Mechanochemical synthesis of oxygenated alkynyl carbon materials with excellent Hg(Ⅱ) adsorption performance from CaC2 and carbonates

Adsorptive removal of heavy metal ions from wastewater is very important,and the key is the development of efficient sorbents.In this work,oxygenated alkynyl carbon materials(OACMs)were synthesized via mechanochemical reaction of CaC_(2) and a carbonate(CaCO_(3),Na2CO_(3),or NaHCO_(3))at ambient temperature.The resultant OACMs are micro mesoporous carbon nanomaterials with high specific area(>648 m2 g^(-1)),highly crosslinked texture,and rich alkynyl and oxygenated groups.The OACMs exhibit excellent Hg(Ⅱ)adsorption due to the soft acid-soft base interaction between alkynyl and Hg(Ⅱ),and OACM-3 derived from CaC_(2) and NaHCO_(3) has the saturated Hg(Ⅱ)adsorbance of 483.9 mg g^(-1)along with good selectivity and recyclability.The adsorption is mainly chemisorption following the Langmuir mode.OACM-3 also shows high adsorbance for other heavy metal ions,e.g.256.6 mg g^(-1)for Pb(II),232.4 mg g^(-1)for Zn(II),and 198.7 mg g^(-1)for Cu(II).This work expands the mechnochemical reaction of CaC_(2)with carbonates and possibly other oxyanionic salts,provides a new synthesis approach for functional alkynyl carbon materials with excellent adsorption performance for heavy metal ions,as well as a feasible approach for CO2 resource utilization.

The alkynyl-containing compounds from mushrooms and their biological activities

Mushrooms have been utilized by humans for thousands of years due to their medicinal and nutritional properties.They are a crucial natural source of bioactive secondary metabolites,and recent advancements have led to the isolation of several alkynyl-containing compounds with potential medicinal uses.Despite their relatively low abundance,naturally occurring alkynyl compounds have attracted considerable attention due to their high reactivity.Bioactivity studies have shown that alkynyl compounds exhibit significant biological and pharmacological activities,including antitumor,antibacterial,antifungal,insecticidal,phototoxic,HIV-inhibitory,and immunosuppressive properties.This review systematically compiles 213 alkynyl-containing bioactive compounds isolated from mushrooms since 1947 and summarizes their diverse biological activities,focusing mainly on cytotoxicity and anticancer effects.This review serves as a detailed and comprehensive reference for the chemical structures and bioactivity of alkynyl-containing secondary metabolites from mushrooms.Moreover,it provides theoretical support for the development of chemical constituents containing alkynyl compounds in mushrooms based on academic research and theory.

氧化石墨烯对靶向吸氢纳米复合材料吸氢性能影响研究

以氧化石墨烯(GO)作为载体的有机吸氢材料和其催化剂的复合材料,在低温真空领域具备较优的应用前景。为研究载体材料GO对复合材料的形貌和吸氢性能的影响,制备了氧化石墨烯基纳米复合材料(Alkyne-PVA-(GO-PdO)),通过XRD、^(1)H-NMR、SEM和TEM对其进行了表征,并与无氧化石墨烯的纳米复合材料(PdO@Alkyne-PVA)进行对比。结果表明,PdO和炔基化聚乙烯醇(Aklyne-PVA)能够成功负载在GO上,Alkyne-PVA-(GO-PdO)上的PdO纳米粒子分布良好,平均粒径为2.1 nm。采用静态膨胀法对两种吸氢材料的吸氢性能进行研究对比发现,Alkyne-PVA-(GO-PdO)在平衡压力为463.8 Pa时,吸氢量达到了11048.25 Pa·L/g,而PdO@Alkyne-PVA在平衡压力为560.21 Pa下,吸氢量仅达到4528.35 Pa·L/g。这归因于GO较高的比表面积和表面大量的含氧官能团、缺陷和空位改善了PdO纳米粒子的团聚问题。此外,GO在吸氢反应过程中保证了PdO纳米粒子不会因发生团聚现象而阻碍后续吸氢反应,使得产物钯金属发挥了其最优的催化性能,同时GO的氢溢流效应加速了解离后的氢原子的扩散,有效增强了复合材料的吸氢性能。文章验证了GO在吸氢领域中良好的应用潜力,为以GO为基底的吸氢材料的实现提供了可能。

手性磷酸催化非环状N,N′-缩酮的不对称合成

手性N,N′-缩酮是药物分子和生物活性化合物最重要的核心结构之一,也是有机合成中重要的催化剂或配体。因此,不对称合成N,N′-缩酮具有重要意义。通过手性磷酸、溶剂、催化剂负载量和投料比的筛选,确定了最佳的反应条件:在手性磷酸的催化下,以1,4-二氧六环作为溶剂,5-氨基异噁唑与β,γ-炔基-α-酮亚胺酯在室温下发生区域选择性的氮杂-曼尼希反应,实现异噁唑的不对称N—H烷基化,以中等至良好的收率(46%~83% yield)和较好的对映选择性(82%~92%ee)合成非环状的N,N′-缩酮。所有产物结构由^(1)H NMR,^(13)C NMR和HR-MS(ESI)确证,绝对构型通过X-射线晶体结构分析确定。

