全文获取类型
收费全文 | 14171篇 |
免费 | 2406篇 |
国内免费 | 7663篇 |
专业分类
化学 | 13404篇 |
晶体学 | 459篇 |
力学 | 851篇 |
综合类 | 514篇 |
数学 | 3377篇 |
物理学 | 5635篇 |
出版年
2024年 | 113篇 |
2023年 | 400篇 |
2022年 | 550篇 |
2021年 | 691篇 |
2020年 | 504篇 |
2019年 | 595篇 |
2018年 | 422篇 |
2017年 | 634篇 |
2016年 | 757篇 |
2015年 | 800篇 |
2014年 | 1145篇 |
2013年 | 1323篇 |
2012年 | 1363篇 |
2011年 | 1268篇 |
2010年 | 995篇 |
2009年 | 1339篇 |
2008年 | 1396篇 |
2007年 | 1368篇 |
2006年 | 1387篇 |
2005年 | 1223篇 |
2004年 | 1077篇 |
2003年 | 672篇 |
2002年 | 521篇 |
2001年 | 480篇 |
2000年 | 523篇 |
1999年 | 507篇 |
1998年 | 288篇 |
1997年 | 183篇 |
1996年 | 156篇 |
1995年 | 151篇 |
1994年 | 166篇 |
1993年 | 205篇 |
1992年 | 236篇 |
1991年 | 218篇 |
1990年 | 158篇 |
1989年 | 145篇 |
1988年 | 94篇 |
1987年 | 52篇 |
1986年 | 38篇 |
1985年 | 36篇 |
1984年 | 22篇 |
1983年 | 20篇 |
1982年 | 13篇 |
1981年 | 3篇 |
1959年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
921.
A three-coordinate Ag(I) complex, [Ag(Mepzpy)(PAr3)]BF4·H2O(1, Mepzpy = 3-methyl-1-(2-pyridyl)pyrazole, PAr3 = tri(o-tolyl)phosphine), was synthesized from the reaction of Ag(CH3CN)4BF4, PAr3 and Mepzpy in CH3 CN at room temperature. The compound was characterized by UV-vis, NMR and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 10.2251(5), b = 10.6014(5), c = 15.7012(5) , α = 92.963(3), β = 92.641(3), γ = 114.647(4)o, V = 1540.6(1) 3, Z = 2, Mr = 676.24, Dc = 1.458 g/cm3, F(000) = 688, μ = 6.187 mm-1, GOOF = 1.038, the final R = 0.0530 and w R = 0.1493 for 6371 observed reflections with I 2σ(I). Compound 1 is ionic. It is composed of a BF4- anion and a [Ag(Mepzpy)(PAr3)]+ cation. The Ag(I) ion adopts a distorted trigonal pyramidal coordination geometry defined by two nitrogen atoms and a phosphorous atom. The complex emits blue luminescence with maximum peaks at 470 nm in solid state at room temperature. 相似文献
922.
The effect of nanoclay on the phase-separation behavior of poly(methyl methacrylate)/poly(vinyl acetate)(PMMA/PVAc) blends has been mainly investigated by small-angle laser light scattering. It is found that the effect of clay on the thermodynamics and kinetics of phase-separation for PMMA/PVAc blends seems inconsistent. The kinetics phaseseparation rate decreases, while the thermodynamics parameters, cloud points Tc and delay time tD of isothermal phaseseparation also decrease, and the variation amplitude depends on the matrix composition. The affinity of clay to PMMA results in the composition difference between the border layer and the polymer matrix and further causes the concentration fluctuation at the early stage of phase separation to reduce Tc and tD. On the other hand, the decrease of phase-separation rate is caused by the mechanical barrier effect of clay on the macromolecular diffusion of blend matrix. Hence, such seemingly counterintuitive results on the thermodynamics and kinetics of phase-separation are attributed to different dominant factors. 相似文献
923.
The lower critical solution temperature (LCST) behavior of poly(acrylamide-co-diacetone acrylamide) (poly(AM-co-DAM)) copolymer in aqueous solutions was studied. The results demonstrate the LCST linearly decreases as the molar fraction of DAM (fDAM) increases. In the range of fDAM 〈 0.36, the transmittance increases as fDAM decreases because the more hydrophilic copolymer chains can form looser aggregates with a lower refractive index. The transmittance exhibits a minimum when fDAM is less than 0.28 as the chains form micelle-like structure with a size smaller than the wavelength. The LCST decreases with the initial polymer concentration, but it levels off when the polymer concentration is high enough. Moreover, no hysteresis can be observed in the change of transmittance during the heating-cooling process because no additional hydrogen bonds are formed in the collapsed state due to the steric hindrance of the large side groups in DAM units. 相似文献
924.
