全文获取类型
收费全文 | 401篇 |
免费 | 9篇 |
国内免费 | 6篇 |
专业分类
化学 | 252篇 |
晶体学 | 3篇 |
力学 | 5篇 |
综合类 | 1篇 |
数学 | 69篇 |
物理学 | 86篇 |
出版年
2023年 | 2篇 |
2022年 | 16篇 |
2021年 | 26篇 |
2020年 | 13篇 |
2019年 | 14篇 |
2018年 | 9篇 |
2017年 | 9篇 |
2016年 | 15篇 |
2015年 | 11篇 |
2014年 | 13篇 |
2013年 | 48篇 |
2012年 | 20篇 |
2011年 | 15篇 |
2010年 | 16篇 |
2009年 | 11篇 |
2008年 | 18篇 |
2007年 | 19篇 |
2006年 | 22篇 |
2005年 | 16篇 |
2004年 | 11篇 |
2003年 | 5篇 |
2002年 | 13篇 |
2001年 | 10篇 |
2000年 | 6篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1994年 | 2篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 2篇 |
1966年 | 2篇 |
排序方式: 共有416条查询结果,搜索用时 15 毫秒
301.
Mohamed Hilmy Elnagdi Mohamed Riffat Hamza Elmoghayar Ezzat Mohamed Kandeel Mohamed Kamal Ahmed Ibrahim 《Journal of heterocyclic chemistry》1977,14(2):227-230
3-Phenylpyrazole-5-(liazonium chloride ( 1 ) couples with α-chloro derivatives of acetylacetone, ethyl acetoacetate and aceto-o-anisidine to yield the corresponding pyrazole-5-yl hydrazonyl chloride derivatives 2a-c . Compounds 2a,b were cyclised to yield either the pyrazolo[1,5-c]-1,2,4-triazole derivatives 3a,b or the pyrazolo[1,5-c]-as-triazines 4a,b depending on the applied reaction conditions. Compound 2c cyclised only into 3c under different cyclization conditions. The pyrazolo[1,5-c]-as-triazine derivatives 4c-e could be prepared via condensation of 2a with potassium cyanide. Compound 2d reacted with aromatic thioles and with sodium benzene-sulphonate to yield the pyrazolo[1,5-c]-as-triazine derivatives 6a-d . Compound 1 reacted with activated double bond systems to yield pyrazolo[1,5-c]-as-triazines 8a,b and 9 . 相似文献
302.
This Perspective reports the development of mechanistic insight over the past 6 years, on the substitution behaviour of cobalamins that contain a single Co-C bond. The effect of the alkyl group, located in the trans position, on the thermodynamic, kinetic and ground state trans effect, was studied in detail. The substitution reactions of different alkylcobalamins with CN- were investigated, the apparent mechanistic discrepancy reported for the co-enzyme B12 was resolved and a logical explanation could be offered. In addition, a complete picture of the effect of pressure on the UV-Vis spectra of different base-on and base-off cobalamins is presented, which clearly shows the role of the alkyl group in controlling the equilibrium between five- and six-coordinate species, and the possible participation of such species in the studied ligand substitution reactions. The kinetics of the base-on/base-off equilibration was studied for the first time using a pH-jump technique. All in all the novel mechanistic information adds to the understanding of the profound effect that a single metal-carbon bond can have on the reactivity of such Co(III) complexes. 相似文献
303.
Badawi HM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(11):2573-2580
The structural stability of (halocarbonyl)sulfenyl halides XCO-SX (X is F, Cl, and Br) was investigated by DFT-B3LYP and ab initio MP2 calculations using 6-311 + G(**) basis set. From the calculations the molecules were found to exist predominantly in the trans conformation (two halogen atoms are trans to each other). Full energy optimizations were carried out for the minima and the transition states (TS) at the two levels, from which the rotational barriers about C-S bond in the three molecules were calculated to be about 12-13 kcal mol(-1). The vibrational frequencies of (fluorocarbonyl)sulfenyl fluoride (FCO-SF), (chlorocarbonyl)-sulfenyl chloride (ClCO-SCl), and (bromocarbonyl)-sulfenyl bromide (BrCO-SBr) were computed at the DFT-B3LYP level and the vibrational assignments for the normal modes of the stable forms of the compounds were made on the basis of normal coordinate calculations and experimental data of the chloride. 相似文献
304.
