Synthesis and Characterization of Planar Five‐Ring‐Fused Dithiophene‐dione

A series of new organic semiconductors based on s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione was successfully synthesized and characterized. The electron withdrawing carbonyl group lowers the LUMO energy levels, leading to increased electronegativities, which is beneficial for high photo‐stability in air. The n‐alkyl substituted compounds, 1c and 1d , crystallize with the rigid coplanar systems packed into slipped face‐to‐face π‐stacks. Interestingly, 1c and 1d also show liquid crystalline behaviors, which give highly ordered molecular packing over large area.     

Some Graphs with Double Domination Subdivision Number Three

A subset ${S \subseteq V(G)}$ is a double dominating set of G if S dominates every vertex of G at least twice. The double domination number dd(G) is the minimum cardinality of a double dominating set of G. The double domination subdivision number sd _dd (G) is the minimum number of edges that must be subdivided (where each edge in G can be subdivided at most once) in order to increase the double domination number. Atapour et al. (Discret Appl Math, 155:1700–1707, 2007) posed an open problem: Prove or disprove: let G be a connected graph with no isolated vertices, then 1 ≤ sd _dd (G) ≤ 2. In this paper, we disprove the problem by constructing some connected graphs with no isolated vertices and double domination subdivision number three.     

Modulating Endogenous Oxygen Consumption Enhanced AIEgens-Mediated Photodynamic Therapy against Advanced Bladder Tumor

Photodynamic therapy (PDT) plays an important role in tumor therapy. However, PDT outcomes remain poor due to the insufficient reactive oxygen species (ROS) yield of the photosensitizer and the aggravation of hypoxia in the tumor microenvironment through PDT. To solve this issue, a puissant PDT nanoparticles (NPs) platform is developed to defeat tumors by employing powerful PDT in an oxygen-enriched tumor microenvironment and by inhibiting tumor migration through regulating hypoxia-related pathways. Specifically, TFM, as a previously reported AIEgen, does not emit brightly but instead makes use of its nonradiative relaxation for ROS generation, along with oxygen regulator doxycycline (DOXY), both of which are encapsulated in NPs that can specifically penetrate deep into tumor tissue. After released from the NPs, TFM functions as a powerful ROS generator, and DOXY reduces endogenous oxygen consumption via regulating mitochondrial cytochrome oxidase 1, further enhancing TFM-mediated PDT efficacy. Meanwhile, reoxygenation is observed to reduce the expression of hypoxia inducible factor-1α and M2 macrophages induced by PDT. The amplified PDT not only strongly killed tumor but, along with the downregulated hypoxia related pathways during the post-PDT process, inhibited tumor migration. In summary, such NPs exhibit potent anti-tumor effects for advanced bladder cancer therapy.     

新型偶氮苯硫醇衍生物自组装膜的制备与结构表征

自组装单分子膜(ＳＡＭｓ)是近年来引起广泛注意的一种稳定的、二维有序的、致密的有机超薄膜体系,由于其优越的性能,在润滑、吸附、防腐、电化学及微电子等领域中显示出广阔的应用前景[1～4].自组装单分子膜是使用含有各种活性官能团(如-ＣＯＯＨ,-ＳＨ,-Ｓ-Ｓ-,-ＯＨ,-ＣＮ等)的分子,以化学键的形式与相应的基底(如Ａｕ,Ａｇ,Ｃｕ,Ｐｔ,Ｓｉ,Ｍｉｃａ等)相互作用从而自发地形成自组装膜.根据不同的研究或应用目的合理设计组装分子的结构及基底表面,从而得到具有所需功能的自组装单分子膜是近年来界面科学和材料科学等领域研究的热点之一.…     

Improved adsorption and desorption behavior of Cd on thiol-modified bentonite grafted with cysteamine hydrochloride

Clay adsorbents are considered an inexpensive and readily available solution for removing heavy metals, including cadmium, from the environment to reduce pollution. In this study, thiol-modified bentonite (SH-Bent) was prepared by grafting cysteamine hydrochloride onto natural bentonite (Bent). The effects of pH, equilibrium contact time, and temperature on the adsorption–desorption behavior of Cd²⁺ were studied, and adsorption isotherm models were applied to examine the adsorption behavior of SH-bent. SH-Bent demonstrated better performance and stability for Cd²⁺ adsorption than Bent. SH-Bent exhibited an enhanced adsorption capacity for Cd²⁺ at equilibrium of 49.3 mg/g at pH 6, 120 min, and 303 K, which was 42-fold higher than that of Bent under the same conditions. An investigation of the desorption behavior of Cd²⁺ adsorbed on Bent and SH-Bent in simulated acid rain revealed that SH-Bent has high stability, with a desorption rate of 5.73% at pH 4.5, 60 min, and 303 K, which was much lower than that demonstrated by Bent under the same conditions (45.68%). The Langmuir equation was the best-fitted adsorption isotherm model, closely followed by the Freundlich, Tempkin, and Dubinin–Radushkevich models. A significant difference in diffusion was observed between the two types of clay according to the intraparticle diffusion model. The adsorption–desorption processes of SH-Bent and Bent fit the pseudo-second-order model best among the five kinetic models examined. The information provided in this study can be used to apply thiol-modified clay for wastewater treatment or for the removal of cadmium from soil.

