全文获取类型
收费全文 | 15069篇 |
免费 | 2597篇 |
国内免费 | 1907篇 |
专业分类
化学 | 11196篇 |
晶体学 | 232篇 |
力学 | 835篇 |
综合类 | 131篇 |
数学 | 1613篇 |
物理学 | 5566篇 |
出版年
2024年 | 44篇 |
2023年 | 309篇 |
2022年 | 460篇 |
2021年 | 520篇 |
2020年 | 580篇 |
2019年 | 637篇 |
2018年 | 502篇 |
2017年 | 493篇 |
2016年 | 695篇 |
2015年 | 700篇 |
2014年 | 892篇 |
2013年 | 1208篇 |
2012年 | 1407篇 |
2011年 | 1553篇 |
2010年 | 1038篇 |
2009年 | 1013篇 |
2008年 | 1016篇 |
2007年 | 993篇 |
2006年 | 801篇 |
2005年 | 683篇 |
2004年 | 583篇 |
2003年 | 443篇 |
2002年 | 416篇 |
2001年 | 354篇 |
2000年 | 328篇 |
1999年 | 251篇 |
1998年 | 212篇 |
1997年 | 168篇 |
1996年 | 185篇 |
1995年 | 148篇 |
1994年 | 154篇 |
1993年 | 119篇 |
1992年 | 115篇 |
1991年 | 94篇 |
1990年 | 87篇 |
1989年 | 78篇 |
1988年 | 44篇 |
1987年 | 41篇 |
1986年 | 42篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 16篇 |
1982年 | 6篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 11篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1957年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
951.
多巴胺和L-精氨酸制备超轻氮掺杂石墨烯气凝胶吸油性能的研究 总被引:1,自引:0,他引:1
多巴胺和L-精氨酸制备超轻氮掺杂石墨烯气凝胶吸油性能的研究 《燃料化学学报》2017,45(10):1230-1235
采用水热法制备了超轻氮掺杂石墨烯气凝胶。分析表征结果表明,多巴胺不仅为还原剂而且提供氮源,石墨烯溶液前躯体的pH值对水热法制备超轻氮掺杂石墨烯气凝胶很大的影响,通过调节多巴胺和L-精氨酸在石墨烯溶液前躯体的浓度,可制备密度为2.54 mg/cm3超轻氮掺杂石墨烯气凝胶,由于氮掺杂、低密度和大的比表面积,超轻氮掺杂石墨烯气凝胶对各种油品都有良好的吸附性能。 相似文献
952.
采用"碱-酸-碱"合成工艺,在各阶段将OMMT(有机蒙脱土)投入反应体系,制备有机蒙脱土改性脲醛树脂胶黏剂,测试胶黏剂的各项性能,用XRD(X射线衍射仪)、FTIR(傅里叶变换红外光谱)、SEM(扫描电镜)、TG(热重分析)对改性胶黏剂结构进行表征.实验结果表明,随着OMMT的加入,胶黏剂的游离甲醛含量降低,胶合强度增加.第一阶段投入OMMT,降醛效果明显,第二阶段投入OMMT,补强效果明显.SEM图显示,改性胶黏剂中被剥离成片层状的OMMT因受基体的包覆或挤压,呈现出蜷曲的形状;XRD图谱显示,OMMT/UF胶黏剂的结晶度低于UF胶黏剂的结晶度,有机蒙脱土的加入,破坏了脲醛树脂中羰基和氨基的规整性排列;FTIR图谱表明,改性脲醛树脂胶黏剂中存在大量游离的尿素,胶黏剂的游离甲醛含量低;TG分析得出,改性胶黏剂的TG曲线移向高温方向,材料的热分解温度提高. 相似文献
953.
Enzymetically Regulating the Self‐Healing of Protein Hydrogels with High Healing Efficiency
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Yuzhou Gao Prof. Quan Luo Shanpeng Qiao Liang Wang Prof. Zeyuan Dong Jiayun Xu Prof. Junqiu Liu 《Angewandte Chemie (International ed. in English)》2014,53(35):9343-9346
Enzyme‐mediated self‐healing of dynamic covalent bond‐driven protein hydrogels was realized by the synergy of two enzymes, glucose oxidase (GOX) and catalase (CAT). The reversible covalent attachment of glutaraldehyde to lysine residues of GOX, CAT, and bovine serum albumin (BSA) led to the formation and functionalization of the self‐healing protein hydrogel system. The enzyme‐mediated protein hydrogels exhibit excellent self‐healing properties with 100 % recovery. The self‐healing process was reversible and effective with an external glucose stimulus at room temperature. 相似文献
954.
