全文获取类型
收费全文 | 264篇 |
免费 | 15篇 |
国内免费 | 3篇 |
专业分类
化学 | 220篇 |
晶体学 | 5篇 |
力学 | 1篇 |
数学 | 17篇 |
物理学 | 39篇 |
出版年
2023年 | 10篇 |
2022年 | 7篇 |
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 13篇 |
2018年 | 11篇 |
2017年 | 8篇 |
2016年 | 16篇 |
2015年 | 10篇 |
2014年 | 6篇 |
2013年 | 24篇 |
2012年 | 26篇 |
2011年 | 22篇 |
2010年 | 16篇 |
2009年 | 18篇 |
2008年 | 11篇 |
2007年 | 10篇 |
2006年 | 6篇 |
2005年 | 15篇 |
2004年 | 1篇 |
2003年 | 5篇 |
2002年 | 1篇 |
2001年 | 4篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1986年 | 1篇 |
1984年 | 5篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有282条查询结果,搜索用时 265 毫秒
11.
12.
13.
Electroanalytical determination of heavy metals using stripping voltammetry is commonly employed and has many advantages over
other methods. The sensitivity of the technique is greatly improved by employing different modified electrodes. Seven novel
polymer-modified glassy carbon electrodes have been developed in this investigation for the trace analysis of heavy metals
such as zinc, cadmium, lead, arsenic, and copper in formulated samples of waters by square wave stripping voltammetry. Very
good responses have been observed for all the metals, while all the modified electrodes employed. The poly(3,4-ethylenedioxythiophene)-modified
electrode has resulted in very low limit of detection (LOD) value. Comparison is made between literature results of LOD and
the results obtained in this study. An independent atomic absorption spectroscopic analysis of the industrial wastewater sample
was carried out and the results compared. The suitability of the method for practical application was ascertained by applying
the procedure for the wastewater from a plating industry. 相似文献
14.
Arumugam Vasudevan Gayathri Devi Gurusamy Rajkumar Kathiresan Sakthipandi Venkatachlam Rajendran Nallaiyan Rajendran Mani Rajkumar 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):1434-1449
Abstract Phosphate-based bioactive glasses and their glass ceramics for 47P2O5– (30.5)CaO–(22.5 ? x)Na2O–xZrO2 for different ZrO2 contents (x = 0, 1.5, 3.0, 4.5, and 6.0 mol%) were prepared through melt quenching and controlled heat treatment procedures. The amorphous nature of glasses and the presence of crystalline phases in glass ceramics were studied by means of X-ray diffraction (XRD) studies. The density, molar volume, ultrasonic velocities, attenuation, elastic constants, and microhardness of glass and glass ceramics were used to study the structural changes. The formation of hydroxyapatite layer on the surface of glasses and glass ceramics after immersion in simulated body fluid (SBF) was explored through XRD, Fourier transform infrared (FTIR), and scanning electron microscopy (SEM) analyses. The results indicate that the added ZrO2 increases the crosslink density of glasses, resulting in network stability, and also induces the formation of an apatite layer on the surface of glasses. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
15.
Chariklia Sotiriou-Leventis Xiaojiang Wang Sudhir Mulik Arumugam Thangavel Nicholas Leventis 《合成通讯》2013,43(14):2285-2298
Immobilization of catalysts on solid supports is a promising approach to combine the advantages of heterogeneous and homogeneous catalysts. Pd(PPh3)2Cl2, known as an extremely active homogeneous catalyst for the Sonogashira coupling reaction, has been immobilized on high-surface-area MCF (mesocellular foams)–type mesoporous silica powder modified with 3-aminopropyltriethoxysilane and subsequently with diphenylphosphine. The functionalized MCF-type silica and supported catalysts have been characterized by x-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR), elemental analysis, nitrogen sorption porosimetry, and scanning electron microscopy (SEM). Such supported Pd catalysts have proven to be useful recyclable reagents for copper- and amine-free Sonogashira coupling reactions of haloaromatic compounds with terminal alkynes. 相似文献
16.
17.
