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Structural characteristics of phosphorylated cotton prepared by gas-phase procedure 气相法制备磷酸化棉的结构特性
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-03 DOI: 10.1080/10426507.2025.2483814
Irada Buniyat-zadeh , Mustafa Soylak , Solmaz Aliyeva , Nurlana Binnetova , Naila Guliyeva , Sinan Turp , Rasim Alosmanov
This study reports the synthesis of phosphorylated cotton fiber (Ph-CF) via a gas-phase oxidative chlorophosphorylation reaction. The process improved the crystallinity and thermal properties of raw cotton fibers (R-CF). Fourier-transform infrared spectroscopy confirmed the formation of phosphorus-containing groups, while UV-visible spectroscopy revealed increased UV absorption. X-ray diffraction showed increased crystallinity for Ph-CF, with a crystallinity index (Segal method) of 81.41% versus 41.05% for R-CF, which was attributed to the removal of amorphous components. The thermogravimetric analysis demonstrated enhanced thermal stability for Ph-CF, with a char yield of 38% at 560 °C compared to 20% for R-CF. Scanning electron microscopy revealed noticeable changes in surface morphology, including smoother and more compact fiber surfaces after modification. Energy-dispersive X-ray spectroscopy confirmed the incorporation of phosphorus into the fiber structure, with a measured phosphorus content of 2.27% in Ph-CF. The oxidative chlorophosphorylation reaction in the gas phase induced deeper chemical transformations than a similar liquid-phase process, as evidenced by enhanced crystallinity and structural modifications. These results indicate the potential of gas-phase oxidative chlorophosphorylation for functionalizing cotton with improved properties for advanced applications.
本文报道了通过气相氧化氯磷酸化反应合成磷酸化棉纤维(Ph-CF)。该工艺改善了原棉纤维(R-CF)的结晶度和热性能。傅里叶变换红外光谱证实了含磷基团的形成,而紫外可见光谱显示紫外吸收增加。x射线衍射显示Ph-CF的结晶度增加,结晶度指数(Segal法)为81.41%,而R-CF的结晶度指数为41.05%,这是由于去除了非晶态成分。热重分析表明,Ph-CF的热稳定性增强,在560°C时炭收率为38%,而R-CF为20%。扫描电镜显示,改性后的纤维表面形貌发生了明显的变化,纤维表面更光滑、更致密。能量色散x射线光谱证实了磷在纤维结构中的掺入,测得Ph-CF中磷含量为2.27%。气相的氧化氯磷酸化反应比类似的液相过程诱导更深的化学转化,结晶度和结构修饰的增强证明了这一点。这些结果表明,气相氧化氯磷酸化在改善棉花性能方面具有先进的应用前景。
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引用次数: 0
Optimization of ammonium sulfate crystallization under sodium fluoride based on response surface method 基于响应面法优化氟化钠作用下硫酸铵结晶工艺
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-03 DOI: 10.1080/10426507.2025.2479718
Changle Tian , Bangfu Huang , Zhe Shi , Linjing Yang , Gaoyong Zi , Xinchao Fan , Jingyi Zhao
In order to investigate the crystallization mechanism of (NH4)2SO4 under the action of NaF, this paper adopts the laser method to determine the solubility and the width of the metastable zone of (NH4)2SO4 under different NaF addition amount, and then designs the experiments through the response surface method to study the mechanism of the influence of NaF addition amount, pH value and stirring rate and their interactions on the amount of crystallization and the average size of (NH4)2SO4 and to set up their regression models. It is shown that the salting-out effect and hydrogen bonding lead to a decrease in the solubility of (NH4)2SO4 and the occupation of active growth sites by NaF, which leads to an increase in the crystal nucleation the (NH4)2SO4 metastable zone. Three factors have a significant effect on both the crystallization amount and the average particle size of (NH4)2SO4. On the crystallization amount the influence order is: stirring rate > pH value > NaF addition amount, and on the average particle size the influence order is: stirring rate > NaF addition amount > pH value. Because of the collision of solutes with the stirring paddle and crystallizer during the stirring process, secondary nucleation occurs, so the stirring rate significantly affects the amount of crystallization and the average particle size. Through the optimization, the NaF addition of 0.4%, pH value of 5.71 and stirring rate of 329.82 rmp were obtained, and the error between the theoretical and experimental validation values under these conditions was small, which indicated that the model had high reliability.
