全文获取类型
收费全文 | 541篇 |
免费 | 146篇 |
国内免费 | 191篇 |
专业分类
化学 | 378篇 |
晶体学 | 51篇 |
力学 | 47篇 |
综合类 | 32篇 |
数学 | 88篇 |
物理学 | 282篇 |
出版年
2024年 | 2篇 |
2023年 | 2篇 |
2022年 | 23篇 |
2021年 | 11篇 |
2020年 | 12篇 |
2019年 | 11篇 |
2018年 | 19篇 |
2017年 | 34篇 |
2016年 | 21篇 |
2015年 | 26篇 |
2014年 | 40篇 |
2013年 | 55篇 |
2012年 | 38篇 |
2011年 | 48篇 |
2010年 | 56篇 |
2009年 | 31篇 |
2008年 | 72篇 |
2007年 | 60篇 |
2006年 | 44篇 |
2005年 | 57篇 |
2004年 | 30篇 |
2003年 | 21篇 |
2002年 | 20篇 |
2001年 | 31篇 |
2000年 | 21篇 |
1999年 | 15篇 |
1998年 | 8篇 |
1997年 | 13篇 |
1996年 | 10篇 |
1995年 | 9篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1984年 | 2篇 |
1982年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有878条查询结果,搜索用时 31 毫秒
21.
22.
采用高温顶空液相萃取再转移的方法,对中药白术中挥发性成分进行萃取分离富集,采用顶空液液萃取/气相色谱-质谱(HS-LP-LPE/GC-MS)联用法进行测定,并与传统水蒸汽蒸馏法(SD)提取的挥发性成分进行对比。对各种测定条件和影响因素进行了考察,最佳萃取条件为:1.0 mL PEG 400为高温萃取剂,样品用量1.2 g,萃取温度120℃,萃取时间60 min,再将萃取剂用1.0 mL正己烷进行反萃取后进行GC-MS分析;采用HS-LP-LPE/GC-MS鉴定了33个组分,占总组分含量93.18%;SD鉴定了31个组分,占总组分含量97.12%。两种方法共同检测到的组分有29个,均以苍术酮(Atractylone)含量最高。结果表明,两种方法所提取的组分基本相同,可用于白术挥发性成分的测定。 相似文献
23.
利用配体1,5-二(3-羧基吡啶基)-N-甲基二乙胺(L)合成2种稀土金属配合物{[La2L4(H2O)2](ClO4)6·6H2O}n(1)和[Nd2L4(DMF)6(H2O)2]2(ClO4)6·4H2O(2)。用红外光谱和X-射线单晶衍射表征配合物的晶体结构。结构分析表明:配合物1属于三斜晶系,P1空间群,其晶胞参数为a=1.4966(3)nm,b=1.5597(4)nm,c=1.9568(4)nm,α=86.776(6)°,β=77.723(7)°,γ=87.168(7)°,Z=2。在配合物1中,一对La(Ⅲ)原子被2个羧基桥联,形成双核结构;双核结构进一步被羧基连接,从而形成平行于c轴的一维链。值得注意的是配合物1的晶体结构中包含着由氢键连接的6个H2O分子组成的水分子簇。配合物2属于三斜晶系,P1空间群,晶胞参数为a=1.0408(4)nm,b=1.3541(5)nm,c=2.975(1)nm,α=94.390(8)°,β=91.720(7)°,γ=95.230(4)°,Z=2。配合物2中4个羧基连接一对Nd(Ⅲ)原子,形成四轮状结构,其中2个羧基采取syn-syn双原子桥联模式,而其余2个羧基则采取单原子桥联模式。 相似文献
24.
LI Siying PAN Yangang TENG Honggang SHAN Yuping YANG Guocheng WANG Hongda 《高等学校化学研究》2022,38(3):838-842
The rabies virus is a neurotropic virus that causes fatal diseases in humans and animals. Although studying the interactions between a single rabies virus and the cell membrane is necessary for understanding the pathogenesis, the internalization dynamic mechanism of single rabies virus in living cells remains largely elusive. Here, we utilized a novel force tracing technique based on atomic force microscopy(AFM) to record the process of single viral entry into host cell. We revealed that the force of the rabies virus internalization distributed at (65±25) pN, and the time was identified by two peaks with spacings of (237.2±59.1) and (790.3±134.4) ms with the corresponding speed of 0.12 and 0.04 μm/s, respectively. Our results provide insight into the effects of viral shape during the endocytosis process. This report will be meaningful for understanding the dynamic mechanism of rabies virus early infection. 相似文献
25.
