全文获取类型
收费全文 | 10953篇 |
免费 | 1931篇 |
国内免费 | 1523篇 |
专业分类
化学 | 8293篇 |
晶体学 | 184篇 |
力学 | 572篇 |
综合类 | 131篇 |
数学 | 1219篇 |
物理学 | 4008篇 |
出版年
2024年 | 46篇 |
2023年 | 253篇 |
2022年 | 495篇 |
2021年 | 469篇 |
2020年 | 552篇 |
2019年 | 550篇 |
2018年 | 437篇 |
2017年 | 451篇 |
2016年 | 611篇 |
2015年 | 594篇 |
2014年 | 757篇 |
2013年 | 872篇 |
2012年 | 988篇 |
2011年 | 962篇 |
2010年 | 712篇 |
2009年 | 707篇 |
2008年 | 733篇 |
2007年 | 641篇 |
2006年 | 594篇 |
2005年 | 462篇 |
2004年 | 373篇 |
2003年 | 265篇 |
2002年 | 358篇 |
2001年 | 302篇 |
2000年 | 212篇 |
1999年 | 191篇 |
1998年 | 125篇 |
1997年 | 94篇 |
1996年 | 105篇 |
1995年 | 65篇 |
1994年 | 86篇 |
1993年 | 46篇 |
1992年 | 30篇 |
1991年 | 62篇 |
1990年 | 48篇 |
1989年 | 34篇 |
1988年 | 16篇 |
1987年 | 17篇 |
1986年 | 13篇 |
1985年 | 26篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1977年 | 3篇 |
1974年 | 4篇 |
1971年 | 2篇 |
1962年 | 1篇 |
1959年 | 3篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Dehydration of Castor Oil over NaHSO4/MCM‐41 Catalyst Modified by n‐Dodecyltriethoxysilane 下载免费PDF全文
Cui‐Xia Yan Jian‐Fei Ding Tian‐Lin Ma Rong Shao Wei Xu Jie He Peng‐Fei Wang 《无机化学与普通化学杂志》2017,643(12):772-779
n‐Dodecyltriethoxysilane (DTEOS) modified NaHSO4/MCM‐41 catalysts (silanized catalysts) were synthesized by different impregnation sequences and evaluated in the liquid‐phase dehydration of castor oil. The samples were evaluated by X‐ray diffraction, nitrogen adsorption‐desorption, SEM, TEM, FT‐IR spectroscopy, XPS, 29Si MAS NMR spectroscopy, contact angle measurements, NH3‐TPD, and pyridine‐FT‐IR spectroscopy. The analyses demonstrated that silanization enhanced the hydrophobicity of the catalysts, and the impregnation sequence of silanized catalysts had a significant effect on the NaHSO4 dispersion, surface area, acid distribution, and hydrophobicity of the silanized catalysts. The catalytic activity of the silanized catalysts was much higher than that of NaHSO4/MCM‐41. Among the silanized catalysts, the catalyst prepared by simultaneous impregnation with DTEOS and NaHSO4 showed the highest iodine value of 141.8 [g(I2) per 100 g] and lowest hydroxyl value of 11.3 [mg(KOH) · g–1]. 相似文献
982.
Syntheses,Structures, and Photophysical Properties of Two Coordination Polymers Based on 2,3‐Dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic Acid 下载免费PDF全文
Two complexes based on the ligand 1,4‐dihydro‐2,3‐quinoxalinedione, namely [Mn(H2L)2(H2O)2]n ( 1 ) and {[Zn2(H2L)2(tz)2] · 5H2O}n ( 2 ) (H3L = 2,3‐dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic acid, Htz = 1,2,4‐triazole) were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, as well as single‐crystal and powder X‐ray diffraction. Complex 1 exhibited a 1D comb‐like chain formed by H2L– anions linking MnII ions, whereas complex 2 was a 2D layer‐like structure with square‐shaped windows and outstretched arms built by combination of H2L– and tz– ligands with ZnII ions. The adjacent chains or layers connected with each other by intermolecular hydrogen bonding and π–π stacking to further extend to a 3D supermolecular framework. In addition, the thermal stabilities, luminescence properties, and optical energy gap of 1 and 2 were investigated in detail. 相似文献
983.
Synthesis,Characterization and Migration of Ionic Polyferrocenyl Compounds of 5‐Ferrocenyl‐1H‐tetrazole and Their Effects During Combustion 下载免费PDF全文
Eighteen ionic polyferrocenyl compounds with 5‐ferrocenyl‐1H‐tetrazolate as anion and mono‐ and dinuclear ferrocenyl‐alkylammonium as cations were synthesized and characterized by 1H NMR, 13C NMR, FT‐IR, and UV/Vis spectroscopy, and elemental analysis. Molecular structures of three compounds were further confirmed by single‐crystal X‐ray diffraction. Their thermal stability was evaluated by TG and DSC and found that they are of high thermal stability. The cyclic voltammetry analysis suggested that each of the compounds exhibits only an irreversible redox wave of the ferrocene units in the molecule. Both migration and volatility test results showed that, on comparison with those of Catocene, all tested compounds exhibit much more excellent anti‐migration ability and most of the tested compounds have lower volatility. Their effects on the thermal disintegration of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were measured by DSC. The results revealed that most of the compounds exhibit significant catalytic effects on the thermal degradation of AP and RDX. Particularly, most of the compounds containing one ferrocene unit in their cations show higher activity than that of Catocene. These compounds can be used as alternatives to Catocene in the composite solid propellants. 相似文献
984.
