一种用于光催化氧化硫醚成亚砜的超薄卟啉的共价有机骨架纳米片

单线态氧(~1O_2)可将硫醚化合物选择性氧化为亚砜,而开发具有高~1O_2量子产率的高效光敏剂至关重要。本文中我们报道了超薄二维共价有机骨架(COFs)纳米片(NSs)COF-367 NSs的制备和表征。COF-367 NSs在各种有机溶剂中的良好分散性和高效率的光收集赋予其在可见光照射下产生~1O_2的显著性能,且远优于块体COF-367。我们还证明了COF-367 NSs是硫醚化合物光催化氧化成亚砜的优良非均相催化剂,具有高效率和选择性以及良好的循环稳定性。     

杯芳烃衍生物萃取剂分离An(Ⅲ)/Ln(Ⅲ)

硝酸体系中三价镧系元素与锕系分离的选择性萃取剂的合成与选择是分离-嬗变的重要研究方向之一。配位基的预组织性对萃取剂的萃取能力和选择性具有重要作用,杯芳烃的结构特征为配位基的预组织提供了理想的平台。上世纪90年代以来,研究者们合成了大量新型杯芳烃衍生物萃取剂,萃取分离硝酸溶液中An(Ⅲ)/Ln(Ⅲ),在杯芳烃衍生物萃取剂的结构与性能关系方面做了大量研究,获得一些共性规律性认识。本文在简要说明配位基预组织性对提高萃取能力和分离能力的作用基础上,详细综述了近20年在二苯基氨基甲酰甲基氧化膦(CMPO)、烷基氧化膦、吡啶酰胺等配位基修饰杯芳烃分离An(Ⅲ)/Ln(Ⅲ)的研究进展,阐明了杯芳烃衍生物的结构与配位基的预组织性、萃取能力和An(Ⅲ)/Ln(Ⅲ)分离能力的关系,展望了杯芳烃衍生物结构修饰研究方向及其在乏燃料后处理中的应用前景。     

5,7-二溴-8-羟基喹啉锰配合物催化H_2O_2选择氧化乙苯

设计合成了5,7-二溴-8-羟基喹啉锰的四齿和六齿配合物(Q2MnⅡ和Q3MnⅢ),并用傅里叶变换红外(FT-IR)光谱对两个配合物进行了表征.以醋酸铵和醋酸为助剂,丙酮-水作溶剂,两个锰配合物在室温20℃下能高选择性催化双氧水氧化乙苯制苯乙酮的反应,Q3MnⅢ比Q2MnⅡ具有更高的催化活性和选择性.在优化的反应条件下,乙苯转化率达27%,苯乙酮的选择性95%;而且催化剂稳定性良好,可循环使用三次.     

氮杂冠醚取代非对称双Schiff碱配合物催化氧化对二甲苯研究

将一系列苯并-10-氮杂-15-冠-5或吗啉基取代的不对称双Schiff碱配合物作为催化剂,在常压和120℃条件下用于催化氧化对二甲苯研究。探讨了Schiff配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基等对催化氧化对二甲苯反应活性及其氧化产物选择性的影响。实验结果表明:配合物中氮杂冠醚的存在能显著缩短反应诱导期、提高催化活性和选择性;Schiff碱Mn(Ⅲ)配合物比Schiff碱Co(Ⅱ)和Schiff碱Cu(Ⅱ)具有更高的催化活性;氮杂冠醚Schiff碱Mn(Ⅲ)配合物催化氧化二甲苯的转化率和产物选择性分别达75%和90%。     

相转移催化下Mn（Ⅲ）／Mn（Ⅱ）体系对醇类的选择性电氧化

以Mn(Ⅲ)/Mn(Ⅱ)为间接氧化还原体系,用间接电氧化的方法,在相转移催化条件下对醇类的氧化进行了研究。结果表明,在所用实验条件下,Mn(Ⅲ)可以方便地在电极上生成及再生,对苄醇类及二级脂肪醇类能高产率地选择性氧化成相应的羰基化合物。     

苄基醚选择性间接电氧化的研究

以Mn(Ⅲ) / Mn(Ⅱ)为 间接氧化还原体系研究苄基醚的氧化. 实验结果表明该体系能高产率选择性地氧化苄基醚为 苯甲醛和相应的醇. 阳极液中Mn(Ⅱ)可以循环使用.     

