纳秒级脉冲激光对战场中广泛使用的光电传感器构成了严重威胁。光限幅材料在阻止强激光通过的同时, 不影响低能量信号光的通过, 是目前激光防护领域的研究热点。针对可见-近红外波段光电传感器强激光防护应用需求, 在金属酞菁化合物基础上, 基于增强其共轭体系电子云密度的设计思想制备了一种新型高性能光限幅材料--四枯丁苯氧基氯代酞菁铟, 并对其进行了测试表征。瞬态吸收光谱实验表明,四枯丁苯氧基氯代酞菁铟具有很强且长寿命的激发态吸收。光限幅性能测试证明其光限幅启动阈值为8 mJ/cm2, 光限幅阈值为0.06 J/cm2, 损伤阈值大于4 J/cm2,当输入能流达到3 J/cm2时, 光限幅器件透过率下降到6%。由测试结果可以看出, 该材料光限幅启动阈值及光限幅阈值低, 损伤阈值高, 可见-近红外波段线性透过率高, 具有优异的光限幅性能, 在光电系统激光防护中具有较高的应用前景。

金属酞菁是一类以异吲哚为组成单元的人工合成的平面大环配合物, 它们不仅是高品质的颜料和染料, 也是太阳能电池、液晶材料、信息存储、环境催化等领域的新兴材料。传统的金属酞菁制备往往需要高沸点溶剂的回流反应以及使用浓硫酸纯化产物, 普遍存在毒性高、效率低、耗时长等缺点。从绿色化学的发展和新型金属酞菁材料的制备要求来看, 采用环境友好、成本低廉、易于操作的新方法制备与纯化金属酞菁是未来的发展趋势。本文综述了溶剂热法一步制备金属酞菁晶体的研究进展, 总结了能够通过该方法制备的金属酞菁晶体种类及其相应的反应条件和产物结构, 综合评价了该方法的技术优势, 并对应用溶剂热法制备的金属酞菁晶体的未来发展进行了展望。

Targeted photodynamic therapy (TPDT) based on the photosensitizers responsive for tumor microenvironment is promising because of the better anti-tumor effect and less phototoxicity against normal tissue than the traditional PDT. Nanoparticle-based stimuli-responsive photosensitizers have been widely explored for TPDT. Based on the acidic microenvironments in solid tumors, an ultrasmall pH-responsive silicon phthalocyanine nanomicelle (PSN) (smaller than 10nm) was designed for selective PDT of tumor. PSN had high drug loading efficacy (more than 28%) and exhibited morphological transitions, enhanced fluorescence and improved singlet oxygen yield under acidic environments. PSN was renal clearable and could rapidly accumulate and be retained at tumor sites, achieving a tumor-inhibiting effect better than phthalocyanine micelle without pH response. Tumors of mice treated with PSN for PDT were completely ablated without recurrence. Thus, we have developed a phthalocyanine-based pH-responsive micelle with excellent tumor targeting ability, which is expected to realize the selective PDT of tumor.Targeted photodynamic therapy (TPDT) based on the photosensitizers responsive for tumor microenvironment is promising because of the better anti-tumor effect and less phototoxicity against normal tissue than the traditional PDT. Nanoparticle-based stimuli-responsive photosensitizers have been widely explored for TPDT. Based on the acidic microenvironments in solid tumors, an ultrasmall pH-responsive silicon phthalocyanine nanomicelle (PSN) (smaller than 10nm) was designed for selective PDT of tumor. PSN had high drug loading efficacy (more than 28%) and exhibited morphological transitions, enhanced fluorescence and improved singlet oxygen yield under acidic environments. PSN was renal clearable and could rapidly accumulate and be retained at tumor sites, achieving a tumor-inhibiting effect better than phthalocyanine micelle without pH response. Tumors of mice treated with PSN for PDT were completely ablated without recurrence. Thus, we have developed a phthalocyanine-based pH-responsive micelle with excellent tumor targeting ability, which is expected to realize the selective PDT of tumor.

利用Z扫描技术研究了曙红Y、酞菁锌、曙红Y/酞菁锌复合薄膜的非线性吸收特性。在脉冲能量为130 μJ、脉宽为4 ns、波长为532 nm的激光作用下，实验显示曙红Y具有较强的饱和吸收，酞菁锌具有较强的反饱和吸收，吸收特性随着质量分数的增加而增强，重复测试表明两者都具有良好的稳定性。曙红Y/酞菁锌复合的聚乙烯醇（PVA）薄膜兼备饱和吸收与反饱和吸收特性，通过调整质量分数配比可调控透过率，调节材料的非线性吸收系数，实现材料限幅特性的“加法”。此种复合材料可用于新型光限幅器和光开关等光学器件。

The detection of hydrogen sulfide (H₂S) is essential because of its toxicity and abundance in the environment. Hence, there is an urgent requisite to develop a highly sensitive and economical H₂S detection system. Herein, a zinc phthalocyanine (ZnPc) thin film-based K+-exchanged optical waveguide (OWG) gas sensor was developed for H₂S detection by using spin coating. The sensor showed excellent H₂S sensing performance at room temperature with a wide linear range (0.1 ppm – 500 ppm), reproducibility, stability, and a low detection limit of 0.1 ppm. The developed sensor showed a significant prospect in the development of cost-effective and highly sensitive H₂S gas sensors.

