
2023年 | 16篇 |
2022年 | 15篇 |
2021年 | 26篇 |
2020年 | 47篇 |
2019年 | 37篇 |
2018年 | 28篇 |
2017年 | 17篇 |
2016年 | 44篇 |
2015年 | 54篇 |
2014年 | 69篇 |
2013年 | 83篇 |
2012年 | 151篇 |
2011年 | 140篇 |
2010年 | 74篇 |
2009年 | 85篇 |
2008年 | 153篇 |
2007年 | 142篇 |
2006年 | 138篇 |
2005年 | 133篇 |
2004年 | 97篇 |
2003年 | 60篇 |
2002年 | 50篇 |
2001年 | 17篇 |
2000年 | 9篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 9篇 |
1979年 | 3篇 |
1978年 | 8篇 |
1977年 | 9篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 9篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有1806条查询结果,搜索用时 15 毫秒
61.
Daisuke Sawai Mika Miyamoto Tetsuo Kanamoto Masayoshi Ito 《Journal of Polymer Science.Polymer Physics》2000,38(19):2571-2579
No systematic study has been reported on the lamellar thickening in atactic poly(acrylonitrile) (PAN) upon annealing because PAN, in the form of solution‐cast films or their drawn products, generally shows no small‐angle X‐ray scattering (SAXS) maximum corresponding to the lamellar thickness. In this work, PAN crystals were precipitated during the thermal polymerization of acrylonitrile in solution. The nascent PAN film, obtained by the filtration of the crystal suspension, exhibited a clear SAXS maximum revealing the lamellar structure. The lamellar thickening upon annealing of the nascent PAN films was studied in the temperature range 100–180 °C, where the degradation was minimal, as confirmed by the absence of an IR absorption band at 1605 cm−1 ascribed to the cyclized nitrile groups. Above 190 °C, the degradation of the samples was significant, and the SAXS became too broad to determine the scattering maximum. The long period was significantly affected by the annealing time (ta) and the temperature (Ta). Depending on ta, three stages were observed for the lamellar thickening behavior. The lamellar thickness stayed constant in stage I (ta = 0.5–3 min, depending on Ta), rapidly increased in stage II (ta = 0.5–8 min), and stayed at a constant value characteristic for each Ta at yet longer ta's in stage III. The lamellar thickness characteristic for Ta increased rapidly with increasing Ta at 165 °C (or higher), which was 152 °C lower than the estimated melting temperature of PAN (Tm = 317 °C). A possible mechanism for such lamellar thickening in PAN far below the Tm is discussed on the basis of the enhanced chain mobility in the crystalline phase above the crystal/crystal reversible transition at 165–170 °C detected by differential scanning calorimetry and wide‐angle X‐ray diffraction. The structural changes associated with annealing are also discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2571–2579, 2000 相似文献
62.
Koji Ishizu Daisuke Takahashi Hisashi Takeda 《Macromolecular rapid communications》2000,21(10):660-664
Two poly(4‐methylstyrene) (P4MS)‐block‐polystyrene (PS)‐block‐P4MS triblock copolymers were prepared by successive anionic addition of styrene and 4‐methylstyrene monomers as the core backbone ( CB ) for the architecture of block‐graft polymers. Both terminal 4‐methylstyrene blocks of CB were metalated with a sec‐butyllithium (sec‐BuLi)/tetramethylethylenediamine (TMEDA) complex in cyclohexane. The first‐generation block‐graft polymer ( 1BG ) was prepared by anionic polymerization of α‐methylstyrene by the lithiated CB in tetrahydrofuran (THF) at –78°C and subsequently the terminal graft ends were capped with a small amount of 4‐methylstyrene. The characterization of those block‐graft polymers was carried out in detail. 相似文献
63.
Sudo Y Shirasaki D Harada S Nishida A 《Journal of the American Chemical Society》2008,130(38):12588-12589
1-Methoxy-3-trimethylsiloxy-1,3-butadiene (Danishefsky's diene) is recognized as a synthetically useful diene due to its high reactivity in the Diels-Alder reaction with electron-deficient alkenes to give oxygen-functionalyzed cyclohexenes and substituted cyclohexenones, which are important building blocks for the total synthesis of natural products. However, the development of catalytic enantioselective versions of Diels-Alder reactions using Danishefsky type dienes with electron-deficient alkenes has been difficult because of the instability of the dienes under Lewis acidic conditions. Only highly reactive CO and CN double bonds are employed in a hetero-Diels-Alder reaction which proceeds under catalysis of chiral Lewis acids. We have developed a new chiral ligand, BINAMIDE, which is easily prepared from 1,1'-binaphtyl-2,2'-diamine by acylation. The highly diastereo- and enantioselective Diels-Alder reaction of Danishefsky type dienes with electron-deficient alkenes in the presence of an Yb(III)-BINAMIDE complex has been developed. The reaction proceeded in an exoselective mode and gave chiral highly functionalized cyclohexene derivatives in good yields. 相似文献
64.
Dr. Jiawei Zhang Dr. Daisuke Ishikawa Dr. Michael M. Koza Prof. Dr. Eiji Nishibori Dr. Lirong Song Dr. Alfred Q. R. Baron Prof. Dr. Bo B. Iversen 《Angewandte Chemie (International ed. in English)》2023,62(13):e202218458
Loosely bonded (“rattling”) atoms with s2 lone pair electrons are usually associated with strong anharmonicity and unexpectedly low thermal conductivity, yet their detailed correlation remains largely unknown. Here we resolve this correlation in thermoelectric InTe by combining chemical bonding analysis, inelastic X-ray and neutron scattering, and first principles phonon calculations. We successfully probe soft low-lying transverse phonons dominated by large In1+ z-axis motions, and their giant anharmonicity. We show that the highly anharmonic phonons arise from the dynamic lone pair expression with unstable occupied antibonding states induced by the covalency between delocalized In1+ 5s2 lone pair electrons and Te 5p states. This work pinpoints the microscopic origin of strong anharmonicity driven by rattling atoms with stereochemical lone pair activity, important for designing efficient materials for thermoelectric energy conversion. 相似文献
65.