钠型离子交换树脂催化过氧化氢选择性氧化硫醚的研究

在以钠型强酸性离子交换树脂为催化剂和过氧化氢为氧化剂的反应条件下,首次研究了选择性氧化苯甲硫醚生成苯甲亚砜的反应,优化得到了合成苯甲亚砜的最佳合成条件为:反应底物苯甲硫醚8mmol、过氧化氢9.6mmol、反应溶剂甲醇10mL、反应温度为常温、反应时间为8h、催化剂用量为底物摩尔量的50%。此反应的转化率大于90.0%,选择性大于99.9%。催化剂重复使用15次未见其活性和选择性明显下降。在类似的反应条件下,其他5种硫醚也被高效和高选择性地氧化为相应的亚砜。     

微波促进合成苝单酰亚胺类化合物

以3,4;9,10-苝四甲酸酐为原料,经微波促进反应探讨了反应底物用量、反应时间和反应温度等条件对反应收率的影响,合成了系列苝单酰亚胺类化合物,其中2,6-二异丙基苯胺修饰的苝单酰亚胺化合物N-2’,6’-二异丙基苯胺基-3,4-苝单酰亚胺(PMI-1)在30min的反应时间内,分离收率可达64.1%.     

光催化应用于药物合成反应实验教学的设计与改革

可见光诱导的光催化具有绿色、高效、可持续等特点,在有机医药中间体和药物分子的合成上极具创新性。近年来,将前沿性、创新性的科研成果实施于本科实验教学项目中已成为高校实验教学改革的重点与趋势之一。本实验利用苝二酰亚胺作为光催化剂,在温和的光照条件下高效选择性氧化硫醚得到亚砜。通过本实验的学习,为学生实践绿色、低能耗的有机化学提供了理想的平台,拓展了学生对当今合成技术前沿的视野,调动了对于合成新技术、新应用的兴趣,激发了挑战传统合成手段的热情,培养了科研创新理念以及独立思考、分析解决问题的能力。     

2-羟基-3-三乙氨基丙基辛基硫醚(HAPOS)对Au(Ⅲ)的萃取作用

研究了新型表面活性剂 2 羟基 3 三乙氨基丙基辛基硫醚 (HAPOS) ,在酸性条件下对Au(Ⅲ )的萃取分离作用。在实验条件下 ,一次萃取率可达 95%以上 ,并具有较高的选择性。     

Advanced Photosensitizer Activation Strategies for Smarter Photodynamic Therapy Beacons

Photodynamic therapy (PDT) is a clinical treatment in which a light‐absorbing drug called a photosensitizer (PS) is combined with light and molecular oxygen to generate cytotoxic singlet oxygen. PDT provides additional tissue selectivity compared to conventional chemotherapy as singlet oxygen is generated only in areas in which PS accumulates and that are simultaneously illuminated by a light source with sufficient irradiance and dose. Early PDT beacons built on this concept by adding an analyte‐responsive element that simultaneously turns on PDT and fluorescence, providing both an additional layer of selectivity and real‐time feedback of the PS′s activation state. More recent PDT beacons have expanded this idea, with new methods now available for sensing analytes, generating singlet oxygen, and reporting treatment status. In this Minireview, we consider developments in advanced activation strategies implemented in therapeutic and theranostic beacons.     

4-(4-甲基-苯基)-6-苯基-2,2′-联吡啶铂(Ⅱ)光致产氢研究

本文以氯离子配位的4-(4-甲基-苯基)-6-苯基-2,2′-联吡啶铂(Ⅱ)配合物为光敏剂,Co(dmgH)2pyCl为催化剂,三乙醇胺(TEOA)为电子牺牲体,在pH为8.5的乙腈/水混合溶剂中构建了光致产氢体系.体系光照(λ>400nm)19h后产氢量达到1.8mL,反应的转换数(TON)达到804(vs.光敏剂).     

水溶性卟啉配合物的合成及光敏化行为

在低沸点的氯仿溶剂中合成了中-四(对二甲基丙磺酸基氨基)苯基卟啉(简记为H₂TPS),在乙酸溶剂中合成了相应的金属卟啉[简记为MeTPS,Me=Zn(Ⅱ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅲ),Mn(Ⅱ)],并进行了表征。TEOA-MeTPS-MV²⁺-DMSO(H₂O)(75:25,V/V)体系的光敏化还原MV²⁺反应的研究结果表明,Zn(Ⅱ)TPS、Mn(Ⅱ)TPS及H₂TPS是较好的光敏剂,且以Zn(Ⅱ)TPS为最好。     

An Assembled Nanocomplex for Improving both Therapeutic Efficiency and Treatment Depth in Photodynamic Therapy

Photodynamic therapy (PDT) shows unique selectivity and irreversible destruction toward treated tissues or cells, but still has several problems in clinical practice. One is limited therapeutic efficiency, which is attributed to hypoxia in tumor sites. Another is the limited treatment depth because traditional photosensitizes are excited by short wavelength light (<700 nm). An assembled nano‐complex system composed of oxygen donor, two‐photon absorption (TPA) species, and photosensitizer (PS) was synthesized to address both problems. The photosensitizer is excited indirectly by two‐photon laser through intraparticle FRET mechanism for improving treatment depth. The oxygen donor, hemoglobin, can supply extra oxygen into tumor location through targeting effect for enhanced PDT efficiency. The mechanism and PDT effect were verified through both in vitro and in vivo experiments. The simple system is promising to promote two‐photon PDT for clinical applications.     

