全文获取类型
收费全文 | 2134篇 |
免费 | 117篇 |
国内免费 | 4篇 |
专业分类
化学 | 1771篇 |
晶体学 | 19篇 |
力学 | 24篇 |
数学 | 76篇 |
物理学 | 365篇 |
出版年
2023年 | 15篇 |
2022年 | 15篇 |
2021年 | 30篇 |
2020年 | 49篇 |
2019年 | 39篇 |
2018年 | 37篇 |
2017年 | 23篇 |
2016年 | 51篇 |
2015年 | 73篇 |
2014年 | 76篇 |
2013年 | 106篇 |
2012年 | 173篇 |
2011年 | 159篇 |
2010年 | 91篇 |
2009年 | 95篇 |
2008年 | 176篇 |
2007年 | 154篇 |
2006年 | 168篇 |
2005年 | 155篇 |
2004年 | 112篇 |
2003年 | 73篇 |
2002年 | 57篇 |
2001年 | 25篇 |
2000年 | 13篇 |
1999年 | 21篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 14篇 |
1993年 | 7篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 19篇 |
1989年 | 10篇 |
1988年 | 15篇 |
1987年 | 7篇 |
1986年 | 11篇 |
1985年 | 10篇 |
1984年 | 10篇 |
1983年 | 11篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 16篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 7篇 |
1974年 | 12篇 |
1973年 | 4篇 |
排序方式: 共有2255条查询结果,搜索用时 31 毫秒
971.
Daisuke Sawai Kazuyo Takahashi Toshiyuki Imamura Koh Nakamura Tetsuo Kanamoto Suong‐Hyu Hyon 《Journal of Polymer Science.Polymer Physics》2002,40(1):95-104
Melt‐crystallized, low molecular weight poly(L ‐lactic acid) (PLLA) consisting of α crystals was uniaxially drawn by solid‐state extrusion at an extrusion temperature (Text) of 130–170 °C. A series of extrusion‐drawn samples were prepared at an optimum Text value of 170 °C, slightly below the melting temperature (Tm) of α crystals (~180 °C). The drawn products were characterized by deformation flow profiles, differential scanning calorimetry (DSC) melting thermograms, wide‐angle X‐ray scattering (WAXD), and small‐angle X‐ray scattering as a function of the extrusion draw ratio (EDR). The deformation mode in the solid‐state extrusion of semicrystalline PLLA was more variable and complex than that in the extensional deformation expected in tensile drawing, which generally gave a mixture of α and β crystals. The deformation profile was extensional at a low EDR and transformed to a parabolic shear pattern at a higher EDR. At a given EDR, the central portion of an extrudate showed extensional deformation and the shear component became progressively more significant, moving from the center to the surface region. The WAXD intensities of the (0010)α and (003)β reflections on the meridian as well as the DSC melting thermograms showed that the crystal transformation from the initial α form to the oriented β form proceeded rapidly with increasing EDR at an EDR greater than 4. Furthermore, WAXD showed that the crystal transformation proceeded slightly more rapidly at the sheath region than at the core region. This fact, combined with the deformation profiles (shear at the sheath and extensional at the core), indicated that the crystal transformation was promoted by shear deformation under a high pressure rather than by extensional deformation. Thus, a highly oriented rod consisting of only β crystals was obtained by solid‐state extrusion of melt‐crystallized, low molecular weight PLLA slightly below Tm. The structure and properties of the α‐ and β‐form crystals were also studied. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 95–104, 2002 相似文献
972.
