Novel Cyanine Dyes: Synthesis,Characterization and Photosensitization‐Structure Correlation

Novel furo, thieno and pyrrolo[2,3‐b]pyrazole cyanine dyes were synthesized. The structure‐photosensitization properties correlation of the dyes were examined in 95% ethanol solution by absorption spectroscopy. The chemical structure of the starting biheterocyclic compounds and their derived cyanine dyes were confirmed by elemental analysis, IR and ¹H NMR spectroscopy.     

Photostability of novel copolymers functionalized with laser dyes based on modified rhodamine 6G and 1,8-naphthalimide

Modified rhodamine 6G molecules (Rh-Al or Rh-Aln) with polymerizable double bonds had been copolymerized with 1,8-naphthalimide derivatives. In copolymers PRNAM, naphthalimide moieties are connected to rhodamine moieties at nitrogen atom of rhodamine moiety, and in copolymers PRNM naphthalimide moieties are connected to rhodamine moieties at ester group of rhodamine moiety. We report on their photostability in liquid solution and in solid film. The photodegradation kinetics of novel copolymers functionalized with laser dyes based on modified rhodamine 6G and 1,8-naphthalimide has been studied by UV-VIS absorption spectroscopy. The results show that the rates of the photofading reactions of these novel copolymers follow quasi-first-order. The photostability of the copolymers functionalized with laser dyes in solid films is better than that in solutions. The different type of the copolymer shows the different photostability.     

三维树枝状C/PbWO4催化剂的制备及其对不同染料的光催化降解性能

采用水热法合成了一种高结晶度的3D树枝状C/PbWO₄复合光催化剂（其中碳的质量分数分别为0.13%、0.26%、0.52%、0.78%）。应用X射线衍射、N₂物理吸附、扫描电子显微镜、透射电子显微镜、能量色散X射线光谱、紫外可见漫反射光谱、光致发光光谱和光电流响应等手段对合成样品进行了表征。研究结果表明,当C的复合量为0.52%时,催化剂在降解偶氮染料酸性橙Ⅱ、甲基橙和罗丹明B呈现出最高的光催化活性,在光照100 min内对20 mg·L^-1酸性橙Ⅱ的降解率达到97%,为纯PbWO₄的2.48倍。C/PbWO₄复合光催化剂活性提高的主要原因是掺杂在催化剂表面的C成为了电子俘获中心,有效俘获光生电子,促进光生电子和空穴分离的显著效果,从而产生更多活性物种（·OH、h⁺）参与染料分子的降解,提升光催化活性。     

高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱筛查和确证纺织品中的致癌染料

建立了高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱(HPLC-LTQ/Orbitrap MS)筛查和确证生态纺织品中致癌染料的方法。样品在水浴(95 ℃)中用吡啶/水(1/1, v/v)振荡(150 r/min)提取,上清液过聚四氟乙烯(PTFE)滤膜后,CAPCELL PAK C₁₈色谱柱(100 mm×2.0 mm, 5 μm)分离,以乙腈和5 mmol/L乙酸铵水溶液(含0.01%甲酸)、乙腈和5 mmol/L乙酸铵水溶液分别作为正、负电喷雾离子化(ESI)模式的色谱流动相梯度洗脱。在m/z 200~800范围内进行一级质谱全扫描。以准分子离子峰的精确质量数和提取的色谱图峰面积进行筛查分析和定量,以保留时间和数据依赖扫描(data-dependent scan)模式获得的子离子质谱图进行定性确证。9种染料的质量准确度小于5×10^-6(5 ppm),线性良好,相关系数大于0.99,方法检出限为0.125~25 mg/kg。3个添加水平的回收率范围为62.13%~116.28%,相对标准偏差小于15%。应用该方法检测了棉、涤纶及混纺纤维等20余件纺织品样品中的致癌染料残留。该方法准确、可靠。     

New Dual Donor–Acceptor (2D‐π‐2A) Porphyrin Sensitizers for Stable and Cost‐Effective Dye‐Sensitized Solar Cells

A series of porphyrin sensitizers that featured two electron‐donating groups and dual anchoring groups that were connected through a porphine π‐bridging unit have been synthesized and successfully applied in dye‐sensitized solar cells (DSSCs). The presence of electron‐donating groups had a significant influence on their spectroscopic, electrochemical, and photovoltaic properties. Overall, the dual anchoring groups gave tunable electronic properties and stronger attachment to TiO₂. These new dyes were readily synthesized in a minimum number of steps in gram‐scale quantities. Optical and electrochemical data confirmed the advantages of these dyes for use as sensitizers in DSSCs. Porphyrins with electron‐donating amino moieties provided improved charge separation and better charge‐injection efficiencies for the studied dual‐push–pull dyes. Attenuated total reflectance–Fourier‐transform infrared (ATR‐FTIR) and X‐ray photoelectron spectroscopy of the porphyrin dyes on TiO₂ suggest that both p‐carboxyphenyl groups are attached onto TiO₂, thereby resulting in strong attachment. Among these dyes, cis-Zn2BC2A , with two electron‐donating 3,6‐ditertbutyl‐phenyl‐carbazole groups and dual‐anchoring p‐carboxyphenyl groups, showed the highest efficiency of 4.07 %, with J_SC=9.81 mA cm^?2, V_OC=0.63 V, and FF=66 %. Our results also indicated a better photostability of the studied dual‐anchored sensitizers compared to their mono‐anchored analogues under identical conditions. These results provide insight into the developments of a new generation of high‐efficiency and thermally stable porphyrin sensitizers.     