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
26.
高效液相色谱-电喷雾串联质谱法测定畜禽粪便中四环素类抗生素 总被引:1,自引:0,他引:1
建立了高效液相色谱-电喷雾串联质谱法(HPLC-MS/MS)测定畜禽粪便中四环素类抗生素的分析方法。样品经甲醇-乙酸-水(体积比6∶3∶1)溶液提取,OASIS HLB小柱净化后,采用Waters Symmetry C18色谱柱(150×3.9mm,5μm)进行分离,以0.3%甲酸水溶液-0.3%甲酸乙腈溶液梯度洗脱,电喷雾正离子模式多反应监测(MRM)模式定量分析。在优化的色谱条件下,四环素、土霉素和金霉素在0.05~1.0mg/L范围内具有良好的线性,其检出限分别为0.025、0.084、0.098mg/kg;样品回收率为80%~103%。实验结果表明,该方法较液相色谱法具有更高的准确性和灵敏度,可满足畜禽粪便中四环素类抗生素残留的检测要求。 相似文献
27.
中药川芎超临界CO2提取液的液相色谱-电喷雾多级质谱研究 总被引:2,自引:1,他引:1
采用HPLC-MSn技术分析和鉴定了中药川芎超临界CO2提取液中的主要成分:洋川芎内酯A、Z-藁本内酯、新蛇床内酯、3-丁基苯酞和苯酞二聚体。液相色谱-离子阱质谱联用在正离子电喷雾电离、自动多级质谱模式下进行分析。样品在ECLIPSE XDB C18色谱柱上以含0.25%乙酸水溶液和含0.25%乙酸甲醇梯度洗脱分离。对藁本内酯等苯酞内酯电喷雾电离后的碰撞裂解机理进行了探讨。Z-藁本内酯的碰撞裂解的两个主要途径为:侧链断裂脱烯和开环脱水再脱羰。实验中没有观察到孤立的脱羰过程。而这些主要成分的加钠离子的碰撞裂解过程完全不同。 相似文献
28.
Nanosized hydroxyapatite(nsHAp) was synthesized to examine its possibility as a controlled release carrier of protein. To achieve effective protein release from nanosized hydroxyapatite, the study of the adsorptive properties of protein on nsHAp and different influence parameters such as pH, calcium, and phosphate concentrations during the adsorption process is necessary. Ovalbumin(OVA) was selected as the model of growth factors. The results show that the amount of OVA adsorbed onto nsHAp in acetic buffer(pH=3.6) is more than that in acetic buffer(pH=5.6) because of the electric interaction. The amount of OVA adsorption in phosphate buffer solution(PBS) is smaller than that in acetic buffer because of surface complexation and surface hydroxylation. The presence of Ca2 dramatically increases the adsorbed amount of OVA in acetic buffer on maintaining the same pH. Meanwhile, the release kinetics of OVA adsorbed onto nsHAp(nsHAp-OVA) was also examined. The amount of released OVA in PBS(pH=5.6) was significantly smaller than that released in solution of pH=7.0. All the results suggest that nanosized hydroxyapatite particles could be successfully used as controlled released carrier of protein. 相似文献
29.
30.
WU Shi TENG Qi-Wen① 《结构化学》2006,25(6):694-698
1 INTRODUCTION After Guo[1] synthesized and detected C60-nBn and C70-nBn by mass spectra, investigations on fullerenes doped by other atoms became more and more interesting. Andreoni[2] studied the impurity states of the doped fullerenes C59B; Dong[3] calculated the structural and electronic properties of C59B; Wang[4] assessed the stability of heterohedral fullerenes C60-xBx. Lamparth[5] prepared C59N and C69N , and put forward the possible structures for C59N . Sahoo[6] obtained… 相似文献