全文获取类型
收费全文 | 2328篇 |
免费 | 137篇 |
国内免费 | 452篇 |
专业分类
化学 | 2438篇 |
晶体学 | 83篇 |
力学 | 18篇 |
综合类 | 7篇 |
数学 | 2篇 |
物理学 | 369篇 |
出版年
2024年 | 4篇 |
2023年 | 23篇 |
2022年 | 37篇 |
2021年 | 44篇 |
2020年 | 55篇 |
2019年 | 58篇 |
2018年 | 49篇 |
2017年 | 70篇 |
2016年 | 78篇 |
2015年 | 96篇 |
2014年 | 115篇 |
2013年 | 219篇 |
2012年 | 142篇 |
2011年 | 136篇 |
2010年 | 120篇 |
2009年 | 128篇 |
2008年 | 133篇 |
2007年 | 155篇 |
2006年 | 141篇 |
2005年 | 143篇 |
2004年 | 149篇 |
2003年 | 120篇 |
2002年 | 91篇 |
2001年 | 68篇 |
2000年 | 70篇 |
1999年 | 78篇 |
1998年 | 68篇 |
1997年 | 52篇 |
1996年 | 41篇 |
1995年 | 44篇 |
1994年 | 39篇 |
1993年 | 19篇 |
1992年 | 24篇 |
1991年 | 24篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1966年 | 2篇 |
排序方式: 共有2917条查询结果,搜索用时 31 毫秒
1.
Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates. 相似文献
2.
Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo
Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):69
Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (An system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time. 相似文献
3.
The prepared amorphous
γ-ZrP\SiO2 composite had a complicated composition,
since a part of γ-ZrP is converted to α-form during the exfoliation
of it. The γ-ZrP\SiO2 composite have specific surface
area of 421 m2g–1.
The acidic P–OH groups of the lamellae species placed on the surface
(it is ≈1.0 meq g–1), do not destroy until
the temperature of 1030 K. During the thermal treatment the total mass loss
of 7.79% was found. This value corresponds to 0.42 mole of H2O
per molecule unit. The water loss process was found very slow, because of
the placing of bilamellar species in the composite. 相似文献
4.
Sally Dixon 《Tetrahedron》2004,60(6):1401-1416
A wide range of carbenoids (1-lithio-1-halo species), including those with α-SiR3, OEt, SPh, SO2Ph, P(O)(OEt)2, and CN substituents, insert into 5-member zirconacycles (saturated and unsaturated, mono- and bi-cyclic) to afford functionalized 6-member zirconacycles. 1-Lithio-1-haloalkenes insert to afford 6-member zirconacycles with an alkylidene substituent next to the metal. Unexpected double insertion of some carbenoids, and evidence for endocylic β-hydride transfer processes provide additional mechanistic interest. 相似文献
5.
本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。 相似文献
6.
Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N2C6H14)[(UO2)(AsO4)]2(H2O)3, DabcoUAs, {NH(C2H5)3}[(UO2)2(AsO4)(AsO3OH)], TriethUAs, and (N2C4H12)(UO2)[(UO2)(PO4)]4(H2O)2, PiperUP. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (DabcoUAs, TriethUAs, PiperUP) wR2=5.6%, 8.3%, 7.2% for all data, and R1=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (|Fo|?4σF), respectively. DabcoUAs is monoclinic, space group C2/m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å3, Dcalc=3.50 g/cm3. TriethUAs is monoclinic, space group P21/n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å3, Dcalc=3.41 g/cm3. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å3, Dcalc=4.41 g/cm3. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H2O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H2O groups in the cavities of the structure. 相似文献
7.
The behavior of zirconium atoms at the W(100) surface associated with oxygen adsorption at different sample temperatures has been studied by Auger electron spectroscopy (AES), ion scattering spectroscopy (ISS), and the relative change of the work function (Δф) measured by the onset of the secondary electron energy distribution. The results have revealed: (i) adsorption of zirconium onto the W(100) surface followed by the elevation of the sample temperature up to 1710 K in an oxygen partial pressure of 2.7 × 10−4 induces complete diffusion of zirconium atoms into the W(100) substrate; (ii) further exposure of oxygen induces co-existence of oxygen and tungsten on the surface at 1710 K, resulting in a work function of 4.37 eV; (iii) keeping the sample temperature at 1710 K, simple evacuation of the system has resulted in surface segregation of zirconium atoms to the surface to form a zirconium atomic layer on the top-most surface, reducing the work function to 2.7 eV. The results have revealed that this specific behavior of zirconium atoms at high temperature assures, with very good reproducibility, the highly stable performance and long service life of Zr---O/W(100)-emitters in practical use, even in a low vacuum of 10−6 Pa. 相似文献
8.
9.
10.
The investigated materials have similar routes of thermal decomposition; i.e. they lose their crystal water first, then at
a higher temperature their structural one. At least the result TiP2O7 goes through a phase change at about 1000 K. The amorphous titanium phosphate lost its crystal and structural water at higher
temperature than those of crystalline forms. Both α- and γ-titanium phosphates and also their transition metal containing
forms have layered structure. In case of α- and γ-forms after the loss of crystal water a phase change occurs which is followed
by the decomposition of the molecule. Various transition metals containing γ-titanium phosphates lose their crystal water
at the same temperature, with the exception of Ni containing ones. The process is finished in this case at temperature 90
K higher than that of the others.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献