全文获取类型
收费全文 | 25432篇 |
免费 | 1058篇 |
国内免费 | 4713篇 |
专业分类
化学 | 28835篇 |
晶体学 | 297篇 |
力学 | 53篇 |
综合类 | 231篇 |
数学 | 17篇 |
物理学 | 1770篇 |
出版年
2024年 | 41篇 |
2023年 | 266篇 |
2022年 | 791篇 |
2021年 | 744篇 |
2020年 | 756篇 |
2019年 | 756篇 |
2018年 | 649篇 |
2017年 | 794篇 |
2016年 | 955篇 |
2015年 | 897篇 |
2014年 | 1042篇 |
2013年 | 2280篇 |
2012年 | 1790篇 |
2011年 | 1411篇 |
2010年 | 1223篇 |
2009年 | 1453篇 |
2008年 | 1535篇 |
2007年 | 1689篇 |
2006年 | 1587篇 |
2005年 | 1483篇 |
2004年 | 1345篇 |
2003年 | 1081篇 |
2002年 | 992篇 |
2001年 | 693篇 |
2000年 | 668篇 |
1999年 | 550篇 |
1998年 | 444篇 |
1997年 | 471篇 |
1996年 | 426篇 |
1995年 | 390篇 |
1994年 | 335篇 |
1993年 | 287篇 |
1992年 | 279篇 |
1991年 | 203篇 |
1990年 | 158篇 |
1989年 | 172篇 |
1988年 | 122篇 |
1987年 | 84篇 |
1986年 | 59篇 |
1985年 | 49篇 |
1984年 | 55篇 |
1983年 | 29篇 |
1982年 | 42篇 |
1981年 | 28篇 |
1980年 | 23篇 |
1979年 | 20篇 |
1978年 | 22篇 |
1977年 | 5篇 |
1973年 | 5篇 |
1968年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 17 毫秒
81.
《Arabian Journal of Chemistry》2022,15(12):104368
Protein hydrolysates have the potential to be natural and safer sources of bioactive peptides. In this study, two proteases were used to hydrolyze Chinese sturgeon (Acipenser sinensis) protein, and the hydrolysates were then purified to yield antioxidant peptides. The degree of hydrolysis of 23.56 % and 18.14 % was obtained using papain and alcalase 2.4L, respectivly, and hydrolysates had 96.80 % and 87.24 % total amino acid content, respectivly. The papain hydrolysate (PH) and alcalase 2.4L hydrolysate (AH) showed good antioxidant activity against DPPH? (IC50 of 3.64 and 3.15 mg/mL) and ABTS?+ (IC50 of 1.92 and 1.58 mg/mL), respectively. The low-molecular-weight (<1000 Da) fraction of both hydrolysates demonstrated the highest antiradical activity (IC50 of 2.59 and 2.31 mg/mL, DPPH) and (IC50 of 1.54 and 1.36 mg/mL, ABTS), respectively. Nine peptides were separated from both hydrolysates using reverse phase high performance liquid chromatography (RP-HPLC). The IC50 for ABTS?+ scavenging activity of peptide P5 with valine, glycine and asparagine (MW of 282.13 Da) from PH, and peptide P3 with histidine, glycine and alanine (MW of 302.74 Da) from AH was 0.89 and 0.72 mg/mL, respectively. The fractions and purified peptides obtained from Chinese sturgeon hydrolysates could be utilized as natural antioxidant substitutes in pharmaceuticals and food products. 相似文献
82.
A method of quickly determining ascorbic acid and sorbic acid by capillary zone electrophoresis with ultraviolet detection was developed. The choice of background electrolyte, wavelength, injection time and applied voltage were discussed. Ascorbic acid and sorbic acid were well separated in 80 mmol L−1 boric acid-5 mmol L−1borax (pH = 8.0) in 5 min at the detecting wavelength of 270 nm. Under the optimum condition, the method has linear ranges of 2.54-352.00 mg L−1 for ascorbic acid and 1.08-336.39 mg L−1 for sorbic acid with the detection limit of 1.70 mg L−1 for ascorbic acid and 0.54 mg L−1 for sorbic acid, respectively. Other organic acids in fruit juices have no effect on the detection. This method is very feasible and simple and can be used to detect ascorbic acid and sorbic acid in fruit juices. 相似文献
83.
Transference numbers of HCl(aq) solutions at 25°C, from 0.01 to 13.6 mol-kg–1(m) have been obtained by measuring the emf of cells with transference using hydrogen gas/platinum electrodes. Good agreement is obtained at concentrations up to 1 m with all previous data, and our results strongly corroborate those of King and Spiro over the 2–8m concentration range. The transference numbers of the hydronium ion fit the empirical equation,
H
HCl
= 0.821 + 0.0457m
1/2 – 2.476×10–2m – 1.90×10–4
m
2 – 1.45×10–5
m
3 the maximum deviation in T
H
HCl
being 0.003. 相似文献
84.
85.