为了研究NaF作用下(NH4)2SO4的结晶机理,本文采用激光法测定不同NaF添加量下(NH4)2SO4的溶解度和亚稳区宽度,然后通过响应面法设计实验,研究NaF添加量的影响机理。研究pH值和搅拌速率及其对(NH4)2SO4结晶量和平均粒径的相互作用,并建立它们的回归模型。结果表明,盐析作用和氢键作用导致(NH4)2SO4的溶解度降低,NaF占据活性生长位点,导致(NH4)2SO4亚稳区晶核增大。三个因素对(NH4)2SO4的结晶量和平均粒径均有显著影响。对结晶量的影响顺序为:搅拌速率>; pH值>; NaF添加量;对平均粒径的影响顺序为:搅拌速率>; NaF添加量>; pH值。由于在搅拌过程中溶质与搅拌桨和结晶器发生碰撞,发生二次成核,因此搅拌速率对结晶量和平均粒径有显著影响。通过优化得到NaF添加量0.4%、pH值5.71、搅拌速率329.82 rpm,在此条件下理论验证值与实验验证值误差较小,表明模型具有较高的可靠性。
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引用次数: 0
Silicon’s defensive role against biotic and abiotic stress: a review 硅对生物和非生物胁迫的防御作用综述
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-03 DOI: 10.1080/10426507.2025.2482090
Sehla Khursheed , Sana Bashir Surma , Abdel Rahman Mohammad Al Tawaha , Mehraj D. Shah , Bilal A. Padder , Baseerat Afroza , Rizwan Rashid , Abdel Razzaq Al-Tawaha
Silicon enhances developmental processes and controls the enzymatic and functional properties of plants. It is considered a quasi-element in the earth’s crust, absorbed and translocated to aerial parts through transpiration. Silicon reduces various plant stress conditions, with plants displaying both direct and indirect defensive mechanisms. Indirect defense involves the release of volatiles that attract the pathogen’s natural enemies, while morphological, biochemical, and molecular impediments constitute direct defense. Both mechanisms are strengthened by silicon treatment. Silicon enhances the polymerization of silicic acid in intercellular spaces and beneath cuticles as phytoliths, establishing a defense against pathogens. Silicon activates multiple pathways, encouraging the accumulation of supplementary metabolites, thereby enhancing plant defenses against abiotic and biotic challenges. It also contributes significantly to defensive mechanisms mediated by phytohormones. Studies show that silicon positively affects plants during severe stress by modifying several metabolites. Phytohormones are essential to crop plants’ biochemical and physiological functions under unfavorable environmental circumstances. Frontline phytohormones, such as auxin, cytokinin, ethylene, gibberellin, salicylic acid, abscisic acid, brassinosteroids, and jasmonic acid regulate abiotic stress tolerance pathways intrinsically linked with silicon. This review highlights silicon’s functionality in various biotic and abiotic stresses.