通过调控对六联苯(p-6P)诱导层和酞菁锌(ZnPc)蒸镀工艺条件, 研究了有机半导体小分子的结晶生长成膜与ZnPc有机薄膜晶体管(OTFT)器件电性能的关系。结果表明, p-6P在180~190 ℃较高的衬底生长温度和3~4 nm的生长厚度下能够形成更大的结晶畴以及对二氧化硅衬底表面更好的覆盖, 有利于诱导ZnPc小分子的结晶生长, 使晶畴的排列更加有序。同时通过X射线衍射分析晶体结构, 结果表明p-6P衬底温度的升高会明显提高ZnPc薄膜的结晶性。电性能研究发现, ZnPc蒸镀厚度的增加会显著提高器件的饱和电流和迁移率, 在异质诱导条件下, p-6P薄膜厚度为3 nm、ZnPc蒸镀厚度为20 nm时, 器件的饱和电流为1.08×10-6 A, 迁移率为1.66×10-2 cm2·V-1·s-1。

通过浸渍提拉法制备出TiO2薄膜/锡掺杂玻璃复合光波导(OWG)元件,在其表面利用旋转甩涂法固定一层酞菁锌(ZnPc)敏感层,制备了高灵敏度的硫化氢(H2S)复合OWG气体传感器。优化传感器的制备条件,当提拉机的提拉速度为80 mm·min -1、匀胶机转速为1600 r·min -1、ZnPc的质量分数为0.05%时,该传感器对H2S气体的选择性响应最佳,可以检测到体积分数为1×10 -9的H2S气体。此外,该传感器在一个月内表现出良好的稳定性。

通过共价键合将二氨基二枯丁苯氧基氯代铟酞菁(Pc)与羧基化氧化石墨烯(GO-COOH)键合在一起, 得到二氨基二枯丁苯氧基氯代铟酞菁-氧化石墨烯键合产物(Pc-GO-COOH), 并以键合产物为原料反应得到引发剂。以甲基丙烯酸甲酯(MMA)为聚合反应单体, 通过原子转移自由基聚合(ATRP)反应得到四种不同分子量的聚合物样品。采用凝胶渗透色谱(GPC)对聚合物分子量分布测试, 结果表明, 所制备的聚合物的分子量分布范围较窄, 聚合反应具有良好的可控性。采用Z-扫描方法对聚合物样品溶液进行的三阶非线性测试结果表明, 所制备的聚合物具有优良的三阶非线性光学性质, 且当聚合物的分子量分别为9 063和12 196时, 三阶非线性极化率值分别为8.1×10-11、2.1×10-11 esu。同时对聚合物样品的光限幅性能测试结果表明, 两种样品的有效激发态与基态吸收截面比分别为2.69和2.20, 具有较好的光限幅能力, 具有较大的应用前景。

Atomic scale manufacturing is a necessity of the future to develop atomic scale devices with high precision. A different perspective of the quantum realm, which includes the tunnelling effect, leakage current at the atomic-scale, Coulomb blockade and Kondo effect, is inevitable for the fabrication and hence, the mass production of these devices. For these atomic-scale device development, molecular level devices must be fabricated. Proper theoretical studies could be an aid towards the experimental realities. Electronic transport studies are the basis to realise and interpret the problems happening at this minute scale. Keeping these in mind, we present a periodic energy decomposition analysis (pEDA) of two potential candidates for moletronics: phthalocyanines and porphyrins, by placing them over gold substrate cleaved at the (111) plane to study the adsorption and interaction at the interface and then, to study their application as a channel between two electrodes, thereby, providing a link between pEDA and electronic transport studies. pEDA provides information regarding the bond strength and the contribution of electrostatic energy, Pauli’s energy, orbital energy and the orbital interactions. Combining this analysis with electronic transport studies can provide novel directions for atomic/close-toatomic- scale manufacturing (ACSM). Literature survey shows that this is the first work which establishes a link between pEDA and electronic transport studies and a detailed pEDA study on the above stated molecules. The results show that among the molecules studied, porphyrins are more adsorbable over gold substrate and conducting across a molecular junction than phthalocyanines, even though both molecules show a similarity in adsorption and conduction when a terminal thiol linker is attached. A further observation establishes the importance of attractive terms, which includes interaction, orbital and electrostatic energies, in correlating the pEDA study with the transport properties. By progressing this research, further developments could be possible in atomic-scale manufacturing in the future.