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71.
Precise conductance measurements are reported on dilute aqueous solutions of the sodium and potassium salts of orthophosphoric
acid at 25 ∘C. Conductance measurements on solutions of electrolytes such as these phosphate salts that exist in solution as complicated
mixtures of ions have previously proved difficult to interpret. To overcome this, a mathematical method has been developed
to calculate the concentrations of all the species in the aqueous system M3PO4/M2HPO4/M2HPO4/H3PO4 (M = Na or K) over a continuous range of stoichiometries. The Lee–Wheaton conductance equation has been used to interpret
the conductance of these multicomponent solutions in terms of the limiting ionic conductances and concentrations of all the
ions in the solution. The limiting molar conductances of the ions H2PO4
− and HPO4
2− and the ion-pair formation constants of these ions with sodium and potassium ions were determine
This work has enabled the accurate determination of solution parameters for the important hydrogenphosphate ions in water
and provides an excellent example of the use of an advanced conductance theory in the analysis of the conductance of multicomponent
electrolyte systems. 相似文献
72.
73.
Frey PA 《Chemical record (New York, N.Y.)》2001,1(4):277-289
Research on the mechanism of action of coenzyme B12, adenosylcobalamin, as a graduate student introduced the author to the field of organic free radicals in enzymology. Twenty years later, related work on S-adenosylmethionine (SAM) as a "poor man's coenzyme B12" was initiated in a detailed analysis of the mechanism of action of lysine 2,3-aminomutase (LAM). The interconversion of L-lysine and L-beta-lysine is catalyzed by LAM, which requires SAM, pyridoxal-5'-phosphate (PLP), and a [4Fe-4S] cluster as coenzymes. The mechanism of this reaction has been delineated as a radical isomerization, in which radical formation is initiated by the [4Fe-4S]-dependent cleavage of the SAM into methionine and the 5'-deoxyadenosyl radical. The mechanism of this process is discussed, together with the role of this radical in hydrogen abstraction from lysine to initiate the substrate radical isomerization. The chemistry underlying the functions of SAM, PLP, and [4Fe-4S] in the action of LAM is novel in all respects, except for the formation of a lysine-PLP aldimine at the active site. Of the four free radicals in the mechanism, three have been characterized by EPR spectroscopy. In the suicide inactivation of adenosylcobalamin-dependent dioldehydrase (DDH) by glycolaldehyde, the formation of cob(II)alamin and 5'-deoxyadenosine is accompanied by the conversion of glycolaldehyde to cis-ethanesemidione radical at the active site. The cis-ethanesemidione radical has been characterized by EPR spectroscopy. Its exceptional stability at the active site is the basis for the inactivation of DDH by glycolaldehyde. 相似文献
74.
Yang Jie Wu Shou Quan Huo Li Yang Chen Xia Du 《Journal of organometallic chemistry》1995,490(1-2):249-254
Three series of cyclomercurated ferrocenylimines (2-chloromercurio-ferrocenylimines) have been studied using 13C NMR spectroscopy. Good to excellent linear relationships have been found to exist between the chemical shifts of the carbon atoms in the ferrocenyl moiety and normal Hammett substituent constants σm and σp. The δ values of the iminyl carbon atoms show excellent linear correlations with the σ values. In three series of the ferrocenes, the sensitivity of the carbon atoms to the substituent effect is different, which is discussed in terms of the twist angle between the N-phenyl ring and the C---C=N---C plane. The relative sensitivity of the chemical shifts on different positions in ferrocenyl moiety to the substituent effect has also been presented. 相似文献
75.
用火焰原子吸收法检测了深圳市1408例13岁以下儿童发中钙,铁,镁的元素含量,并探讨了元素含量与年龄,性别的关系,结果显示,性别差异有显著意义,钙,镁含量随年龄增长有相似变化。 相似文献
76.
77.
《Electroanalysis》2006,18(1):35-43
A new method is presented for the determination of electrochemically labile iron in estuarine and coastal seawater. The method is based on differential pulse anodic stripping voltammetry (DPASV) at a rotating silver‐alloy disk electrode. The voltammetric parameters include a plating potential of ?1.5 V and an activation potential of ?5 V for 10s; the seawater is at the original sample pH. The main finding is the presence of a peak for low nmol L?1 levels of iron at ?0.55 V ascribed to elemental iron deposited on the bare silver alloy electrode. The peak increased linearly with the iron concentration between <1 and 14 nmol L?1 using a 900 s plating time. At higher concentrations an additional iron peak appeared at ?0.7 V which was also found to increase linearly with the iron concentration but at a higher concentration range from ca. 15 to 90 nmol L?1 using a 300 s plating time. The second peak was ascribed to iron deposited on iron. Additions of chelating agents (EDTA and a siderophore) to seawater caused the iron peak to be masked indicating that this method is suitable for iron speciation as only the electrochemically labile fraction is determined. The detection limit was 0.3 nmol L?1 using a 900 s plating time. The method was used to determine iron in the range of 5 to 50 nmol L?1 in samples from the Mersey estuary near Liverpool and its potential use for in situ monitoring was demonstrated by using it to monitor labile iron (at 2–3 nmol L?1) over a period of 4 days at 1 h intervals in coastal waters in the Trondheim fjord, Norway. 相似文献
78.
A.A. FilaretovM.G. Zhizhin L.N. KomissarovaV.P. Danilov V.V. ChernyshevB.I. Lazoryak 《Journal of solid state chemistry》2002,166(2):362-368
A new ammonium indium phosphate (NH4)In(OH)PO4 was prepared by hydrothermal reaction in the In2O3-NH4H2PO4-NH3/OH system (T=200°C, autogenous pressure, 7 days). The formula (NH4)In(OH)PO4 was determined on the basis of chemical and thermal analysis (TG/DSC), X-ray powder diffraction and IR-spectroscopy. (NH4)In(OH)PO4 crystallizes in the tetragonal system with space group P43212 (No. 96); a=9.4232(1) Å, c=11.1766(1) Å, V=992.45(2) Å3; Z=8. The crystal structure was refined by the Rietveld method (Rw=6.35%, Rp=5.10%). The second-harmonic generation study confirmed that structure of (NH4)In(OH)PO4 does not have a center of symmetry. The cis-InO4(OH)2 octahedra form helical chains, parallel to the c-axis. The In-O-In bonds are nearly equidistant. The chains are interconnected by phosphate tetrahedra and create tunnels containing the NH4+ ions along the c-axis. (NH4)In(OH)PO4 is isostructural with RbIn(OH)PO4. 相似文献
79.
80.
磷酸酯甜菜碱两性表面活性剂的合成与性能 总被引:7,自引:1,他引:7
磷酸酯甜菜碱从皮肤溶出的氨基酸量少,脱脂低,毒性和刺激性低,易降解,是一类性能优良两性表面活性剂[1,2]。它的合成大多以长链卤烷或胺为原料,成本较高。本文以高级脂肪醇、氯乙醇以及二甲胺为原料、P2O5为磷酸化剂,合成了C12H25OCH2CH(OOCCH3)CH2N+(CH3)2CH2CH2OP(O)(O )(OH)磷酸酯甜菜碱。测定了表面张力、泡沫性能、钙皂分散力及增溶能力。1 合成十二烷基缩水甘油醚(Ⅰ)[2] 在500ml三颈烧瓶中加入月桂醇0 2mol,正已烷200ml和四丁基溴化铵0 01mol;在室温和强烈搅拌下加入50%的NaOH水溶液48g,滴加环氧氯丙烷0 4mol后升… 相似文献