Synthesis and Molecular Properties of Acceptor‐Substituted Squaraine Dyes

A broad series of more than 20 acceptor‐substituted squaraines was synthesized that feature different acceptor functionalities at the central squaraine four‐membered ring. The influence of these acceptor units on the reactivity of semisquaraine precursors and stability of the respective squaraines were explored. Thereby the dicyanovinyl group was found to be the most versatile acceptor group that enabled various modifications at the donor moiety of the squaraine scaffold, leading to an extended series of dicyanovinyl‐functionalized squaraines. The variation of donor units afforded a set of NIR fluorophores that cover a wavelength region from the visible at about 650 nm far into the NIR up to 920 nm with fluorescence quantum yields between 0.93 and 0.11 and outstanding optical brightness. This excellent optical property is related to a rigid molecular scaffold that is fixed in an all‐cis configuration by the additional dicyanovinyl acceptor unit. The change of the molecular symmetry from C_2h to C_2v upon functionalization of the squaraine core with dicyanovinyl acceptor group has been confirmed in solution by electro‐optical absorption (EOA) spectroscopy, revealing permanent ground‐state dipole moments μ_g in the range between 4.3 and 6.4 D. These dipole moments direct an antiparallel packing of the molecules in the solid state according to single‐crystal X‐ray analyses achieved for four dicyanovinyl‐functionalized squaraines. The structural properties, the EOA results, as well as the band shapes of the optical spectra indicate that these polymethine dyes are cyanine‐type chromophores. It is worth noting that the orientation of the dipole moment vectors is orthogonal to the orientation of the transition dipole moment vectors, which is an uncommon but characteristic feature of this rather novel class of polymethine dyes. With regard to applications of these dyes in organic solar cells, their redox properties were also studied by cyclic voltammetry.     

Zinc Porphyrins with a Pyridine‐Ring‐Anchoring Group for Dye‐Sensitized Solar Cells

Anchoring groups are extremely important in controlling the performance of dye‐sensitized solar cells (DSCs). The design and characterization of sensitizers with new anchoring groups, in particular non‐carboxylic acid groups, has become a recent focus of DSC research. Herein, new donor? π? acceptor zinc? porphyrin dyes with a pyridine ring as an anchoring group have been designed and synthesized for applications in DSCs. Photophysical and electrochemical investigations demonstrated that the pyridine ring worked effectively as an anchoring group for the porphyrin sensitizers. DSCs that were based on these new porphyrins showed an overall power‐conversion efficiency of about 4.0 % under full sunlight (AM 1.5G, 100 mW cm^?2).     

冠醚硒菁染料的合成

合成了对称和非对称两个新的冠醚硒菁染料2,2'-二乙基-45,4'5'-双并-(15-冠-5)硒碳菁碘化季铵盐和2,2'-二乙基-4,5-并-(15-冠-5)硒碳菁碘化季铵盐以用三种新的中间体2,2'-二硝基-4,5,4',5'-双并-(15-冠-5)二苯基二硒化物, 2-甲基-5,6-并-(15-冠-5)苯并硒唑和2-甲基-3-乙基-5,6-并-(15-冠-5)苯并硒碘化季铵盐。报道了它们的红外、紫外、核磁共振、质谱数据。     

Scratch and Abrasion Resistant Coatings on Plastic Lenses—State of the Art,Current Developments and Perspectives

The manufacturing of ophthalmic lenses is one of the most important markets worldwide and, therefore, strong research efforts are undertaken to continuously improve the quality of the products, either silicate glasses or organic polymer lenses. Hybrid sol-gel based materials play a major role in this highly competitive field and have contributed significantly to the commercial success of the organic base materials. Recent developments concern fast curing and patternable coatings that might soon become part of this business. The compatibility of hybrid sol-gel materials either with organic dyes or with inorganic vacuum borne coatings offers further possibilities to develop highly sophisticated lenses meeting not only customer needs like perfect corrective function, high optical quality and protection, but also high durability as well as cosmetic and decorative aspects. An overview and a few recent developments are outlined below.