硅促进了植物的发育过程,控制了植物的酶和功能特性。它被认为是地壳中的一种准元素,通过蒸腾作用被吸收并转移到空中。硅降低了植物的各种胁迫条件,植物表现出直接和间接的防御机制。间接防御包括释放挥发性物质吸引病原体的天敌,而形态、生化和分子障碍则构成直接防御。硅处理强化了这两种机制。硅增强了硅酸在细胞间隙和角质层下作为植物岩的聚合,建立了对病原体的防御。硅激活多种途径,促进补充代谢物的积累,从而增强植物对非生物和生物挑战的防御。它还对植物激素介导的防御机制有重要作用。研究表明,在严重的逆境中,硅通过改变几种代谢物对植物产生积极影响。植物激素是作物在不利环境下发挥生理生化功能所必需的激素。一线植物激素,如生长素、细胞分裂素、乙烯、赤霉素、水杨酸、脱落酸、油菜素类固醇和茉莉酸调节与硅内在相关的非生物胁迫耐受途径。本文综述了硅在各种生物和非生物胁迫下的功能。
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引用次数: 0
Effect of crystallization temperature, stirring rate, and pH on the crystallization of ammonium sulfate in the presence of calcium sulfate 在硫酸钙存在下,结晶温度、搅拌速率和pH对硫酸铵结晶的影响
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-04-03 DOI: 10.1080/10426507.2025.2482879
Xinchao Fan , Bangfu Huang , Gaoyong Zi , Zhe Shi , Linjing Yang , Liubin Luo , Fu Yuan , Keying Zhu , Daoping Zhan
This article investigated the effects of crystallization temperature, stirring rate, and pH on the crystallization of ammonium sulfate (NH4)2SO4) mother liquor containing calcium sulfate (CaSO4). This study measured the metastable zone width, average particle size, and coefficient of variation of (NH4)2SO4 after CaSO4 was added. CaSO4 was found to cover the active nucleation sites of (NH4)2SO4, leading to a widening of the metastable zone. The increase in crystallization temperature increased the rate of molecular thermal movement, resulting in a narrowing of the metastable zone. The increase in stirring rate accelerated solute diffusion; thus, the metastable zone width became narrower. When the stirring rate was 250 rpm, crystals with a large average size were obtained, which was conducive to solid-liquid separation. The decrease in pH caused the solution viscosity to increase; thus, the metastable zone width decreased. When the pH was 4.5, crystallization could be controlled within a better metastable zone width, and burst nucleation did not occur easily, which resulted in the formation of regular-shaped crystals.
研究了结晶温度、搅拌速率和pH对含硫酸钙母液(NH4)2SO4结晶的影响。本研究测量了加入CaSO4后(NH4)2SO4的亚稳区宽度、平均粒径和变异系数。发现CaSO4覆盖了(NH4)2SO4的活性成核位点,导致亚稳区扩大。结晶温度的升高提高了分子热运动速率,导致亚稳区变窄。搅拌速率的增加加速了溶质的扩散;因此,亚稳区宽度变窄。当搅拌速度为250 rpm时,可获得平均粒径较大的晶体,有利于固液分离。pH值降低导致溶液粘度增大;因此,亚稳区宽度减小。当pH为4.5时,晶化可以控制在较好的亚稳区宽度内,不易发生爆裂成核,形成规则形状的晶体。
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引用次数: 0
Sulfur: –redefining versatility in crop protection and production 硫:重新定义作物保护和生产的多功能性
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-03-04 DOI: 10.1080/10426507.2025.2477176
Sujoy Saha (Conceptualization Resources Writing – review & editing) , Shital Pawar (Methodology Writing – original draft) , Nutan Napte (Methodology Writing – original draft)
Sulfur (S) is the fourth vital nutrient for the growth, health and development of plants. It plays a key role in the structure of proteins, the function of enzymes, in photosynthesis and the defence of plants against stresses, diseases and pests, as also in the keeping quality of produce. A wide range of recently developed sulfur-containing agrochemicals, constitute a distinct class of chemical compounds with novel modes of action. Over 30% of today’s agrochemicals, mostly fungicides, acaricides, and insecticides, contain at least one sulfur atom in different forms. Sulfur has a plethora of attributes in enhancing crop productivity with a simultaneous robust role in protecting the quality produce. This article, is an attempt to summarize the available scattered literature on the aforementioned aspects and highlights. The objective of this review is to provide an update on recent findings related to these subjects, the versatile domains of sulfur, vis-à-vis the role of different input organizations in fostering the molecule against various diseases of crops.