催化弱配位基团参与的C—H炔基化反应研究

炔烃是药物和天然产物结构中的一种非常重要的骨架,其炔基可以与多种化合物反应转化为其他官能团的产物,所以其合成一直是有机化学家研究的重点。近些年,C—H活化反应被广泛研究,可以直接被官能团化,而不需要事先进行活化。因此,用金属直接催化进行C—H炔化反应已成为一种非常有前景的合成炔烃的方法,以获得炔类化合物。文章旨在[RuCl_(2)(p-cymene)]_(2)催化剂的催化作用下,在导向基团硫代酰胺的导向下,使二茂铁环与炔基化试剂进行反应生成一种高产率的双炔基化的二茂铁硫代酰胺化合物。

双烯丙醇一锅法合成的有机化学综合实验教学设计

结合课题组的前期研究成果,介绍了一个格氏试剂、炔基砜和查尔酮的一锅法合成双烯丙醇的有机化学综合实验教学设计。产物结构经过^(1)H NMR、^(13)C NMR和HRMS表征,并通过自动熔点仪测定出产物的熔点。实验中涉及格氏试剂的制备以及化学性质的研究,丰富了有机化学实验的教学内容。将科研成果融入到有机化学综合实验教学中,不仅能够锻炼学生的综合实验技能和提高学习兴趣,而且能够拓宽学生的科学研究视角和激发学生的创新思维能力;同时,这也能为学生本科毕业论文设计的开展打下扎实的基础。

A new synthesis of alkynyl tellurides promoted by CsOH and 4 MS

The mixture of cesium hydroxide and terminal alkynes in dry DMF in the presence of 4 A molecular sieves was stirred for 3.0 h at room temperature under N2, then aryltellurenyl bromide in THF was added, and the reaction mixture was stirred for 2.0 h. Alkynyl tellurides were obtained in about 90% yields by flash chromatography.

Triphenylphosphine-catalyzed isomerization of alkynyl ketones in aqueous solution

An efficient isomerization of alkynyl ketones to (E,E)-diene ketones was developed. The reaction catalyzed by 20 mol% triphenylphosphine in aqueous media gave the desired products in good yields.

High extraction ability of 1,3-dialkynyl calixarene towards mercury(Ⅱ) ion

The reaction of 1,3-dipropyn-2-yloxycalix[4]arene with mercury（U） acetate could give mercury-containing alkynyl calixarene polymer. The extraction behavior of 1,3-dipropyn-2-yl-oxycalix[4]arene towards mercury（Ⅱ） ion was examined. When the mole ratio of Hg^2＋/calixarene was 1：1, the extractive percent can reach to 99.1%, and the extraction capacity was up to 431 mg/g. It could also decrease the Hg^2＋ concentration from 5 to 0.85 mg/L, which was only 17% of the national standard of effluent and satisfied the national standard of drinking water. The extraction process included chemical reaction.

Recyclable polymer functionalization via end-group modification and block/random copolymerization

Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via end-group modifications and block/random copolymerizations.Di-n-butylmagnesium was selected to catalyze ring-opening polymerization(ROP)of(R)-M in the presence of a series of functional alcohols as the initiators.Block/random copolymerizations of(R)-M andε-caprolactone(ε-CL),L-lactide(L-LA)and trimethylene carbonate(TMC)were performed to control the onset decomposition temperature(T_(d)),melting temperature(T_(m))and glass transition temperature(T_(g)).These functionalized recyclable polymers would find broad applications as the sustainable plastics.

The applications of Schiff bases in Ti-catalyzed asymmetric alkynylation of aldehydes

Sciff bases 1 and 2, .which were derived from chiral aminoalcohols, were used as figands in Ti-catalyzed asymmetric alkynylation of aldehydes. Good enantioselectivities （up to 88% ee） and high chemical yields （80-90%） were obtained.

Synthesis,Structure and Photophysical Properties of Heteronuclear Pt_2Cu Alkynyl Complexes

Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses,ESI-MS,^1H and ^31P{^1H} NMR spectroscopy,and X-ray crystallography for 2.Their photophysical properties in the solid state and in solutions at room temperature and in frozen glasses at 77 K were studied.Both complexes 1 and 2 show strong orange-red emission in the solid state at room temperature and in frozen glasses at 77 K,and weak emission in solutions.

Stereoslective Synthesis of (Z)-1, 2-Bis(arylseleno)-1-alkene by Addition of Cesium Arylselenolate to Alkynyl Selenide

Alkynyl selenide reacted with cesium arylselenolate in commercial THF at r.t under N2 to afford (Z)-1, 2-bis(arylseleno)-1-alkene in high yields.