This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis(phenoxyimine) ligands. Six phenoxy-imine Ti(IV) complexes {6-R1-2-[CH=N(2,6-difluoro-3,5-diR2-4-R3Ph)]C6H3O}2TiCl2(1: R1 = H, R2 = H, R3 = H; 2: R1 = H, R2 = H, R3 = 4-vinylphenyl; 3: R1 = CH3, R2 = H, R3 = H; 4: R1 = CH3, R2 = H, R3 = 4-vinylphenyl; 5: R1 = CH3, R2 = F, R3 = H; 6: R1 = CH3, R2 = F, R3 = 4-vinylphenyl) have been synthesized and evaluated for ethylene polymerization using dried MAO(simplified as DMAO) as cocatalyst. An obvious catalytic heterogeneity of Cat 2(Complex 2/DMAO) towards ethylene polymerization was observed, which was illustrated by decreased activity, multimodal molecular weight distribution and partially improved particle morphology comparing with Cat 1. Moreover, Cat 3 exhibits "living" characteristics in the process under certain conditions(25 °C, less than 20 min). Otherwise, the moderate to high ethylene polymerization activity of ca. 105-106 g PE/(mol Ti·h) and high molecular weight(Mw = 105-106) of polyethylene can be obtained by changing the skeleton structure of these complexes. 相似文献
925.
926.
以氯乙酰氯、N-乙基对碘苯胺为原料,经酰化反应合成了N-乙基-N-(4-碘苯基)氯乙酰胺,接着与1-甲基咪唑反应,随后在水溶液中和四氟硼酸钠发生阴离子交换,合成了四氟硼酸1-甲基-3-(N-乙基-4-碘苯氨基甲酰甲基)咪唑鎓盐,该四氟硼酸盐在过氧化氢/三氟乙酸酐体系中氧化得到一种新的离子负载的双(三氟乙酰氧基)碘苯试剂四氟硼酸(1-甲基-3-{N-乙基-4-[双(三氟乙酰氧基)碘]苯氨基甲酰甲基}咪唑鎓盐)。所合成的碘苯试剂没有吸湿性,在空气中长期放置不变质。以这种新试剂为氧化剂,室温下乙酰苯胺及其衍生物与乙酸区域选择性地发生乙酰氧基化反应,产率较高。该离子负载型碘苯试剂可回收后再生,而再生试剂用于乙酰氧基化反应时活性几乎保持不变。 相似文献
927.
合成了二丁基二硫代氨基甲酸砷[(C9H18NS2)3As(Ⅲ)](1)和二甲基二硫代氨基甲酸铋[(C3H6NS2)3Bi(Ⅲ)](2)两种配合物。通过元素分析、红外光谱、1HNMR、热重对其进行表征,并用X-射线单晶衍射测定了晶体结构。配合物1属于三斜晶系,P 空间群,晶胞参数为:a = 1.075 0(15) nm,b = 1.214 3(16) nm,c = 1.621(3) nm,α = 69.15(2)°, β = 75.36(3)°, γ = 88.17(2)°;配合物2也属于三斜晶系,P 空间群,晶胞参数为:a = 0.992 9(3) nm,b = 0.993 0(3) nm,c = 1.142 7(3) nm,α = 64.495(4)°, β = 80.400(4)°, γ = 64.772(4)°。利用琼脂扩散法测试了配合物的抑菌活性, 结果表明配合物1对5种受试菌株具有较强的抑菌活性,配合物2则仅有弱的拟菌活性。 相似文献
928.
由(S)-脯氨醇衍生的N-Boc-2-氨甲基吡咯烷与与邻苯二甲酸酐经缩合、脱Boc反应,合成了手性酰亚胺化合物4,研究了该类有机小分子催化剂在辅助添加剂2,4-二氯苯甲酸存在下,催化丙酮或环己酮与邻硝基苯甲醛的不对称Aldol反应,产物的产率分别为75%,82%,e.e.值分别为34%,29%。 相似文献
929.
研究了在紫外光(UV)照射下,Fe(Ⅲ)-富马酸盐体系对p-硝基苯酚(PNP)的光降解反应,考察了溶液pH、Fe(Ⅲ)、富马酸盐和PNP的初始浓度对PNP降解率的影响。结果表明,UV/Fe(Ⅲ)-富马酸盐体系对PNP有光降解作用,相比于只含Fe(Ⅲ)或者富马酸盐体系,同时加入Fe(Ⅲ)与富马酸盐构成的体系在降解PNP方面有协同作用。在pH 3.0~6.0范围内,PNP的降解率随着pH和PNP初始浓度的增大而降低,而随着Fe(Ⅲ)和富马酸盐的初始浓度的增大而增大。氯仿猝灭法证实,该体系在降解PNP反应过程中产生了超氧负离子自由基;采用荧光法和异丙醇猝灭法证实了该体系在反应过程中产生了羟基自由基,同时证实了羟基自由基为PNP光降解反应的主要反应物质。 相似文献
930.
报道了1-(2-苯并噻唑)-3-(3,5-二溴吡啶)三氮烯(BTDPT)的合成及其与Cu(Ⅱ)的荧光反应研究。在pH 9.16的Na2B4O7-NaOH缓冲溶液中,该试剂与Cu(Ⅱ)形成2:1的稳定络合物,体系的激发和发射波长分别为359和401 nm。Cu质量浓度在0.5~80.0μg/L范围内与△F呈良好的线性关系,其线性回归方程为:ΔF=-0.178+0.209ρ(μg/L),相关系数r=0.9956,检出限为0.2μg/L,用于测定环境水中痕量Cu,结果与原子吸收光谱法相符。样品6次测定值相对标准偏差小于5%,加标回收率为98.5%~103.0%。 相似文献