Kure B Ogo S Inoki D Nakai H Isobe K Fukuzumi S 《Journal of the American Chemical Society》2005,127(41):14366-14374
An open capsule-type octanuclear heterometallic sulfide cluster without an intramolecular inversion center [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoO(mu(3)-S)(3)}(CuI)(2)](2) (5) has been synthesized for the first time by stepwise connection of three mononuclear building blocks, i.e., (i) [RuCl(2)(eta(6)-C(6)Me(6)){P(OMe)(3)}] (1a) as an octahedral terminal building block to control the direction of cluster expansion, (ii) [MoOS(3)](2)(-) as a tetrahedral polydentate building block owing to the strong coordination ability of the S atoms, and (iii) a CuI building block to form a trigonal planar (mu-S)(2)CuI unit or to form a linkage unit of two incomplete cubane-type octanuclear frameworks. The stepwise connection was made in the following order: [RuCl(2)(eta(6)-C(6)Me(6)){P(OMe)(3)}] (1a, mononuclear) --> [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoOS(mu(2)-S)(2)}] (2a, dinuclear) --> [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoO(mu(2)-S)(2)(mu(3)-S)}CuI] (3a, butterfly-type trinuclear) --> [Ru(eta(6)-C(6)Me(6)){P(OMe)(3)}{MoO(mu(3)-S)(3)}(CuI)(2)](2) (5). When P(OMe)(3) was replaced by P(OEt)(3), which is more bulky than P(OMe)(3), in the starting ruthenium building block [RuCl(2)(eta(6)-C(6)Me(6)){P(OEt)(3)}] (1b, mononuclear), only the tetranuclear incomplete single cubane cluster [Ru(eta(6)-C(6)Me(6)){P(OEt)(3)}{MoO(mu(3)-S)(3)}(CuI)(2)] (6) was generated, owing to the steric effect of P(OEt)(3). 相似文献
973.
One-pot synthesis of metalated pyridines from two acetylenes, a nitrile, and a titanium(II) alkoxide
Tanaka R Yuza A Watai Y Suzuki D Takayama Y Sato F Urabe H 《Journal of the American Chemical Society》2005,127(21):7774-7780
Four-component coupling process involving two acetylenes, a nitrile, and a divalent titanium alkoxide reagent, Ti(O-i-Pr)(4)/2i-PrMgCl, directly yielded titanated pyridines in a highly selective manner. The reaction can be classified into four categories: (i) a combination of an internal acetylene, a terminal acetylene, sulfonylnitrile, and the titanium reagent to yield alpha-titanated pyridines, (ii) a combination of an internal acetylene, a (sulfonylamino)acetylene, a nitrile, and the titanium reagent to yield alternative alpha-titanated pyridines, (iii) a combination of an internal acetylene, a (sulfonylamino)acetylene, a nitrile, and the titanium reagent to yield titanated aminopyridines, and (iv) a combination of an acetylenic amide, a terminal acetylene, a nitrile, and the titanium reagent to yield pyridineamides with their side chain titanated. Some of these reactions enabled virtually completely regioselective coupling of two different, unsymmetrical acetylenes and a nitrile to form a single pyridine. Synthetic applications of these reactions have been illustrated in the preparation of optically active pyridines and medicinally useful compounds. 相似文献
974.
Sunazuka T Shirahata T Tsuchiya S Hirose T Mori R Harigaya Y Kuwajima I Omura S 《Organic letters》2005,7(5):941-943
The stereoselective synthesis of tetracyclic intermediate, the indoline spiroaminal 3 for neoxaline (1) and oxaline (2), has been accomplished. The key step of the stereoselective synthesis of 3 was the Lewis acid mediated transcyclization of 4 to the diaminal 18, and the tungstate-catalyzed oxidation of 18 to obtain the nitrone 19, which easily cyclizes to the indoline spiroaminal framework 3. [structure: see text] 相似文献
975.
[chemical reaction: see text]. A solid phase approach is presented for the synthesis of azapeptide inhibitors and activity based probes (ABPs) for cysteine proteases. This synthetic method allows the incorporation of diverse reactive warheads linked to different peptide recognition elements. Application of this method to the synthesis of a series of caspase probes is described. 相似文献
976.