Mohamed Bouhrim Hayat Ouassou Salima Boutahiri Nour Elhouda Daoudi Hamza Mechchate Bernard Gressier Bruno Eto Hamada Imtara Amal A. Alotaibi Mohammed Al-zharani Abderrahim Ziyyat Hassane Mekhfi Abdelkhaleq Legssyer Mohammed Aziz Mohamed Bnouham 《Molecules (Basel, Switzerland)》2021,26(6)
Opuntia dillenii Ker Gawl. is one of the medicinal plants used for the prevention and treatment of diabetes mellitus (DM) in Morocco. This study aims to investigate the antihyperglycemic effect of Opuntia dillenii seed oil (ODSO), its mechanism of action, and any hypoglycemic risk and toxic effects. The antihyperglycemic effect was assessed using the OGTT test in normal and streptozotocin (STZ)-diabetic rats. The mechanisms of action were explored by studying the effect of ODSO on the intestinal absorption of d-glucose using the intestinal in situ single-pass perfusion technique. An Ussing chamber was used to explore the effects of ODSO on intestinal sodium-glucose cotransporter 1 (SGLT1). Additionally, ODSO’s effect on carbohydrate degrading enzymes, pancreatic α-amylase, and intestinal α-glucosidase was evaluated in vitro and in vivo using STZ-diabetic rats. The acute toxicity test on mice was performed, along with a single-dose hypoglycemic effect test. The results showed that ODSO significantly attenuated the postprandial hyperglycemia in normal and STZ-diabetic rats. Indeed, ODSO significantly decreased the intestinal d-glucose absorption in situ. The ex vivo test (Ussing chamber) showed that the ODSO significantly blocks the SGLT1 (IC50 = 60.24 µg/mL). Moreover, ODSO indu\ced a significant inhibition of intestinal α-glucosidase (IC50 = 278 ± 0.01 µg/mL) and pancreatic α-amylase (IC50 = 0.81 ± 0.09 mg/mL) in vitro. A significant decrease of postprandial hyperglycemia was observed in sucrose/starch-loaded normal and STZ-diabetic ODSO-treated rats. On the other hand, ODSO had no risk of hypoglycemia on the basal glucose levels in normal rats. Therefore, no toxic effect was observed in ODSO-treated mice up to 7 mL/kg. The results of this study suggest that ODSO could be suitable as an antidiabetic functional food. 相似文献
305.
Mohamed Rifaat Hamza Elmoghayer Mohamed Ali Elsayed Khalifa Mohamed Kamal Ahmed Ibraheim Mohamed Hilmy Elnagdi 《Monatshefte für Chemie / Chemical Monthly》1982,113(1):53-57
The reaction of ethyl cyanoacetate with -cyanochalcone (1) leads to the formation of -enaminoesters (3) viaMichael addition. Compound3 reacts with phenylmagnesium bromide to give the -enaminoketone5. Acetylation of3 gives the acetyl product4. Each of compounds1 and3 reacts with malononitrile to give -enaminonitrile6. Phenylhydrazine reacts with3 to give the hydrazone7. Similarly 3-phenyl-5-aminopyrazole reacts with3 to give theSchiff base8.
Reaktionen mit heterocyclischen -Enaminoestern: Eine neue Synthese von 2-Amino-3-ethoxycarbonyl-(4H)-pyranen
Zusammenfassung Die Reaktion von Ethylcyanacetat mit -Cyanchalcon1 führt über eineMichael-Addition zum -Enaminoester3.3 gibt mit Phenylmagnesiumbromid das -Enaminoketon5. Acetylierung von3 gibt das Acetylderivat4.1 und3 reagieren mit Malodinitril zum -Enaminonitril6.3 gibt mit Phenylhydrazin das Hydrazon7; 3-Phenyl-5-aminopyrazol reagiert mit3 zurSchiff-Base8.相似文献
306.
Simple chromatogaphic method for the separation and estimation of gibberellic acid in crude products
M. F. Abdel-Wahab S. W. Amin M. M. Badawi 《Fresenius' Journal of Analytical Chemistry》1966,219(3):275-278
Summary The estimation of gibberellic acid by a direct spectrophotometric method is described. For the separation a paper-chromatographic technique is used with a modified solvent and with a colour reaction of alkaline permanganate. Comparative data proved that the new method is superior to other techniques and can be applied to pure gibberellic acid or crude preparations as no interference occurs after chromatographic separation.
Zusammenfassung Zur Bestimmung der Gibberellinsäure wird eine spektralphotometrische Methode angegeben. Dabei wird zunächst papierchromatographisch abgetrennt und dann eine Farbreaktion mit alkalischem Permanganat ausgewertet. Die Methode, die früheren überlegen ist, kann zur Bestimmung von Gibberellinsäure in reinen Produkten sowie in Rohprodukten verwendet werden.相似文献
307.
Badawi HM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(7):1445-1451
The structure and conformational stability of vinylsulfonamide CH2CHSO2NH2 were investigated by DFT-B3LYP/6-311+G** and ab initio MP2/6-311+G** calculations. From the calculations the molecule was predicted to exist predominantly in the gauche-syn (vinyl group nearly eclipses one of the SO bonds and the NH2 and the SO2 moieties eclipse each other) conformation with the possibility of low abundance of the cis-syn and the gauche-anti forms. The asymmetric potential function for the internal rotation about CS bond was determined for the molecule. The vibrational frequencies were computed at DFT-B3LYP level for the gauche-syn conformer of the molecule and its d2(C2H3SO2ND2) and d3(C2D3SO2NH2) deuterated species. Normal coordinate calculations were then carried out and the potential energy distributions were calculated for the molecule. 相似文献
308.