硫(S)是植物生长、健康和发育的第四大重要营养素。它在蛋白质的结构、酶的功能、光合作用和植物抵御压力、疾病和害虫以及保持农产品质量方面起着关键作用。最近开发的一系列含硫农用化学品构成了一类独特的化合物,具有新颖的作用方式。今天超过30%的农用化学品,主要是杀菌剂、杀螨剂和杀虫剂,至少含有一个不同形式的硫原子。硫在提高作物生产力方面具有多种特性,同时在保护优质产品方面发挥着强大的作用。本文试图对现有的零散文献对上述方面和重点进行总结。这篇综述的目的是提供最新的发现有关这些主题,硫的多功能域,以及-à-vis不同的输入组织在促进分子对抗作物各种疾病中的作用。
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引用次数: 0
Visible-light induced oxidation of thiols to disulfides using fluorescein as a metal free catalyst 使用荧光素作为无金属催化剂,可见光诱导硫醇氧化为二硫化物
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-03-04 DOI: 10.1080/10426507.2025.2467437
Pritesh Khobrekar , Sandesh Bugde
In this work, we describe a mild, affordable, and visible-light-mediated oxidative coupling of thiols to the corresponding disulfides utilizing a commercially available, metal-free photocatalyst. Herein, we demonstrate the use of fluorescein as a photoredox catalyst for visible-light-driven oxidative coupling of thiols to disulfides. The use of ammonium thiocyanate as an oxidant, mild reaction conditions, and a wide range of substrates suggest that this technology is feasible for disulfide synthesis.
在这项工作中,我们描述了一种温和的、负担得起的、可见光介导的硫醇与相应的二硫化物的氧化偶联,利用一种市售的、无金属的光催化剂。在这里,我们展示了荧光素作为可见光驱动硫醇氧化偶联的光氧化还原催化剂的使用。硫氰酸铵作为氧化剂,反应条件温和,底物范围广,表明该技术是可行的二硫化物合成。
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引用次数: 0
Synthesis of new phenolic-containing hydroxyacyl probe and its colorimetric fluorescence detection of S2- 新型含酚羟基酰基探针的合成及其对S2-的比色荧光检测
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-03-04 DOI: 10.1080/10426507.2025.2465796
Xiaohua Cai , Benyue Yao , Mei Han , Le Liang , Xiaohong Li , Yanli Leng
The excessive S2- can lead to a variety of serious physiological diseases, so the quickly detection of S2- is of great significance for human. In this paper, a new simple and easily probe Y was designed and synthesized with hydrazine and substituted salicylaldehyde. It can detect S2- with good performance in a highly water contain solution (DMSO/H2O, v/v = 1/9), both colorimetric and fluorescence spectroscopy have obvious changes after adding 50-folds of S2-, and other common fifteen anions have almost no influence in the detection. The detection limit and complexation constant were calculated using fluorescence titration data to be 3.88 μmol/L and 3.68×106 L/mol, respectively. Job’s plot experiment showed that the binding ratio of the host with S2- is 1:1. The NMR titration was employed to verify the recognition mechanism, three protons in two hydroxyl groups (-OH) and one imine (-NH) are disappeared after adding excessive S2-, which shown that probe Y undergo a deprotonation process. Preliminary application experiments show that probe Y can detect S2- in water samples and soil.