A series of metal–organic frameworks built from a propionate-functionalized purine-containing ligand 3-(6-oxo-6,9-dihydro-1H-purin-1-yl)propanoic acid (H2L), {[La(HL)3(H2O)2]·2H2O}n (1), {[Ce(HL)3(H2O)2]·4H2O}n (2), [Co(HL)2(H2O)2]n (3), {[Cd(L)(H2O)]·0.5H2O}n (4) and {[Pb(HL)(C2O4)0.5(H2O)]·2H2O}n (5), was synthesized and characterized. Isostructural 1 and 2 have polymeric chain structures further linked into 3-D porous supramolecular frameworks with 1-D open channels through complicated interchain hydrogen bonding interactions. At 77 K and 1 bar, the dehydrated porous materials 1 and 2 show adsorption behaviors with maximum nitrogen uptakes of 14 and 23 mL g?1, respectively. Complexes 3–5 are 2-D coordination polymers but have different topological structures. Metallohelicate 3 has (4,4) nets composed of left- and right-handed metal–organic helices sharing the common metal centers, but metallohelicate 4 possesses (4·82) topology and 5 has 63-topological structure. In 3 and 5, the polymeric layers are further assembled through regular interlayer hydrogen bonding interactions to form 3-D supramolecular frameworks. Additionally, the thermostabilities of 1–5 as well as the magnetism of 3 were also investigated. 相似文献
985.
986.
The determination of rosiglitazone in dietary supplements by direct analysis in real-time mass spectrometry normally provides low repeatability. The [M+H]+ signal sharply decreased in the presence of strong-base and weak-acid ionic compounds because rosiglitazone decomposition occurred due to the hydrolysis of strong-base and weak-acid anions. The repeatability was improved and the influence of ionic compounds was minimized by the use of pioglitazone as an internal standard. Orbitrap mass spectrometry was used to provide high resolution in which isotopic interferences from M?+?1 of pioglitazone upon M of rosiglitazone were eliminated. This approach was used to determine rosiglitazone in tablet and dietary supplements in 1?min per sample. 相似文献
987.
Ana R. Almeida Rui M.B. Carrilho Andreia F. Peixoto Artur R. Abreu Artur Silva Mariette M. Pereira 《Tetrahedron》2017,73(17):2389-2395
Different families of new amino compounds were efficiently synthesized, through optimized sequential processes, involving rhodium catalyzed hydroformylation as the key step. The selection of appropriate hydroformylation catalytic systems and reaction conditions allowed obtaining aldehydes derived from several n-alkyl olefins, cholest-4-ene and 3-vinyl-1H-indole, which were subsequently transformed, in one-pot, in to α-amino acids via hydroformylation/Strecker reaction, and in to tertiary amines via hydroaminomethylation, with excellent yields. 相似文献
988.
Xiankun Shao Shibin Nie Liangzhi Shao Baoshan Zhang Benxia Li 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2017,91(13):2629-2635
The carbon nanotubes/TiO2 (CNTs/TiO2) composite photocatalysts composed of TiO2 nanoparticles and multiwalled carbon nanotubes (CNTs) were prepared by a facile hydrothermal method. The photocatalysts were characterized by a range of analytical techniques including X-ray powder diffraction, field emission scanning electron microscope, thermal gravimetric analysis and UV–Vis optical absorption spectra, etc. The amount of TiO2 nanoparticles growing on CNTs could be tuned by adjusting the dosage of precursor in the reaction solution. Both the adsorptivity and photocatalytic activities of pure CNTs, pure TiO2, and the CNTs/TiO2 nanocomposites were tested by the removal of methylene blue from water in dark and under a simulated sunlight, respectively. By comparison, the improved photocatalytic activity of the CNTs/TiO2 nanocomposite is mainly due to that the CNTs can disperse the active component of TiO2 nanoparticles, provide a larger the specific surface area, as well as act as an electron sink to accelerate the separation of the photogenerated charges. 相似文献
989.
The first cationic water-soluble pillar[7]arene CWP7 was prepared. 1H NMR, 13C NMR, and MALDI-TOF-MS were performed to provide converging evidences of the structure of obtained CWP7. Host–guest complexation between this novel pillar[7]arene-based host and sodium pyren-1-olate guest G was fully investigated in aqueous solution. Increased fluorescence intensity was observed during the inclusion complexation. Driven by the cooperativity of electrostatic interactions, π-stacking interactions and hydrophilic/hydrophobic interactions, the guest penetrated into the cavity of CWP7 to form a pseudorotaxane-type inclusion complex with relatively high binding affinity. 相似文献
990.
利用~1H NMR、紫外吸收光谱和荧光光谱等方法考察了七元瓜环(Q[7])对2'-羟基查尔酮(CET)的包结作用.结果表明,Q[7]与CET形成了摩尔比为1∶1的包结配合物,紫外吸收光谱和荧光光谱测得的结合稳定常数分别为1.0248×10~6和1.253×10~6.相溶解度法研究结果表明,当Q[7]的浓度为1×10~(-3)mol/L时,可使CET在水中的溶解度增加52倍.紫外吸收光谱随时间变化的研究结果表明,Q[7]使CET的稳定性增加3.5倍.采用体外抗氧化活性测定(ABTS法)考察了Q[7]对CET抗氧化活性的影响,发现CET@Q[7]包结配合物以及游离CET均对ABTS自由基有较好的清除作用.IC50值分别为3.4×10~(-5)和2.4×10~(-5)mol/L,表明Q[7]不仅能增加CET的溶解性和稳定性,同时对CET抗氧化活性的影响不大. 相似文献