The conformational behavior and structural stability of chloro- and fluoromethylsulfonyl isocyanates were investigated by quantum mechanical DFT and ab initio MP2 calculations. The 6-311++G** basis set was employed to include polarization and diffuse functions in the calculations. The molecules were found to exist in a mixture of two stable gauche conformations. The potential scans were calculated from which the rotational barriers could be estimated. The vibrational frequencies and spectra were computed at B3LYP/6-311++G** level. The potential energy distributions were then calculated to provide tentative vibrational assignment for the normal modes of the stable conformers of both molecules. 相似文献
309.
Copper(I) Complexes with 1-Azadiene Chelate Ligands and Their Reaction with Oxygen The reaction of the bidendate 1-azadiene ligands Me2N? (CH2)n? N?CH? CH?CH? Ph with CuX results in the formation of the dimeric compounds [ A CuX]2 and [ B CuX]2 ( A : n = 2, B : n = 3, X: I, Cl). The structure of complex 1 [ A CuI]2 was determined by X-ray crystal structure analysis. 1 consists of two tetrahedrally coordinated Cu atoms connected by two iodo bridges. (Cu? Cu bond length: 261 pm). The ligand Me? N(CH2CH2N?CH? CH?CH? Ph)2 ( C ) reacts with CuX to form the monomeric complexes [ C CuX] ( 5 : X?I, 6 : X?Cl). The crystal structure of 5 shows that the ligand acts as a tridendate ligand. The bond lengths of the CuN(sp2) bonds are significantly shorter than the Cu? N(sp3) distance. Reacting the podand-type ligands N(CH2CH2? N?CH? R)3 ( D : R?Ph, E : R?-CH?CH? Ph) with CuX yields the ionic complexes 7 [ D Cu][CuCl2] and 8 [ E Cu][CuCl2]. 7 was characterized by X-ray analysis which confirmed that D acts as a four-dendate podand ligand. The compounds 1 ? 8 are unreactive towards CO2 but take up O2 even at deep temperatures. At ?78°C the orange-red complex 4 [ B CuCl]2 reacts with O2 in CH2Cl2 to form a deep violet solution, but the primary product of the oxidation could not be isolated. It reacts at room temperature to form the green complex 9 [μ-Cl, μ-OH][ B CuCl]2. The X-ray structure analysis of 9 confirms that a dimeric CuII complex is formed in which both a chloro- and a hydroxo group are bridging the monomeric units. The CuII centers exhibit a distorted tetragonal-pyramidal coordination. The pathway of the reaction with O2 will be discussed. 相似文献
310.
Hamza Kherfi Mohamed Al Amine Benhacine Malika Hamadne Fadila Balegroune 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(11):1524-1534
Single crystals of two new bimetallic oxalate compounds with the formula [ACr(C2O4)2(H2O)4]n (A = Li or Na), namely catena‐poly[[diaqualithium(I)]‐μ‐oxalato‐κ4O1,O2:O1′,O2′‐[diaquachromium(III)]‐μ‐oxalato‐κ4O1,O2:O1′,O2′], ( I ), and catena‐poly[[diaquasodium(I)]‐μ‐oxalato‐κ4O1,O2:O1′,O2′‐[di‐aquachromium(III)]‐μ‐oxalato‐κ4O1,O2:O1′,O2′], ( II ), have been synthesized, characterized and their crystal structures elucidated by X‐ray diffraction analysis and compared. The compounds crystallize in the monoclinic space group C2/m for ( I ) and in the triclinic space group P for ( II ); however, they have somewhat similar features. In the asymmetric unit of ( I ), the Li and Cr atoms both have space‐group‐imposed 2/m site symmetry, while only half of the oxalate ligand is present and two independent water molecules lie on the mirror plane. The water O atoms around the Li atom are disordered over two equivalent positions separated by 0.54 (4) Å. In the asymmetric unit of ( II ), the atoms of one C2O42? ligand and two independent water molecules are in general positions, and the Na and Cr atoms lie on an inversion centre. Taking into account the symmetry sites of both metallic elements, the unit cells may be described as pseudo‐face‐centred monoclinic for ( I ) and as pseudo‐centred triclinic for ( II ). Both crystal structures are comprised of one‐dimensional chains of alternating trans‐Cr(CO)4(H2O)2 and trans‐A(CO)4(H2O)2 units μ2‐bridged by bis‐chelating oxalate ligands. The resulting linear chains are parallel to the [101] direction for ( I ) and to the [11] direction for ( II ). Within the two coordination polymers, strong hydrogen bonds result in tetrameric R44(12) synthons which link the metal chains, thus leading to two‐dimensaional supramolecular architectures. The two structures differ from each other with respect to the symmetry relations inside the ligand, the role of electrostatic forces in the crystal structure and the molecular interactions of the hydrogen‐bonded networks. Moreover, they exhibit the same UV–Vis pattern typical of a CrIII centrosymmetric geometry, while the IR absorption shows some differences due to the oxalate‐ligand conformation. Polymers ( I ) and ( II ) are also distinguished by a different behaviours during the decomposition process, the precursor ( I ) leading to the oxide LiCrO2, while the residues of ( II ) consist of a mixture of sodium carbonate and CrIII oxide. 相似文献