过量的S2-可导致多种严重的生理疾病,因此快速检测S2-对人类具有重要意义。本文以肼和取代水杨醛为原料,设计并合成了一种简单易探测的新型Y。该方法在高含水溶液(DMSO/H2O, v/v = 1/9)中检测S2-性能良好,添加50倍的S2-后比色和荧光光谱变化明显,其他常见的15种阴离子对检测几乎没有影响。利用荧光滴定数据计算其检出限为3.88 μmol/L,络合常数为3.68×106 L/mol。Job的plot实验表明,宿主与S2-的结合比例为1:1。用核磁共振滴定法验证了识别机理,添加过量的S2-后,2个羟基(- oh)和1个亚胺(- nh)中的3个质子消失,表明探针Y发生了去质子化过程。初步应用实验表明,Y型探针可以探测水样和土壤中的S2-。
{"title":"Synthesis of new phenolic-containing hydroxyacyl probe and its colorimetric fluorescence detection of S2-","authors":"Xiaohua Cai ,&nbsp;Benyue Yao ,&nbsp;Mei Han ,&nbsp;Le Liang ,&nbsp;Xiaohong Li ,&nbsp;Yanli Leng","doi":"10.1080/10426507.2025.2465796","DOIUrl":"10.1080/10426507.2025.2465796","url":null,"abstract":"<div><div>The excessive S<sup>2-</sup> can lead to a variety of serious physiological diseases, so the quickly detection of S<sup>2-</sup> is of great significance for human. In this paper, a new simple and easily probe <strong>Y</strong> was designed and synthesized with hydrazine and substituted salicylaldehyde. It can detect S<sup>2-</sup> with good performance in a highly water contain solution (DMSO/H<sub>2</sub>O, v/<em>v</em> = 1/9), both colorimetric and fluorescence spectroscopy have obvious changes after adding 50-folds of S<sup>2-</sup>, and other common fifteen anions have almost no influence in the detection. The detection limit and complexation constant were calculated using fluorescence titration data to be 3.88 μmol/L and 3.68×10<sup>6</sup> L/mol, respectively. Job’s plot experiment showed that the binding ratio of the host with S<sup>2-</sup> is <strong>1:1</strong>. The NMR titration was employed to verify the recognition mechanism, three protons in two hydroxyl groups (-OH) and one imine (-NH) are disappeared after adding excessive S<sup>2-</sup>, which shown that probe <strong>Y</strong> undergo a deprotonation process. Preliminary application experiments show that probe <strong>Y</strong> can detect S<sup>2-</sup> in water samples and soil.</div></div>","PeriodicalId":20056,"journal":{"name":"Phosphorus, Sulfur, and Silicon and the Related Elements","volume":"200 3","pages":"Pages 261-267"},"PeriodicalIF":1.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis and biological evaluation of methylene spacer incorporated 4-methylsulfonyl phenyl semicarbazones as dual FAAH-MAGL inhibitors 含4-甲基磺酰基苯基氨基脲的亚甲基间隔剂的合成及生物学评价
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-03-04 DOI: 10.1080/10426507.2025.2467438
Shivani Jaiswal , Senthil Raja Ayyannan
Building upon our previous work, we investigated the impact of a methylene spacer on the dual fatty acid amide hydrolase (FAAH) and monoacylglycerol lipase (MAGL) inhibition activity of 4-methylsulfonylphenyl semicarbazones by designing and synthesizing a set of extended semicarbazone analogs. The inhibition data demonstrated that several compounds had a good inhibitory activity against both FAAH and MAGL. Compound 15h, [1-(4-hydroxyphenyl)ethylidene]-2-{[4-(methylsulfonyl)phenyl]amino}acetohydrazide, exhibited a well-balanced FAAH and MAGL inhibition activity with IC50 values of 48 nM and 40 nM, respectively. The enzyme kinetics studies demonstrated that compound 15h inhibits FAAH and MAGL reversibly with noncompetitive and mixed inhibition mode, respectively. Moreover, these experimental results were also supported by molecular modeling and simulation studies. The dual FAAH-MAGL inhibitor 15h, exhibited no cytotoxicity on human neuronal SH-SY5Y cell lines and showed significant neuroprotection in LPS-induced toxicity. Further, compound 15h showed potent analgesic activity and relieved oxidative stress in rats induced by chronic constriction injury (CCI) surgery. Furthermore, compound 15h was non-hepatotoxic up to 2000 mg/kg (po). Overall, the present study identified compound 15h as a promising dual FAAH-MAGL inhibitor and anti-nociceptive agent that merits further investigation.