Graphical abstract

     

用于扫描探针显微镜研究的原子级平整金基底的制备

报导了一种用于扫描深外显微镜（SPM）研究的原子级平整全基底的制备方法．采用这种方法，得到了25um2范围内，膜的平均粗糙度小平0.4nm的原子级平整基底，并且得到金以（111）面取向在云母表面沉积的实验证据，同时使用电化学循环伏安法和X光电子能谱对这种膜的自组装性能进行了考察．     

含酰胺结构的巯基自组装膜的设计与结构表征

提出了一种简便通用的合成巯基化合物的途径，以分子中的羧基CO2H为起始基团，与2-流基乙胺的氨基选择性缩合；合成了一系列具有RC（O）NHCH2CH2SH（R分别为偶氯苯衍生物，双炔衍生物及直链烷基）结构的化合物，并用接触角测量，电化学和掠角反射红外光谱（GIR-IR）等手段对这些化合物在金表面形成的自组装单分子膜进行了表征。发现4-（N－（2‘-巯基已基））酰胺偶氮苯的自组装膜表现出良好的电活性，电化学测定表面浓度为4．21×10(－10)mol·cm(-2)．当R为烷基链时，随烷基链的增长，膜的致密度与有序度增加GIR-IR证明在自组装腹中CH3（CH2）6C（O）NHCH2CH2SH的C＝O和N－H键与Au表面平行，分子轴线与Au表面近似垂直．     

喹啉衍生物自组装单分子膜的制备与结构

由于自组装单分子膜（SeifAssewhledMonolnyer,SAM）技术提供了在分子水平上构造理想界面的方便手段,而且所得到的膜具有优于传统m膜的均一性与稳定性,所以近年来SAM成为研究的热点．大量的研究工作表明SAM在润滑、防腐、催化老u蚀、电子转移反应研究、分子器件、非线性光学等众多领域都有广泛的应用前景［‘］．在以前的工作中我们曾报导了含酸胺键［’］、偶氮苯基团”,‘］等链内取代基的SAM的电化学与红外研究的结果,并采用化学力显微镜（CF）技术对末端为竣基的SAM进行了力滴定研究l’1．由于受合成等因素的制约,目前国…     

偶氮苯衍生物-β-环糊精包合物的自组装行为

研究了4-N（2’-巯基-乙基）羧基酰胺偶氮苯（Azo）与β-环糊精（β-CD）形成的包合物在金表面上的自组装行为．X射线光电子能谱（XPS）结果证实,Azo和Azo与β-CD形成的包合物均可在金表面上自组装形成单分子层膜．在包合物形成的自组装膜中,Azo与β-CD的摩尔比约为1：1．Azo自组装膜的电化学反应表现速率常数（Kobs）随组装时间的延长而明显减小,反映出自组装膜的排列随时间延长而趋于更加致密,从而抑制了偶氮苯基团的电化学诱导构型转化,降低了其电活性．而Azo与β-CD包合物自组装膜的Kobs值随组装时间变化不大,在组装76h以后,包合物自组装膜的Kobs比单纯偶氮苯自组装膜的Kobs高2个数量级以上．表明环糊精能够将偶氮苯分子隔开,从而抑制了偶氮苯在自组装膜中的聚集作用,有效地提高其电化学活性．     

红壤可变电荷矿物的酸碱缓冲能力及表面络合模型

氧化铁和高岭石是红壤中可变电荷的主要来源,对红壤的酸碱变化起到缓冲作用.本研究基于红壤矿物的表征和酸碱滴定实验结果,采用1-site/2-pK表面络合模型获得了其表面活性位点浓度H_s、密度D_s、酸碱平衡常数pK_a^int以及电荷零点pH_pzc等相关参数,定量解析了氧化铁和高岭土的酸碱缓冲能力.结果表明：该模型能较好地适用于分析针铁矿、赤铁矿及高岭石的表面酸碱性质;针铁矿、高岭石表面活性位点浓度H_s较高,说明其对酸具有较好的缓冲效果.根据上述酸碱性质参数,模拟计算了不同pH下的矿物表面化学物种,揭示了矿物表面反应缓冲土壤酸碱变化的机制.采用上述酸碱滴定方法及模型计算方法,分析实际林地红壤样品的酸碱缓冲能力,并采用表面络合模型计算了其表面化学物种,验证了该方法用于林地红壤酸碱缓冲能力分析的可行性.