Chao Liang Shu‐ying Han Jun‐qin Qiao Hong‐zhen Lian Xin Ge 《Journal of separation science》2014,37(22):3226-3234
A strategy to utilize neutral model compounds for lipophilicity measurement of ionizable basic compounds by reversed‐phase high‐performance liquid chromatography is proposed in this paper. The applicability of the novel protocol was justified by theoretical derivation. Meanwhile, the linear relationships between logarithm of apparent n‐octanol/water partition coefficients (logKow′′) and logarithm of retention factors corresponding to the 100% aqueous fraction of mobile phase (logkw) were established for a basic training set, a neutral training set and a mixed training set of these two. As proved in theory, the good linearity and external validation results indicated that the logKow′′–logkw relationships obtained from a neutral model training set were always reliable regardless of mobile phase pH. Afterwards, the above relationships were adopted to determine the logKow of harmaline, a weakly dissociable alkaloid. As far as we know, this is the first report on experimental logKow data for harmaline (logKow = 2.28 ± 0.08). Introducing neutral compounds into a basic model training set or using neutral model compounds alone is recommended to measure the lipophilicity of weakly ionizable basic compounds especially those with high hydrophobicity for the advantages of more suitable model compound choices and convenient mobile phase pH control. 相似文献
955.
通过溶液聚合法制备了具有空心结构的聚氰基丙烯酸乙酯纳米纤维,纤维直径为50~100 nm.研究了3种溶液体系对形成聚氰基丙烯酸乙酯纳米纤维形貌与直径的影响,并探讨了其形成机理.通过调控溶液体系内外环境可得到不同形貌的聚合物纤维,且纤维表面表现出疏水性质.该方法适用于平整且具有粗糙结构的表面.所形成的聚氰基丙烯酸乙酯纳米纤维涂层可用于基底的疏水改性. 相似文献
956.
Controlled Synthesis of N‐Doped Carbon Nanospheres with Tailored Mesopores through Self‐Assembly of Colloidal Silica
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Gang Wang Prof. Yuhan Sun Prof. Debao Li Dr. Hai‐Wei Liang Dr. Renhao Dong Prof. Xinliang Feng Prof. Klaus Müllen 《Angewandte Chemie (International ed. in English)》2015,54(50):15191-15196
Limited strategies have been established to prepare monodisperse mesoporous carbon nanospheres (MCNs) with tailored pore sizes. In this work, a method is reported to synthesize MCNs by combining polymerization of aniline with co‐assembly of colloidal silica nanoparticles. The controlled self‐assembly behavior of colloidal silica enables the formation of uniform composite nanospheres and convenient modulation over mesopores. After carbonization and removal of sacrificial templates, the resultant MCNs possess tunable mesopores (7–42 nm) and spherical diameters (90–300 nm), as well as high surface area (785–1117 m2 g?1), large pore volume (1.46–2.01 cm3 g?1) and abundant nitrogen moieties (5.54–8.73 at %). When serving as metal‐free electrocatalysts for the oxygen reduction reaction (ORR), MCNs with an optimum pore size of 22 nm, compared to those with 7 and 42 nm, exhibit the best ORR performance in alkaline medium. 相似文献
957.
Screening of drugs of abuse and toxic compounds in human whole blood using online solid‐phase extraction and high‐performance liquid chromatography with time‐of‐flight mass spectrometry
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Xiaomei Teng Chen Liang Rong Wang Tao Sun Yulan Rao Chunfang Ni Libo Zeng Lingjuan Xiong Yuan Li Yurong Zhang 《Journal of separation science》2015,38(1):50-59
A novel method for the screening of 151 drugs of abuse and toxic compounds in human whole blood has been developed and validated by online solid‐phase extraction with liquid chromatography coupled to time‐of‐flight mass spectrometry. Analytes were extracted and separated by using a fully automated online solid‐phase extraction liquid chromatography system with total chromatographic run time of 26 min. Time‐of‐flight mass spectrometry screening of 151 drugs of abuse and toxic compounds was performed in a full‐scan (m/z 50–800) mode using an MSE acquisition of molecular ions and fragment ions data at two collision energies (one was 6 eV and another one was in the range of 5–45 eV). The compounds were identified based on retention times and exact mass of molecular ions and fragment ions. The limit of detection ranged from 1 to 100 ng/mL and the recovery of the method ranged from 6.3 to 163.5%. This method is proved to be a valuable screening method allowing fast and specific identification of drugs in human whole blood. 相似文献
958.
