全文获取类型
收费全文 | 11788篇 |
免费 | 396篇 |
国内免费 | 1758篇 |
专业分类
化学 | 9374篇 |
晶体学 | 132篇 |
力学 | 100篇 |
综合类 | 191篇 |
数学 | 1104篇 |
物理学 | 3041篇 |
出版年
2023年 | 117篇 |
2022年 | 153篇 |
2021年 | 128篇 |
2020年 | 202篇 |
2019年 | 186篇 |
2018年 | 159篇 |
2017年 | 225篇 |
2016年 | 213篇 |
2015年 | 175篇 |
2014年 | 307篇 |
2013年 | 1044篇 |
2012年 | 795篇 |
2011年 | 515篇 |
2010年 | 432篇 |
2009年 | 584篇 |
2008年 | 648篇 |
2007年 | 756篇 |
2006年 | 662篇 |
2005年 | 642篇 |
2004年 | 637篇 |
2003年 | 442篇 |
2002年 | 371篇 |
2001年 | 337篇 |
2000年 | 1132篇 |
1999年 | 772篇 |
1998年 | 729篇 |
1997年 | 198篇 |
1996年 | 191篇 |
1995年 | 187篇 |
1994年 | 176篇 |
1993年 | 158篇 |
1992年 | 137篇 |
1991年 | 96篇 |
1990年 | 62篇 |
1989年 | 54篇 |
1988年 | 35篇 |
1987年 | 34篇 |
1986年 | 21篇 |
1985年 | 32篇 |
1984年 | 26篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 35篇 |
1980年 | 16篇 |
1979年 | 15篇 |
1978年 | 17篇 |
1977年 | 11篇 |
1976年 | 9篇 |
1974年 | 9篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
硒是动植物及人体生长必需的十五种微量元素之一,具有清除体内自由基、抗氧化、增强免疫力等功能,但其安全剂量的范围却很窄。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体,粒径范围在17~200 nm之间,平均粒径138 nm。XRD衍射图谱中的特征峰与FeS2衍射图谱中各峰位置基本一致,因此判定硫铁矿中主要化学组分为FeS2,且图谱中基本没有杂峰,表明制备过程中并未混入杂质,样品纯度较高。实验结果表明,该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪(XPS)对硫铁矿去除水体中SeO2-3的机理进行了研究。研究结果表明, (1)在较为广泛的实验pH范围(pH 2.2~11.5),硫铁矿均能有效去除水体中SeO2-3,去除效率(除pH值7.8以外)均达到90%以上;(2)硫铁矿与SeO2-3发生反应后,其主要组成元素的XPS特征峰结合能有所减小,表明硫铁矿表面发生了一定化学变化;(3)酸碱环境下硫铁矿去除SeO2-3的机理不完全相同,酸性环境下,硫铁矿对SeO2-3的去除是单纯的氧化还原过程,即硫铁矿中被酸活化的S2-2将SeO2-3还原为单质Se(0),并且酸性越强,SeO2-3去除效果越好;碱性环境下,SeO2-3的去除过程中氧化还原与络合反应并存,硫铁矿表面有络合态Fe(OH)SeO3和单质Se(0)两种存在形态,且碱性越强,络合态Fe(OH)SeO3含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-3为代表的可变价金属阴离子提供重要理论依据和应用基础。 相似文献
2.
Synthesis of trialkyl semithioglycolurils from alkylthiourea-glyoxal cyclic adducts and dialkylureas
《Mendeleev Communications》2022,32(6):771-773
Condensation of 1-alkyl-4,5-dihydroxyimidazolidine-2-thiones (monoalkylthiourea-glyoxal cyclic adducts) with 1,3-dialkylureas affords novel 1,4,6-trialkylsemithio- glycolurils having non-substituted NH group linked to C=S function. Such compounds can be accessed in two-stage one-pot reaction sequence from alkylthioureas and glyoxal followed by treatment of the resulting adduct with 1,3-dialkylureas 相似文献
3.
Federica Valentini Giulia Brufani Benedetta Di Erasmo Luigi Vaccaro 《Current Opinion in Green and Sustainable Chemistry》2022
The great challenge for modern research is to define the most efficient tools to make more sustainable the industrial production and manufacturing. Among the different aspects that require attention the replacement of toxic and/or non-renewable solvents it is certainly playing a crucial role. Dealing with widely used dipolar aprotic solvents, among the different alternatives proposed in the literature γ-valerolactone (GVL) plays a pivotal role covering different application area. In this contribution, the benefits derived from the use of GVL as a circular, safe, biomass-derived reaction medium are highlighted covering most recent publications (2021). The presentation has been divided into three major sections: (i) biomass valorization, (ii) materials synthesis, manufacturing and recycle and (iii) new synthetic methodologies. 相似文献
4.
