全文获取类型
收费全文 | 522篇 |
免费 | 58篇 |
国内免费 | 141篇 |
专业分类
化学 | 677篇 |
晶体学 | 1篇 |
力学 | 6篇 |
综合类 | 9篇 |
数学 | 5篇 |
物理学 | 23篇 |
出版年
2024年 | 2篇 |
2023年 | 6篇 |
2022年 | 37篇 |
2021年 | 50篇 |
2020年 | 30篇 |
2019年 | 27篇 |
2018年 | 21篇 |
2017年 | 20篇 |
2016年 | 27篇 |
2015年 | 26篇 |
2014年 | 35篇 |
2013年 | 46篇 |
2012年 | 39篇 |
2011年 | 22篇 |
2010年 | 34篇 |
2009年 | 30篇 |
2008年 | 25篇 |
2007年 | 18篇 |
2006年 | 19篇 |
2005年 | 28篇 |
2004年 | 17篇 |
2003年 | 31篇 |
2002年 | 28篇 |
2001年 | 17篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 11篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1959年 | 2篇 |
排序方式: 共有721条查询结果,搜索用时 31 毫秒
1.
Michiel Janssen Prof. Dirk E. De Vos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(45):10724-10734
The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing PtIV with a more economically viable oxidant, particularly O2. We report the potential of employing FeCl2 as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O2 in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O2 in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt0 was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N2 in the gaseous atmosphere. Finally, stability tests revealed the involvement of PtII and FeCl2 in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O2 is presented. 相似文献
2.
芳环羟基化HPLC分离荧光法检测Cu(Ⅱ)-H2O2体系中产生的·OH 总被引:4,自引:3,他引:1
采用L-苯丙氨酸为探针,使用液相色谱分离荧光检测(FLD)和荧光分光光度分析(FS)两种方法平行检测Cu(Ⅱ)-H2O2 体系中产生的·OH.试验采用的激发波长277 nm,发射波长306 nm.体系在反应前后的荧光变化,可反映·OH产生量.对FLD与FS所得数据进行了比较分析,结果显示两种方法具有较高一致性.FS使用混合体系检测,易对荧光的产生造成干扰,而FLD法没有干扰. 相似文献
3.
Highly Effective Phenol Hydroxylation over Ti-ZSM-5 Catalyst Prepared Using B-ZSM-5 as Precursor 以B-ZSM-5为母体合成Ti-ZSM-5高效苯酚羟基化催化剂 总被引:3,自引:0,他引:3
以改进方法合成的B-ZSM-5为母体,采用气固相同晶取代法合成了较小晶粒的Ti-ZSM-5分子筛. 考察了样品的物化性能和催化苯酚羟基化性能. 结果表明: 所合成的小晶粒Ti-ZSM-5具有较高的结晶度,尺寸为100~200 nm,且不含锐钛矿型TiO2,对苯酚羟基化反应的催化性能优异. 相似文献
4.
谢晓梅 《广东微量元素科学》2002,9(8):18-22
在预培红壤中加入定量的有机肥和葡萄糖及不同浓度的Cu,25℃培养14d,测定了土壤微生物生物量C(Cmic),N(Nmic)。结果表明,存在有机肥和葡萄糖时,土壤中Cmic和Nmic随着Cu浓度的增加而降低;Cmic/Nmic随着Cu浓度的增加而增大。施加有机肥和葡萄糖的土壤中,在所有Cu处理浓度下,土壤中Cmic和Nmic均比未加有机物质处理高,特别是有机肥处理中土壤Cmic和Nmic均比其它处理高得多,说明有机肥可明显减轻Cu对土壤微生物生物量的毒性,同时也说明有机肥可提供微生物N源。不含Cu时,加入有机肥和葡萄糖导致土壤中Cmic和Nmic增加,其中有机肥明显。 相似文献
5.
6.
铬(Ⅲ)邻菲咯啉,8—羟基喹啉配合物/Y型分子筛的制备及苯酚催化羟化 总被引:2,自引:0,他引:2
制备了铬(Ⅲ)邻菲咯啉,8-羟基喹啉配合物/Y型分子筛,利用元素分析,SEM,UV-VisBET及XRD等方法确定了分子筛选笼中金属配合物的生在及其晶体结构,考察了实验参数对苯酚转化率及产物选择性的影响。 相似文献
7.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
8.
0IntroductionRareearthsarenowappliedwidelyinChina,whichcanimprovecropsyieldsandthetheirqualit-ies犤1犦.Thebeneficialeffectsmaybeduetothestimu-latoryeffectsoftheseelementsonthenutrientuptakebyplantsorontheincreasingofchlorophyllsynthesisintheplants犤2犦.Whilealotofresearcheshavebeendoneontheimprovednutritionofcropsafterapplica-tionofrareearths,muchlessattentionhasbeenpaidtothedeteriorationofsoilqualityduetotheapplicationofrareearthsforyears犤3犦.Scientistshavediscoveredthataccumula… 相似文献
9.
Barros N. Feijóo S. Simoni A. Critter S. A. M. Airoldi C. 《Journal of Thermal Analysis and Calorimetry》2000,63(2):577-588
The microcalorimetric method was used to calculate the metabolic enthalpy change per mol of glucose degraded by soil microorganisms,
ΔH
met. This parameter has been calculated by microcalorimetry for many organic, inorganic and biochemical reactions, but there
is only some information about its quantification for microbial growth reactions in soils. Values of ΔH
met were calculated for different soil samples collected in Galicia (Spain) and Campinas (Săo Paolo, Brazil). Exponential microbial
growth was stimulated in all soil samples by the addition of glucose and power-time curves were recorded. Results showed changes
in the values of ΔH
met calculated for all the soil samples, suggesting a dependence of this value with the microbial growth rate constant, with
the percentage of growth, with the initial number of microorganisms of soil samples, with the quantity of glucose added and
with the strain of bacteria growing in soil.
The interpretation of variations of ΔH
met provides important qualitative and quantitative information. It reports data that allow to interpret from a qualitative point
of view, the increase in biomass as a consequence of the degradation of the organic matter in soil, to understand changes
in the percentages of soil organic matter and to know if the microbial population growing in differential soil samples is
homogeneous. Therefore, to report that value would be very important in ecological studies, but beforehand, it is necessary
to solve some problems that can appear in the experiments done to make the quantification
.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
10.
Ti接枝MCM-41催化剂的结构设计及化学亲和选择性研究 总被引:3,自引:0,他引:3
用二氯化钛茂作为活性物种的来源,利用Si-MCM-41催化剂表面羟基的反应性,得到了Ti接枝MCM-41催化剂的两种结构模型.结构表征结果表明,Ti接枝MCM-41催化剂不仅长程结构好,孔径分布均一,而且催化剂表面活性中心含量高.两种结构模型催化剂上芳烃羟化反应性能表明,Ti接枝MCM-41催化剂表面的亲水/憎水性可以在较宽的范围内调变,从而可实现控制芳烃羟化的化学亲和选择性.另外,研究结果还表明,Ti接枝MCM-41催化剂具有很好的活性稳定性. 相似文献