合成并通过单晶衍射表征了3个稀土配合物Ln(L)(NO3)3(H2O)(L=N-苯基-2-(5-氯-8-喹啉氧基)乙酰胺,Ln=Eu(1),Gd(2),Er(3)),结构与拥有相同有机配体的Pr,Nd和Sm配合物同构。在每个配合物中,十配位的稀土离子采取扭曲的双帽四方反棱柱配位构型,分别与来自1个配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根和1个水分子配位。配合物1能够发射Eu(Ⅲ)离子特征荧光,荧光寿命为437 μs。 相似文献
959.
Energy‐resolved technique for discovery and identification of malonyl‐triterpene saponins in Caulophyllum robustum by UHPLC‐electrospray Fourier transform mass spectrometry
下载免费PDF全文
![点击此处可从《Journal of mass spectrometry : JMS》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yong‐Gang Xia Jun Liang Guo‐Yu Li Bing‐You Yang Hai‐Xue Kuang 《Journal of mass spectrometry : JMS》2016,51(10):947-958
Malonyl‐triterpene saponins (MTSs) attract scientific attentions because of their structural diversities and valuable bioactivities. However, its thermal instability brings a huge amount of challenges for isolation and purification of this class of compounds. To our best knowledge, there has been no report on isolation and analysis of MTSs from genus Caulophyllum. In this study, a strategy combining data acquisition using an energy‐resolved technique and the narrow widow extracted ion chromatograms as data mining method was developed for discovery and identification of MTSs in Caulophyllum robustum hair roots by ultra high liquid chromatography coupled to electrospray ionization Fourier transform mass spectrometry. The method was performed at an independent MS full scan using our bottom‐up energies by in‐source collision induced dissociations with 0, 25, 50 and 100 eV in both positive and negative modes. Precursor ion as well as fragment ion information was simultaneously collected from four energy‐resolved MS spectra in a single run of 18 min. The fragmentation pathways of intact deprotonated, protonated and sodium ions of MTSs were proposed for the structural elucidation of Caulophyllum MTSs. A flowchart involving a stepwise procedure based on key fragments from ESI?/ESI+‐FT‐MS(1, 1) to MS(1, 4) spectra was constructed for the identification of structural elements in the MTSs. As a result, a total of 23 MTSs were discovered and tentatively identified, which had not been reported from Caulophyllum species before. All of these were potentially new compounds. This study provides an excellent example for discovery and identification of MTSs in herb medicines. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
960.
Synthesis,Structures, and Fluorescent Properties of Three Cobalt‐Based Coordination Polymers with a Rigid Tripodal Carboxylate Ligand
下载免费PDF全文
![点击此处可从《无机化学与普通化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Xiao‐Bin Liu Zhen‐Yu Xiao Ao Huang Wen Wang Liang‐Liang Zhang Rong‐Ming Wang Dao‐Feng Sun 《无机化学与普通化学杂志》2016,642(1):31-35
Three cobalt(II) coordination polymers, [Co2(tatb)2(2,2′‐bipy)2 (H2O)2 · DMA · 2H2O] ( 1 ), [Co2(tatb)2(1,10‐phen)2(H2O)2 · 2H2O] ( 2 ) and [Co(tatb)(1,3‐dpp) · H2O] ( 3 ) (H3tatb = 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl; 1,10‐phen = 1,10‐phenanthroline; 1,3‐dpp = 1,3‐bis(pyridin‐4‐yl)propane), were synthesized solvothermally and characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double‐chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π–π interactions. Complex 3 possesses 2D 44‐sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1 , 2 and 3 were also investigated. 相似文献