汽配件颜色喷涂顺序问题通常以生产线上相邻汽配件颜色切换次数少为最优目标,以进一步降低生产成本.该类问题具有所有汽配件都必须喷涂一次且只喷涂一次的特点,为此提出了TSP转化与建模的方法.将待喷涂汽配件定义为TSP顶点,任意两个待喷涂汽配件的颜色切换定义为顶点的距离,仿照TSP问题构建0-1规划模型;类似于顶点距离,将某些汽配件的颜色或类别不相邻要求定义为0-1矩阵,巧妙地构造了喷涂生产的约束条件.该建模方法简单快速,通用性高,适用于具有类似特点的各类生产实践问题. 相似文献
5.
Redox graphene-MXene(rGO-MXene) nanocomposites were prepared by ion polymerization and used to construct a highly sensitive electrochemical sensor for baicalin(BA) detection. The synergistic effect of rGO and MXene increased the specific surface area and electron transport capacity of the electrode, and significantly enhanced the electrochemical response of BA. The cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behavior of BA on the sensor. Under the optimal conditions, the peak current exhibited a good linear relationship with BA concentration in the range of 0. 05-10 μmol / L, and the limit of detection was as low as 28 nmol / L. The method was applied to analyze traditional Chinese medicine preparations containing baicalin, such as Qingkailing Capsule and Sanhuang Tablets with good accuracy and spiked recovery. The results were highly consistent with those of high performance liquid chromatography, providing a technical means for the rapid and sensitive detection of traditional Chinese medicine preparations. © 2022, Youke Publishing Co.,Ltd. All rights reserved. 相似文献
6.
Si-Yang Feng Tao Zheng Ai-Jing Sun Zuo-Xiang Wang 《Molecular Crystals and Liquid Crystals》2019,692(1):43-52
AbstractComplexes of [CdL2(NO3)2]·1.5H2O and [Ag2(μ-L)2(NO3)2] were synthesized by the reactions of 2-p-methylphenyl-5-(2-pyridyl)-1,3,4-thiadiazole (L) with Cd(NO3)2·4H2O and AgNO3, respectively. Their structures were determined by single crystal X-ray diffraction. The photophysical property and thermal stability were characterized by FT???IR, UV???Vis absorption, fluorescence, and thermogravimetric analysis (TGA). Both complexes belong to the triclinic system with space group p???1. The central metal of [CdL2(NO3)2]·1.5H2O has a distorted octahedral geometry [CdN4O2], while two central Ag(I) atoms of [Ag2(μ-L)2(NO3)2] exhibit distorted tetrahedral geometries [AgN3O]. 相似文献
7.
通过等温吸附实验,探究了三氯甲烷(CHCl3)与二氯一溴甲烷(CHBrCl2)、二氯乙酸(Cl2CHCOOH)在活性炭上的竞争吸附关系,同时探究了在低浓度条件下CHBrCl2和Cl2CHCOOH浓度变化对活性炭吸附CHCl3的影响。实验结果表明,活性炭吸附CHCl3和CHBrCl2符合Freundlich模型,对Cl2CHCOOH的吸附符合Langmuir模型;活性炭对3种消毒副产物均为优先吸附,吸附能力由大到小依次为CHBrCl2、CHCl3、Cl2CHCOOH;低浓度条件下,活性炭对消毒副产物的吸附效果随体系中物质种类的增加而降低;低浓度条件下,Cl2CHCOOH的浓度变化对CHCl3的吸附效果影响不大,但吸附效果随水体中CHBrCl2浓度的升高而降低。 相似文献
8.
9.
Hongyu Jiang Hanzhou Jiang Guofei Chen Xingzhong Fang 《Journal of polymer science. Part A, Polymer chemistry》2021,59(13):1434-1445
Two isomers of commercial 4,4′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (4,4′-BPADA), that is, 3,4′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (3,4′-BPADA) and 3,3′-(4,4′-isopropylidenediphenoxy) bis(phthalic anhydride) (3,3′-BPADA), were synthesized through aromatic nucleophilic substitution from nitrophthalonitrile and bisphenol A. 3,4′-BPADA was first synthesized from two intermediates, that is, 3-(4-[4-hydroxyphenylisopropylidene] phenoxy) phthalonitrile (3-BPADN) and 3,4′-(4,4′-isopropylidenediphenoxy) bis(phthalonitrile) (3,4′-BPATN). The corresponding three series of polyetherimides (PEIs) were prepared with two representative aromatic diamines (4,4′-oxydianiline and m-phenylenediamine (m-PDA)) via two-step procedure and chemical imidization. Isomeric polyimides showed Tgs from 206 to 256°C in nitrogen and Td5%s from 488 to 511°C in argon, good mechanical properties (tensile moduli of 2.3–3.3 GPa, tensile strengths of 70–96 MPa, and elongations at break of 3.2%–5.1%), and good solubility. With the introduction of 3-substituted phthalimide unit, PEIs displayed higher Tg values, lower strengths and elongations, better solubility and larger d-spacings. The rheological properties of thermoplastic polyimide resins based on the BPADA isomers were investigated, which showed that polyetherimide PEI-3b derived from 3,3′-BPADA and m-PDA had the lowest melt viscosity among the isomers, indicating that the melt processibility had been greatly improved. 相似文献
10.
《Arabian Journal of Chemistry》2021,14(11):103421
Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS+) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC50: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS+ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain. 相似文献