以硫醚为主链的螯合树脂研究──Ⅱ．2－氨基噻唑树脂的合成及吸附性能

聚环硫丙烷和环硫氯丙烷与环氧氯丙烷共聚物，在少量二乙烯三胺存在下制得交联聚合物，将交联聚合物与２－氨基噻唑反应，制得二种侧链带有氨基噻唑的新型螯合树脂．它们对贵金属具有优良的吸附性能和高的吸附选择性．通过Ｘ－射线光电子能谱初步探讨了树脂对金属离子的螯合作用．     

A stable molecular nickel catalyst for the homogeneous photogeneration of hydrogen in aqueous solution

Light-driven H(2) production is catalyzed by [Ni(P(2)(Ph)N(2)(Ph))(2)](BF(4))(2) when irradiated with visible light in water/acetonitrile mixed solvent in the presence of a photosensitizer (PS) and ascorbate. The catalyst gives over 2700 turnovers over 150 h, and does not degrade despite photodecomposition of the PS.     

一种PS给体模型化合物的合成和性能

为了模拟植物光系统的给体部分,设计、合成了配合物2.在该模型化合物中,配体的邻位被2个{[2-羟基-3-(吗啉基-4-甲基)-5-叔丁基-苄基](吡啶-2-甲基)胺基-甲基}取代的苯酚通过酰胺键与光敏体[Ru(bpy)3]2+共价相连.利用ESI-MS和1D,2DNMR(gCOSY,HSQC和HMBC)对化合物结构进行了鉴定,并通过UV-Vis、荧光发射光谱、闪光光解及电化学对其光化学性能和氧化还原特性进行了研究.结果表明,化合物的吸收波长发生红移;激发态寿命长;可螯合双核高价Mn()原子;且Ru3+/Ru2+的氧化电位比Phenol+/Phenol和Mn(,)/Mn()的高,满足自然界PS电子转移的基本要求,可用于PS给体部分的初步研究.     

Highly-efficient photosensitizer based on AIEgen-decorated porphyrin for protein photocleaving

An AIEgen decorated porphyrin (TPETPyP) with ¹O₂ quantun yield as high as 0.85 in PBS was facilely prepared through a simple one-step reaction for efficient photocleavage of proteins in PDT.     

Cationic fullerenes are effective and selective antimicrobial photosensitizers

Fullerenes are soccer ball-shaped molecules composed of carbon atoms, and, when derivatized with functional groups, they become soluble and can act as photosensitizers. Antimicrobial photodynamic therapy combines a nontoxic photosensitizer with harmless visible light to generate reactive oxygen species that kill microbial cells. We have compared the antimicrobial activity of six functionalized C(60) compounds with one, two, or three hydrophilic or cationic groups in combination with white light against gram-positive bacteria, gram-negative bacteria, and fungi. After a 10 min incubation, the bis- and tris-cationic fullerenes were highly active in killing all tested microbes (4-6 logs) under conditions in which mammalian cells were comparatively unharmed. These compounds performed significantly better than a widely used antimicrobial photosensitizer, toluidine blue O. The high selectivity and efficacy exhibited by these photosensitizers encourage further testing for antimicrobial applications.     

Light‐Harvesting Photocatalysis for Water Oxidation Using Mesoporous Organosilica

An organic‐based photocatalysis system for water oxidation, with visible‐light harvesting antennae, was constructed using periodic mesoporous organosilica (PMO). PMO containing acridone groups in the framework (Acd‐PMO), a visible‐light harvesting antenna, was supported with [Ru^II(bpy)₃²⁺] complex (bpy=2,2′‐bipyridyl) coupled with iridium oxide (IrO_x) particles in the mesochannels as photosensitizer and catalyst, respectively. Acd‐PMO absorbed visible light and funneled the light energy into the Ru complex in the mesochannels through excitation energy transfer. The excited state of Ru complex is oxidatively quenched by a sacrificial oxidant (Na₂S₂O₈) to form Ru³⁺ species. The Ru³⁺ species extracts an electron from IrO_x to oxidize water for oxygen production. The reaction quantum yield was 0.34 %, which was improved to 0.68 or 1.2 % by the modifications of PMO. A unique sequence of reactions mimicking natural photosystem II, 1) light‐harvesting, 2) charge separation, and 3) oxygen generation, were realized for the first time by using the light‐harvesting PMO.