Larisa Kuznetsova 《Journal of fluorine chemistry》2004,125(4):487-500
Enantiopure 1-acyl-3-hydroxyl-4-CF2H-azetidin-2-ones and 1-acyl-3-hydroxy-4-CF3-azetidin-2-ones serve as versatile intermediates for the syntheses of CF2- and CF3-containing α-hydroxy-β-amino acids, dipeptides, and taxoid anticancer agents. Both enantiomers of 3-hydroxy-4-CF2H-β-lactams can be obtained in high yields through the diethylaminosulfur trifluoride (DAST) reaction of the corresponding enantiopure 4-formyl-β-lactam that is prepared through [2+2] cycloaddition of acetoxyketene to a 3-methyl-2-butenaldimine, followed by enzymatic optical resolution and ozonolysis. (+)-3-Hydroxy-4-CF3-β-lactams and (−)-3-hydroxy-4-CF3-β-lactams can also be readily obtained in enantiopure form through [2+2] cycloaddition of a CF3-imine with a ketene, followed by enzymatic optical resolution. Practical processes for the preparations of these enantiopure 3-hydroxy-4-Rf-β-lactams as well as their synthetic applications are described. 相似文献
86.
Summary The electrochemical behaviour of Fe and C-steel samples in oxalic acid solutions was studied by the use of cyclic voltammetry. Two peaks were observed; the first one was the anodic peak and the second one an unexpected reductive dissolution peak which could be observed in the cathodic branch of cyclic voltammograms of all electrodes studied. The carbon content was found to increase the active dissolution of steels and to decrease their tendency towards passivation. The inhibitive efficiency of phenyl phthalimide derivatives on the active dissolution of Fe and steel samples in 0.1M oxalic acid were investigated.
Cyclische Voltammogramme von Eisen und C-Stählen in Oxalsäurelösungen und der Einfluß von Phenylphthalimiden als Korrosionsinhibitoren
Zusammenfassung Das elektrochemische Verhalten von Eisen und C-Stählen in Oxalsäurelösungen wurde mit Hilfe cyclischer Voltammetrie studiert. Dabei treten zwei Signale auf: das anodische Signal sowie ein unerwartetes reduktives Lösungssignal. Letzteres wurde im kathodischen Zweig der cyclischen Voltammogramme aller untersuchten Elektroden gefunden. Der Kohlenstoffgehalt erhöht die aktive Auflösung von Stählen und erniedrigt ihre Tendenz zur Passivierung. Die Inhibitionseffizienz von Phenylphthalimiden für die aktive Auflösung von Eisen und Stahlproben in 0.1M Oxalsäure wurde untersucht.相似文献
87.
Julie L. S. Bell David J. Wesolowski Donald A. Palmer 《Journal of solution chemistry》1993,22(2):125-136
The dissociation quotients of formic acid were measured potentiometrically from 25 to 200°C in NaCl solutions at ionic strengths of 0.1, 0.3 1.0, 3.0, and 5.0 mol-kg–1. The experiments were carried out in a concentration cell with hydrogen electrodes. The resulting molal acid dissociation quotients for formic acid, as well as a set of infinite dilution literature values and a calorimetrically-determined enthalpy of reaction, were fitted by an empirical equation involving an extended Debye Hückel term and seven adjustable parameters involving functions of temperature and ionic strength. This regressional analysis yielded the following thermodynamic quantities for 25°C: logK=–3.755±0.002, Ho=–0.09±0.15 kJ-mol–1, So=–72.2±0.5 J-K–1-mol–1, and C
p
o
=–147±4 J-K–1-mol–1. The isocoulombic form of the equilibrium constant is recommended for extrapolation to higher temperatures. 相似文献
88.
A new method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was investigated using high-performance ion-exclusion/cation-exchange chromatography with conductimetric detection on a separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin in the hydrogen-form and an eluent comprising 1.5 mM sulfosalicylic acid–6 mM 18-crown-6 at pH 2.6, operated at 1.5 ml/min. Effective separation and highly sensitive conductimetric detection for the anions and the cations was achieved in about 14 min. Since the ionic balance (equivalents of anions/equivalents of cations) of acid rain waters of different pH (4.40–4.67) ranged from 0.97 to 0.94, evaluation of the water quality of acid rain was possible. This method was successfully applied to the simultaneous determination of the anions and the cations in acid rain transported from mainland China and North Korea to central Japan monitored by a meteorological satellite data analyzer. 相似文献
89.
90.
《Electroanalysis》2006,18(11):1097-1104
Copolymerization of an osmium(II) functionalized pyrrole moiety, osmium‐bis‐N,N'‐(2,2′‐bipyridyl)‐N‐(pyridine‐4‐ylmethyl‐(8‐pyrrole‐1yl–octyl)‐amine)chloride ( I ) with 3‐methylthiophene was carried out. The resulting conducting polymer film exhibited a clear redox couple associated with the Os3+/2+ response and the familiar conducting polymer backbone signature. The effect of film thickness upon the redox properties of the copolymer was investigated in organic electrolyte solutions. Scanning electron micrographs (SEM) along with energy dispersive X‐ray (EDX) spectra of the copolymerized films were undertaken, both after formation and redox cycling in neutral buffer solution. These clearly show that electrolyte is incorporated into the polymer film upon redox cycling through the Os3+/2+ redox system. The Os3+/2+ response associated with the copolymer was seen to be significantly altered in the presence of ascorbic acid both in acidic and neutral pH buffer solutions. This pointed to an electrocatalytic reaction between the ascorbic acid and the Os3+ form of the copolymer. Under acidic conditions the copolymer film exhibited a sensitivity of 1.76 (±0.05) μA/mM with a limit of detection (LOD) of 1.45 μM for ascorbic acid. Under neutral pH conditions the copolymer exhibited a sensitivity of 19.26 (±1.05) μA/mM with a limit of detection (LOD) of 1.28 μM for ascorbic acid. 相似文献