Daisuke Takeuchi Yoshihiko Sakaguchi Kohtaro Osakada 《Journal of polymer science. Part A, Polymer chemistry》2002,40(24):4530-4537
Co2(CO)8 catalyzes the ring‐opening copolymerization of propylene oxide with CO to afford the polyester in the presence of various amine cocatalysts. The 1H and 13C{1H} NMR spectra of the polyester, obtained by the Co2(CO)8–3‐hydroxypyridine catalyst, show the following structure ? [CH2? CH(CH3)? O? CO]n? . The Co2(CO)8–phenol catalyst gives the polyester, which contains the partial structural unit formed through the ring‐opening copolymerization of tetrahydrofuran with CO. The bidentate amines, such as bipyridine and N,N,N′,N′‐tetramethylethylenediamine, enhance the Co complex‐catalyzed copolymerization, which produces the polyester with a regulated structure. Acylcobalt complexes, (RCO)Co(CO)n (R = Me or CH2Ph), prepared in situ, do not catalyze the copolymerization even in the presence of pyridine. This suggests that the chain growth involves the intermolecular nucleophilic addition of the OH group of the intermediate complex to the acyl–cobalt bond, forming an ester bond rather than the insertion of propylene oxide into the acyl–cobalt bond. Co2(CO)8? Ru3(CO)12 mixtures also bring about the copolymerization of propylene oxide with CO. The molar ratio of Ru to Co affects the yield, molecular weight, and structure of the produced copolymer. The catalysis is ascribed to the Ru? Co mixed‐metal cluster formed in the reaction mixture. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4530–4537, 2002 相似文献
977.
The stability of the o-phthalaldehyde (OPA) derivatives of sisomicin obtained using beta-mercaptopropionic acid was investigated by reversed-phase high-performance liquid chromatography. One of the fluorescent derivatives of sisomicin was stable at least for 6 h in 50% methanol under the optimal conditions used (OPA concentration, pH and temperature). When plasma samples spiked with sisomicin were analysed, the response was linear in the calibration range 136-900 pg of sisomicin per injected volume (40 microliters). As little as 0.06 micrograms of sisomicin per 1 ml of plasma could be detected with signal-to-noise ratio greater than or equal to 2. For plasma samples spiked with 0.2 micrograms/ml sisomicin, the recovery was 97.1 +/- 6.6% (mean +/- S.D., n = 5) with a within-run coefficient of variation of 6.8% and a day-to-day coefficient of variation of 7.2%. The method was also applied to plasma samples from rabbit after a subcutaneous injection of 1 mg/kg sisomicin. 相似文献
978.
K. Hirose 《Journal of Radioanalytical and Nuclear Chemistry》1994,181(1):11-24
A sequential leaching experiment for chemical speciation of particulate uranium in seawater was carried out using solution chemistry techniques. Mass action analysis on the leaching processes reveals that the major species of particulate uranium in seawater is an organic complex of uranium(VI), which is dissociated completely in the leaching solution of pH 1.0. Inert uranium, which is not dissolved in the leaching solution of pH 1.0, exists is suspended matter although it is a minor constituent. The result suggests that this species in an organic complex of uranium(IV). The analysis of the experimenmt deduces that an organic binding site in suspended matter reacts as a polydentate ligand, which has more than two stepwise protonation constants within the pH range of 2.0 to 8.2. The conditiona stability constant of the organic uranium complex in suspended matter under the conditions of seawater is within the following range: 12<log Kc,U<16. These findings suggest stronglt that the organic binding site in suspended matter can form stable chelates with metallic elements. 相似文献
979.
H. Hirose H. Matsuda S. Kon 《International Journal of Infrared and Millimeter Waves》1981,2(6):1165-1176
A compact FIR laser cavity having a couple of folding mirrors was designed. By inserting this FIR cavity into the pump TE CO2 laser resonator, we observed 19 FIR NH3 laser lines of which 4 new lines were included. The maximum output power was over 500 W at 90 m. 相似文献
980.
By electrospray ionization (ESI) mass spectrometry, micelle solutions of sodium cholate were investigated in detail in the presence and absence of ethanol. The average aggregation number could be evaluated from the spectra acquired under conditions where soft collisions adequate to measure the micelle solution were induced, and the value agreed well with that obtained previously by other methods. From the dependence on ethanol content, it was also found that the average aggregation number in aqueous solution without organic solvent could be reliably estimated. The ESI method proved to be a useful tool for determining the micelle mass in the original aqueous phase. 相似文献