银催化的环化反应合成异喹啉的研究进展

含有异喹啉骨架的化合物是一类很重要的含氮杂环化合物,广泛存在于具有生物活性的天然产物、有机材料以及药物分子中。传统的合成异喹啉的方法需要苛刻的反应条件,因此,使用温和及简单的方法构建这一骨架的化合物具有重要的现实意义。银类化合物具有路易斯酸特性,能够催化活化三键。利用这一特点并使用含氮的亲核试剂进行分子内亲核加成活化的三键是合成异喹啉衍生物的重要方法。本文主要综述了以2-炔基苄亚胺、2-炔基苄基叠氮、2-炔基苯甲醛肟、2-炔基苯甲醛腙及其(2-(乙炔基)芳基)-1,2,3-三唑为反应物,在银催化条件下构建异喹啉环的研究进展,并对部分反应的机理进行了讨论。

Cobalt-catalyzed reductive alkynylation to construct C(sp)-C(sp^(3))and C(sp)-C(sp^(2))bonds

Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp)-C(sp^(3))and C(sp)-C(sp^(2))bonds.This presented reaction has a broad substrate scope,enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl(pseudo)halides.This presented reaction is conducted under mild conditions,tolerating many functional groups,thus suitable for the modification and synthesis of biologically active molecules.

Boosting thermal stability and crystallization of closed-loop-recyclable biodegradable poly(p-dioxanone) by end-group regulation

A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly,when PPDO wastes can be collected,its monomer p-dioxanone(PDO) will be obtained through chemical recycling of these wastes;when cannot be collected,the wastes are able to be biodegraded into harmless substances.However,unsatisfied thermal stability and low crystallization rate of PPDO restrict its wider applications.Herein,based on end-group regulation,we simultaneously realized the significant enhancement of thermal stability and crystallization of PPDO through the simple melt processing with tributyl phosphite(TBP) or triphenyl phosphite(TPP).The model reactions were conducted to investigate the reaction mechanism and theoretical products during the preparation of PPDO/phosphite compounds.Two kinds of phosphites were proved to act as the end-capped reagent and chain extender in the melt processing,while TBP presented better reactivity.As a result,the activation energy of thermal decomposition was largely elevated,and the unprecedented T_(5%)(the temperature at a weight loss of 5%) and Tmax(the temperature at a maximum rate of weight loss) of PPDO were obtained,i.e.,T_(5%)of ~330 ℃ and Tmaxof ~385 ℃ in N_(2) atmosphere,T_(5%)of ~240 ℃ and Tmaxof ~317 ℃ in air atmosphere,respectively.Furthermore,the increased crystallization rate,crystallinity,crystalline orderliness,and realizable monomer recovery(yield >90%,purity >99.9%) of PPDO/phosphite compounds were confirmed.

Transition-metal-catalyzed remote meta-C-H alkylation and alkynylation of aryl sulfonic acids enabled by an indolyl template

Transition-metal-catalyzed remote sp^(2)C-H functionalization of aryl sulfonic acids was hardly ever real-ized owing to competitive ortho-C-H functionalization of aryl sulfonates and electron-deficient nature of phenyl ring.Herein,with the assistance of a practical biaryl indolyl directing template,palladium-catalyzed remote sp^(2)C-H alkylation of aryl sulfonic acids have been achieved in moderate to good yields with exclusive meta selectivity.Moreover,remote meta-selective C-H alkynylation of aryl sulfonic acids was also accomplished with a rhodium catalyst.These meta-C-H functionalized products proved to be the superior synthetic precursors,which are difficult to access using the conventional strategy.

Visible-light-induced decarboxylative alkynylation of carboxylic acids in batch and continuous flow

A green efficient photoredox-catalyzed decarboxylative alkynylation of carboxylic acids with alkynyl bromides has been developed.This broadly applicable protocol is presented whereinα-amino,aliphatic andα-oxy acids are converted into useful alkynylation products.The commercially-available organic photocatalyst 4CzIPN is used as the photocatalyst,organic base DBU is utilized as the base,and DMSO serves as solvent.This strategy features mild conditions,is metal-free,and is environmentally friendly.The batch and continuous-flow protocols described were applied to obtain a broader substrate scope of functionalization(more than 50 examples).Furthermore,we demonstrate that the use of microflow technology enhanced and intensified the reaction process,achieving significantly reduced reaction times(i.e.,10 min of residence time).

Pd-catalyzed asymmetric carbonyl alkynylation:Synthesis of axial chiral ynones

Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.

Enhancing Photovoltaic Performance of Nonfused-Ring Electron Acceptors via Asymmetric End-Group Engineering and Noncovalently Conformational Locks

By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader light absorption range,more coplanarπ-conjugated backbone,and appropriate crystallinity according to the experimental and theoretical results.The organic solar cells based on J52:NoCA-19 exhibited a power conversion efficiency as high as 12.26%,which is much higher than those of J52:NoCA-17(9.50%)and J52:NoCA-18(11.77%),mainly due to more efficient exciton dissociation,better and balanced charge mobility,suppressed recombination loss,shorter charge extraction time,longer charge carrier lifetimes,and more favorable blend film morphology.These findings demonstrate the great potential of asymmetric end-group engineering in exploring low-cost and high-performance NFREAs.