Dr. Kuppuswamy Arumugam C. Daniel Varnado Jr. Dr. Stephen Sproules Dr. Vincent M. Lynch Prof. Dr. Christopher W. Bielawski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10866-10875
High yielding syntheses of 1‐(ferrocenylmethyl)‐3‐mesitylimidazolium iodide ( 1 ) and 1‐(ferrocenylmethyl)‐3‐mesitylimidazol‐2‐ylidene ( 2 ) were developed. Complexation of 2 to [{Ir(cod)Cl}2] (cod=cis,cis‐1,5‐cyclooctadiene) or [Ru(PCy3)Cl2(?CH‐o‐O‐iPrC6H4)] (Cy=cyclohexyl) afforded 3 ([Ir( 2 )(cod)Cl]) and 5 ([Ru( 2 )Cl2(?CH‐o‐O‐iPrC6H4)]), respectively. Complex 4 ([Ir( 2 )(CO)2Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH2Cl2. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron‐donating ability of the N‐heterocyclic carbene ligand (ΔTEP=9 cm?1; TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η5‐C5H4COMe)Cp][BF4] as well as the subsequent reduction of the corresponding product [ 5 ][BF4] with decamethylferrocene (Fc*) each proceeded in greater than 95 % yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [ 5 ][BF4] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [ 5 ][BF4] were found to catalyze the ring‐closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo‐first‐order rate constants (kobs) of 3.1×10?4 and 1.2×10?5 s?1, respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second‐generation N‐heterocyclic carbene that featured a 1′,2′,3′,4′,5′‐ pentamethylferrocenyl moiety ( 10 ) was also prepared and metal complexes containing this ligand were found to undergo iron‐centered oxidations at lower potentials than analogous complexes supported by 2 (0.30–0.36 V vs. 0.56–0.62 V, respectively). Redox switching experiments using [Ru( 10 )Cl2(?CH‐o‐O‐iPrC6H4)] revealed that greater than 94 % of the initial catalytic activity was restored after an oxidation–reduction cycle. 相似文献
18.
Yu‐Sheng Su Dr. Yongzhu Fu Dr. Bingkun Guo Dr. Sheng Dai Prof. Arumugam Manthiram 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8621-8626
The cathodic reactions in Li–S batteries can be divided into two steps. Firstly, elemental sulfur is transformed into long‐chain polysulfides (S8?Li2S4), which are highly soluble in the electrolyte. Next, long‐chain polysulfides undergo nucleation reaction and convert into solid‐state Li2S2 and Li2S (Li2S4?Li2S) by slow processes. As a result, the second‐step of the electrochemical reaction hinders the high‐rate application of Li–S batteries. In this report, the kinetics of the sulfur/long‐chain‐polysulfide redox couple (theoretical capacity=419 mA h g?1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates. The meso‐/micropores in the interlayer are responsible for accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. Therefore, utilizing the sulfur/long‐chain polysulfide redox couple with an efficient interlayer configuration in Li–S batteries may be a promising choice for high‐power applications. 相似文献
19.
Excessive uric acid levels in the human body (hyperuricemia) are the main causes of kidney stones and diabetes. In this study, a layer-by-layer arrangement of polymers and nanocomposites is used as a new electrode sensing material for rapid and direct electrochemical determination of uric acid (UA). The electrode surface architecture was constructed by the incorporation of poly (amidoamine) dendrimer with 0.5 generation (poly (amidoamine) [PAMAM] [D-G0.5]) of multiwalled carbon nanotube-silver nanoparticles (MWCNT-AgNP) and a poly (neutral-red) (poly [NR]) polymer. The PAMAM (D-G0.5)/MWCNT-AgNP/poly (NR)-coated electrode has a good electrocatalytic activity for the determination of UA using cyclic voltammetry and showed remarkable enhancement in current response at a low-oxidation potential (0.3 V). Under optimal conditions, the developed electrochemical sensor showed an excellent and wide linear range for the determination of UA (i.e. 0.016 μM–2500 μM), and the limit of detection was found to be 0.005 μM. The modified sensor system demonstrated excellent sensitivity and selectivity toward the detection of UA in the presence of interfering substances, which are commonly found in urine and human fluid samples. Furthermore, the developed sensor has represented both reproducibility and excellent stability for the UA determination in real samples (human urine). 相似文献
20.
Raju Suresh Kumar Abdulrahman I. Almansour Natarajan Arumugam D. Kotresha J. Carlos Menéndez Raju Ranjith Kumar 《Journal of heterocyclic chemistry》2021,58(2):580-588
A three-component, [3 + 2]-cycloaddition/annulation domino protocol is described for the synthesis in excellent yield of a polycyclic cage-like heterocyclic hybrid (PCHH) that comprises various advantaged structural units viz., α,β-unsaturated ketone moiety, 4-pyridinone and pyrroloisoquinoline in a cage-like framework. The antitumor activity of PCHH on human breast (MCF7), colon (HCT116), cervical (JURKAT) and lung (NCI-H460) malignant cell lines inhibited the propagation of all cell lines. This hybrid molecule displayed increased broad-spectrum anticancer activity with higher doses of PCHH. Furthermore, the compound induced 45.21% of early apoptosis and 46.32% of late apoptosis in the Jurkat cancer cell line. Cell cycle analysis showed that this cage-like compound caused cell cycle arrest of Jurkat cells at the S phase and sub G0/G1 phase. Additionally, it led to increased DNA fragmentation and mitochondrial membrane permeabilization through activation of caspase-3 enzyme. Present investigation demonstrates the specific cytotoxic activity of the cage-like compound and the induction of apoptosis through the intrinsic pathway of Jurkat cells. 相似文献