全文获取类型
收费全文 | 1465篇 |
免费 | 221篇 |
国内免费 | 390篇 |
专业分类
化学 | 1875篇 |
晶体学 | 32篇 |
力学 | 5篇 |
综合类 | 17篇 |
物理学 | 147篇 |
出版年
2023年 | 28篇 |
2022年 | 17篇 |
2021年 | 45篇 |
2020年 | 75篇 |
2019年 | 35篇 |
2018年 | 52篇 |
2017年 | 46篇 |
2016年 | 74篇 |
2015年 | 76篇 |
2014年 | 86篇 |
2013年 | 149篇 |
2012年 | 124篇 |
2011年 | 131篇 |
2010年 | 91篇 |
2009年 | 75篇 |
2008年 | 101篇 |
2007年 | 104篇 |
2006年 | 107篇 |
2005年 | 81篇 |
2004年 | 97篇 |
2003年 | 79篇 |
2002年 | 71篇 |
2001年 | 30篇 |
2000年 | 36篇 |
1999年 | 35篇 |
1998年 | 34篇 |
1997年 | 32篇 |
1996年 | 35篇 |
1995年 | 27篇 |
1994年 | 25篇 |
1993年 | 11篇 |
1992年 | 17篇 |
1991年 | 14篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有2076条查询结果,搜索用时 15 毫秒
11.
Yu He Yating Guo Yanbin Yu Peifu Luo Honglong Qiu Guoming Huang 《Particle & Particle Systems Characterization》2021,38(5):2100038
In this study, manganese tellurite (MnTeO3) nanoparticles are developed as theranostic agents for magnetic resonance imaging (MRI)-guided photothermal therapy of tumor. MnTeO3 nanoparticles are synthesized via a simple one-step method. The as-synthesized MnTeO3 nanoparticles with uniform size show good biocompatibility. In particular, MnTeO3 nanoparticles exhibit a high photothermal conversion efficiency (η = 26.3%), which is higher than that of gold nanorods. Moreover, MnTeO3 nanoparticles also have high MRI performance. The longitudinal relaxivity (r1) value of MnTeO3 nanoparticles is determined to be 8.08 ± 0.2 mm −1 s−1, which is higher than that of clinically approved T1-contrast agents Gd-DTPA (4.49 ± 0.1 mm −1 s−1). The subsequent MnTeO3 nanoparticles-mediated photothermal therapy displays a highly efficient ablation of tumor cells both in vitro and in vivo with negligible toxicity. It is demonstrated that MnTeO3 nanoparticles can serve as promising theranostic agents with great potentials for MRI-guided photothermal therapy. 相似文献
12.
Jiaqi Ke Yufei Zhang Yibo Zhang Minghui Ye Zicheng Zhang Yongchao Tang Xiaoqing Liu Prof. Cheng Chao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(54):e202201687
Rechargeable zinc-ion batteries (ZIBs) are potential for grid-scale applications owing to their safety, low price, and available sources. The development of ZIBs cathode with high specific capacity, wide operating voltage window and stable cyclability is urgently needed in next-generation commercial batteries. Herein, we report a structurally crystalline-stable Mn(VO3)2 nanobelts cathode for ZIBs prepared via a facile hydrothermal method. The as-synthesized Mn(VO3)2 exhibited high specific capacity of 350 mAh g−1 at 0.1 A g−1, and maintained a capacity retention of 92 % after 10,000 cycles at 2 A g−1. It also showed good rate performance and obtained a reversible capacity of up to 200 mAh g−1 after 600 cycles at 0.2 A g−1 under −20 °C. The electrochemical tests suggest that Mn(VO3)2 nanobelts impart fast Zn2+ ions migration, and the introduction of manganese atoms help make the structures more indestructible, leading to a good rate performance and prolonged cycle lifespan. 相似文献
13.
在DMF/H2O/CH3OH的混合体系中,反应温度为170℃,Mn SO4·4H2O盐溶液在p H=5和7的条件下,加热72小时,最终得到了结构不同的硫酸锰骨架[Mn2(SO4)3]·(H3O)2(1)和[Mn3(SO4)2(OH)2(H2O)2](2)。化合物结构通过单晶X-射线和红外光谱所表征,相应的晶胞参数:化合物1,立方晶系,空间群:P213,a=10.2009(12),V=1061.49(37)3,Goo F=1.158,Flack parameter 0.02(2),R1=0.0186(I2sigma);化合物2,四方晶系,空间群:Pbcm,a=7.3214(15),b=9.984(2),c=13.291(3),V=971.5(4)3,Goo F=1.063,R1=0.0227(I2sigma);单晶X射线分析显示化合物1是一个三维单手性硫酸锰骨架,化合物2是一个非手性羟基硫酸锰骨架。实验结果说明,p H值对硫酸锰骨架的改变起重要作用。 相似文献
14.
A spray‐based technique, originally developed for the production of semiconductor nanocrystals, is utilized for the preparation of high‐quality nanocrystalline thin films, as demonstrated with manganese sulfide. The films are formed by the use of pneumatic‐assisted thermospray or pneumatic nebulizers. Our simple, low‐cost, and low‐temperature process results in a dense and phase‐pure grain structure. The concepts and benefits of this technique are described and discussed. The film characteristics show dependence on the experimental parameters, in particular the rate of solvent vaporization. Three alternative film formation mechanisms are suggested for cases with varied experimental conditions. 相似文献
15.