在之前工作的基础上,我们通过设计和合成一组扩展的缩氨基脲类似物来研究亚甲基间隔物对4-甲基磺酰基苯基缩氨基脲双脂肪酸酰胺水解酶(FAAH)和单酰基甘油脂肪酶(MAGL)抑制活性的影响。抑制数据表明,几种化合物对FAAH和MAGL均有良好的抑制活性。化合物15h[1-(4-羟基苯基)乙基]-2-{[4-(甲基磺酰基)苯基]氨基}乙酰肼具有良好的抑制FAAH和MAGL活性,IC50值分别为48 nM和40 nM。酶动力学研究表明,化合物15h对FAAH和MAGL分别以非竞争性和混合抑制模式可逆抑制。此外,这些实验结果也得到了分子模型和模拟研究的支持。双FAAH-MAGL抑制剂15h对人神经元SH-SY5Y细胞株无细胞毒性,对lps诱导的毒性具有显著的神经保护作用。此外,化合物15h对慢性收缩性损伤(CCI)大鼠具有明显的镇痛作用,并能缓解其氧化应激。此外,化合物15h在2000 mg/kg (po)时无肝毒性。总的来说,本研究确定化合物15h是一种有前景的双FAAH-MAGL抑制剂和抗伤害剂,值得进一步研究。
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引用次数: 0
A convenient method for synthesis of Morita-Baylis-Hillman (MBH) 1,3-diene adducts and their in silico physicochemical, pharmacokinetics, and molecular docking evaluation studies Morita-Baylis-Hillman (MBH) 1,3-二烯加合物的简便合成方法及其硅理化、药代动力学和分子对接评价研究
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-03-04 DOI: 10.1080/10426507.2025.2473917
Ferid Yaccoubi , Haitham Elleuch , Eman S. Abou-Amra , Ahmed M. Hussein
A series of Morita-Baylis-Hillman (MBH) 1,3-diene adducts are obtained according to a new, simple and practical method under mild operating conditions. Indeed, the action of t-BuOK on the cyclic allylic phosphonates of MBH in THF at room temperature leads to the corresponding 1,3-dienes with high stereoselectivity and good yields. The two Z and E isomers are determined by examining the NMR spectra which reveal, that the E configuration isomer is highly predominant. Density functional theory (DFT) computational analyses of compounds 3f and 3 g were performed to figure out the molecular structures and topologies of the predicted more energetic compounds, using the B3LYP functional and the 6-31 G(d,p) basis set. The HOMO- LUMO, and MEP analyses were visualized with the help of the Gaussview program. Multiwfn software is used for electron localization function (ELF) and localized orbital locator (LOL). We docked the synthesized compounds 3a-3g and 3 m into the protein binding sites of cyclooxygenase-1 (PDB ID: 3KK6) and cyclooxygenase-2 (PDB ID: 1CX2) to examine the binding mechanism, non-bonding interactions, and binding affinity of the tested compounds, using the molecular operating environment (MOE) 2015 program. Swiss ADME web tool is used to determine the physicochemical properties of the compounds: absorption, distribution, metabolism, elimination and toxicity (ADME), and drug-likeness characteristics.