Dr. Yoshinobu Kamakura Dr. Chomponoot Suppaso Issei Yamamoto Ryusuke Mizuochi Yusuke Asai Prof. Dr. Teruki Motohashi Prof. Dr. Daisuke Tanaka Prof. Dr. Kazuhiko Maeda 《Angewandte Chemie (International ed. in English)》2023,62(28):e202305923
Certain metal complexes are known as high-performance CO2 reduction photocatalysts driven by visible light. However, most of them rely on rare, precious metals as principal components, and integrating the functions of light absorption and catalysis into a single molecular unit based on abundant metals remains a challenge. Metal-organic frameworks (MOFs), which can be regarded as intermediate compounds between molecules and inorganic solids, are potential platforms for the construction of a simple photocatalytic system composed only of Earth-abundant nontoxic elements. In this work, we report that a tin-based MOF enables the conversion of CO2 into formic acid with a record high apparent quantum yield (9.8 % at 400 nm) and >99 % selectivity without the need for any additional photosensitizer or catalyst. This work highlights a new MOF with strong potential for photocatalytic CO2 reduction driven by solar energy. 相似文献
66.
Choi JC Kohno K Masuda D Yasuda H Sakakura T 《Chemical communications (Cambridge, England)》2008,(6):777-779
Iron triflate, in situ-formed from FeCl3 and triflic acid, or FeCl3 and silver triflate efficiently catalyse the intermolecular addition of carboxylic acids to various alkenes to yield carboxylic esters; the reaction is applicable to the synthesis of unstable esters, such as acrylates. 相似文献
67.
Interaction forces between two gold surfaces with adsorbed poly(amidoamine) (PAMAM) dendrimers (generations G3.0 and G5.0) have been investigated using colloidal probe atomic force microscopy (AFM). In the absence of dendrimers or at their low concentrations, an attractive force derived from the van der Waals interaction was observed. On the other hand, this attractive interaction changed to repulsion with increasing dendrimer concentration. The origin of the repulsion can be attributed to either an electric double layer interaction or a steric effect of the adsorbed dendrimers, depending on the concentration of dendrimer. The steric hindrance was also influenced by the generation of the dendrimer; the force-detectable distance in the presence of PAMAM G5.0 dendrimer was slightly longer than that in the presence of G3.0 dendrimer. In order to estimate the occupied area of each dendrimer adsorbed on gold, quartz crystal microbalance (QCM) measurement was also carried out. 相似文献
68.
Density functional theory (DFT) calculations of possible reaction pathways and mechanisms for the deprotonation of benzene with Mulvey's reagent, TMEDA.Na(micro-R)(micro-TMP)Zn(R) (TMEDA=N,N,N',N'-tetramethylethylenediamine, R = alkyl, TMP = 2,2,6,6-tetramethylpiperidide) indicate that the deprotonation of benzene with Mulvey's reagent proceeds through a stepwise mechanism, not a one-step mechanism. In the first step, deprotonation involving the TMP ligand on the reagent is kinetically more favorable than that involving the alkyl ligand. 相似文献
69.
Tomonari Wakabayashi Daisuke Kasuya Haruo Shiromaru Shinzo Suzuki Koichi Kikuchi Yohji Achiba 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):414-417
Systematic fractional change in the yield of various isomers of fullerenes was revealed to strongly depend on temperature of a buffer gas. A new kinetic consideration is proposed for understanding the observed temperature- and pressure-dependence of yield of fullerenes. The model consists of three competitive reactions in consideration of plausible behaviors of a precursor, (1) decomposition into smaller fragments, (2) isomerization leading to formation of a stable fullerene cage, and (3) growth into a larger carbon cluster. Arrhenius activation energy of formation of stable fullerenes was determined to be 0.8 eV for both C60 and C70, while a higher energy of 2.0?3.3 eV for seven different isomers of higher fullerenes ranging from C76 to C84. Correlation in the activation energy is noted for a series of higher fullerenes with different sizes, suggesting the existence of a specific precursor in their formation processes. 相似文献
70.
Kiyoharu Tadanaga Akira Miyata Daisuke Ando Naoko Yamaguchi Masahiro Tatsumisago 《Journal of Sol-Gel Science and Technology》2012,62(1):111-116
Using hot water treatment of sol–gel derived precursor gel films, Co–Al and Ni–Al layered double hydroxide (LDH) thin films
were prepared. The precursor gel films of Al2O3–CoO or Al2O3–NiO were prepared from cobalt or nickel nitrates and aluminum tri-sec-butoxide using the sol–gel method. Then, the precursor gel films were immersed in a NaOH aqueous solution of 100 °C. Nanocrystallites
of Co–Al and Ni–Al LDH were precipitated with the hot water treatment with NaOH solution. The largest amounts of nanocrystals
were obtained with a solution of pH = 10 for Co–Al LDH, and with that of pH = 9 for Ni–Al LDH. X-ray diffraction measurements
confirmed that this process formed CO3
2− intercalated LDHs. Both Co–Al and Ni–Al LDH thin films were confirmed to work as electrodes for electrochemical devices by
cyclic voltammogram measurements. 相似文献