Qiang Yu Xiangjun Li Diansheng Liu Jianfeng Li 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):545-548
`Picket‐fence' porphyrin compounds are used in the investigation of interactions of hemes with dioxygen, carbon monoxide, nitric monoxide and imidazole ligands. (Cryptand‐222)potassium chlorido[meso‐tetra(α,α,α,α‐o‐pivalamidophenyl)porphyrinato]manganese tetrahydrofuran monosolvate (cryptand‐222 is 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane), [K(C18H36N2O6)][Mn(C64H64N8O4)Cl]·C4H8O or [K(222)][Mn(TpivPP)Cl]·THF [systematic name for TpivPP: 5,10,15,20‐tetrakis(2‐tert‐butanamidophenyl)porphyrin], is a five‐coordinate high‐spin manganese(II) picket‐fence porphyrin complex. It crystallizes with a potassium cation chelated inside a cryptand‐222 molecule; the average K—O and K—N distances are 2.83 (4) and 2.995 (13) Å, respectively. All four protecting tert‐butyl pickets of the porphyrin are ordered. The porphyrin plane is nearly planar, as indicated by the atomic displacements and the dihedral angles between the mean planes of the pyrrole rings and the 24‐atom mean plane. The axial chloride ligand is located inside the molecular cavity on the hindered porphyrin side and the Mn—Cl bond is tilted slightly off the normal to the porphyrin plane by 3.68 (2)°. The out‐of‐plane displacement of the metal centre relative to the 24‐atom mean plane (Δ24) is 0.7013 (4) Å, indicating a noticeable porphyrin core doming. 相似文献
16.
蒋国芬 《中国无机分析化学》2017,7(3):42-45
采用仪器分析方法和化学分析方法相结合测定三元前驱体Ni0.33Co0.33Mn0.33(OH)2中镍、钴、锰主含量,分别采用电感耦合等离子体原子发射光谱(ICP-AES)内标法测定镍、钴、锰的摩尔比例,EDTA滴定法测定镍、钴、锰的摩尔总量,计算得到各元素的含量。通过优化实验条件,进行了准确度和精密度实验,加标回收率为99.2%~101%,相对标准偏差小于0.65%。方法准确、快速,已用于实际的检测工作中。 相似文献
17.
Robbert van Putten Evgeny A. Uslamin Marcel Garbe Chong Liu Dr. Angela Gonzalez-de-Castro Dr. Martin Lutz Dr. Kathrin Junge Prof. Dr. Emiel J. M. Hensen Prof. Dr. Matthias Beller Dr. Laurent Lefort Prof. Dr. Evgeny A. Pidko 《Angewandte Chemie (International ed. in English)》2017,56(26):7531-7534
Catalytic hydrogenation of carboxylic acid esters is essential for the green production of pharmaceuticals, fragrances, and fine chemicals. Herein, we report the efficient hydrogenation of esters with manganese catalysts based on simple bidentate aminophosphine ligands. Monoligated Mn PN complexes are particularly active for the conversion of esters into the corresponding alcohols at Mn concentrations as low as 0.2 mol % in the presence of sub-stoichiometric amounts of KOtBu base. 相似文献
18.
Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co3Mn2@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―Nx (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN− ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.![]()
相似文献
19.
以浓盐酸为浸出剂,以NaOH和NH4HCO3为沉淀剂,利用Mn2+在碱性条件下的氧化反应改变离子的沉淀次序进而分步回收的方案,探究了浓盐酸酸浸处理三元正极材料LiNi0.8Co0.05Mn0.15O2的最佳条件。在分步沉淀过程中,Mn2+被氧化为不溶于非还原性酸的MnO (OH)2,并在酸性条件下回收。Ni、Co则在碱性条件下利用NaOH回收,而Li则利用NH4HCO3回收。该方法中Mn的回收率达到85.1%,产品纯度达到98.6%; Li的回收率达到95.0%,产品纯度达到99.3%。由回收材料重新合成的三元正极组装的软包电池的首圈放电比容量达到了175 mAh·g-1,可以以超过99.5%的库仑效率稳定循环50圈。 相似文献
20.
In this study, tetracarboxylic manganese phthalocyanine coated nano-zinc oxide (MnC4Pc-ZnO) composite material was prepared by in-situ growth method and modified with indium tin oxide (ITO) glass electrode to construct a photoelectrochemical (PEC) sensor. A PEC sensor for the determination of amlodipine besylate (AB) was developed for the first time based on the principle of precipitation reaction between heavy metal ions and dihydropyridine and the recombination suppression effect of the material. The morphology and optical properties of the MnC4Pc-ZnO composites were characterized by scanning electron microscopy (SEM) and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS). Chronoamperometry (i-t) and electrochemical impedance spectroscopy (EIS) were used to study the PEC behavior of ITO electrodes modified by MnC4Pc-ZnO composite material. The study found that the MnC4Pc-ZnO composite material has a good photocurrent response to AB, and there was a good linear relationship between the concentration range of 75 nM-250 μM, the linear equation was I(μA)=−5.2×10−8×lgC+3.2×10−8 (r=0.9947), a limit of detection (LOD) of 20 nM. In addition, MnC4Pc-ZnO/ITO also has good selectivity and stability. The PEC sensor detects amlodipine besylate tablets, amlodipine besylate dispersible tablets, and biological samples, with standard addition recovery rates of 96.11 % and 103.96 %, respectively. The determination result has good accuracy, and the PEC sensor provides a new method for detecting AB. 相似文献