在温和的操作条件下,采用一种简单实用的新方法合成了一系列Morita-Baylis-Hillman (MBH) 1,3-二烯加合物。事实上,t-BuOK在室温下作用于四氢呋喃中的环烯丙基膦酸盐,可以得到立体选择性高、产率高的1,3-二烯。两个Z和E异构体是通过检查核磁共振光谱确定的,这表明,E构型异构体是高度占优势的。利用B3LYP泛函和6-31 g (d,p)基集,对化合物3f和3g进行了密度泛函理论(DFT)计算分析,以确定预测的高能化合物的分子结构和拓扑结构。利用Gaussview程序将HOMO- LUMO和MEP分析可视化。Multiwfn软件用于电子定位函数(ELF)和定位轨道定位器(LOL)。利用分子操作环境(MOE) 2015程序,将合成的化合物3a-3g和3m分别对接到环氧化酶-1 (PDB ID: 3KK6)和环氧化酶-2 (PDB ID: 1CX2)的蛋白结合位点,研究化合物的结合机制、非键相互作用和结合亲和力。瑞士ADME网络工具用于确定化合物的物理化学性质:吸收、分布、代谢、消除和毒性(ADME),以及药物相似特性。
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引用次数: 0
Phospha-Mannich reactions of hypophosphorous acid H3PO2 次磷酸H3PO2的磷酸-曼尼希反应
IF 1.4 4区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-03-04 DOI: 10.1080/10426507.2025.2477186
Dmitry V. Moiseev (Conceptualization Formal analysis Investigation Visualization Writing – original draft Writing – review & editing)
Hypophosphorous (phosphinic) acid H2P(O)OH, due to the acid-promoted equilibrium with the trivalent tautomer – phosphonous acid HP(OH)2, participates in phospha-Mannich reactions with imine/iminium species, or their donors, to give a variety of mono- and bis-(α-aminoalkyl)phosphinic compounds (PO2,N-acetals). These reactions are more complex than those involving phosphines or secondary phosphine oxides, reviewed previously, and are commonly accompanied by several side-reactions, resulted from instability of H3PO2 and the presence of hypophosphite anion, a reductant. Unlike basic phosphines and neutral phosphine oxides, H3PO2 and its phospha-Mannich products can mimic carboxylic acids in biological processes and chemistry, and synthesis of phosphinic analogs of natural α-amino acids, used to design phosphinic pseudopeptides, is one of the major applications of H3PO2 and its synthons, such as phosphonites (RO)2PH (R = SiMe3, alkyl) and alkyl dialkoxymethylphosphinates (R’O)2CHP(O)(OR’)H. H3PO2 is a unique P-nucleophile that can produce relatively stable acetals with a P–H function, widely used for further derivatization. Phospha-Mannich reactions of H3PO2 also provide a variety of (α-aminoalkyl)phosphinic compounds, applied as flame-retardant or chelators of di- and tri-valent metal ions useful in metal-based (radio)pharmaceuticals for imaging and therapy.
次磷(磷酸)酸H2P(O)OH,由于酸促进与三价互变异构体-磷酸HP(OH)2的平衡,参与与亚胺/亚胺物种或它们的供体的磷酸-曼尼希反应,得到各种单-和双-(α-氨基烷基)磷酸化合物(PO2, n -缩醛)。这些反应比先前回顾的涉及磷化氢或二次磷化氢氧化物的反应更复杂,并且通常伴随着几种副反应,这是由H3PO2的不稳定性和亚磷酸阴离子(还原剂)的存在引起的。与碱性膦和中性膦氧化物不同,H3PO2及其磷酸-曼尼希产物在生物过程和化学中可以模拟羧酸,而合成天然α-氨基酸的磷酸类似物,用于设计磷酸假肽,是H3PO2及其合成子的主要应用之一,如膦酸盐(RO)2PH (R = SiMe3,烷基)和烷基二氧甲基膦酸盐(R ' O)2CHP(O)(OR ')H。H3PO2是一种独特的p -亲核试剂,可以生成相对稳定的具有P-H功能的缩醛,广泛用于进一步衍生化。H3PO2的Phospha-Mannich反应也提供了多种(α-氨基烷基)膦化合物,用作二价和三价金属离子的阻燃剂或螯合剂,用于金属基(放射性)成像和治疗药物。
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引用次数: 0
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