Characterization of self-assembled monolayers of iron and cobalt octaalkylthiosubstituted phthalocyanines and their use in nitrite electrocatalytic oxidation

Cobalt and iron phenylthiosubstituted phthalocyanines have been deposited on Au electrode surfaces through the self-assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric and impedance techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of nitrite. The electrocatalytic parameters of the cobalt and iron phenylthiosubstituted phthalocyanines deposited on Au electrodes in nitrite solution were studied. Nitrite overpotentials which are lower than ever reported were obtained in this work for the iron phenylthiosubstituted phthalocyanines with very high stability.     

Synthesis and properties of novel side-chain-sulfonated polyimides from bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone

A novel side-chain-sulfonated aromatic diamine of bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone (BAPSBPS) was synthesized. Sulfonated copolyimides were synthesized by random and sequenced block copolymerization of 1,4,5,8-naphthalene tetracarboxylic dianhydride, BAPSBPS and nonsulfonated diamine. They displayed good solubility in common aprotic solvents and high desulfonation temperature of 350 °C, suggesting the high stability of sulfonic acid groups. The reduced viscosity was in the range of 0.4-1.8 dl/g at 0.5 g/dl and 35 °C. Flexible and tough membranes with reasonably high mechanical strength were prepared. They showed anisotropic membrane swelling with larger swelling in thickness than in plane. They displayed reasonably high proton conductivity (σ), taking their lower ion exchanging capacity (IEC) into account. For example, the membrane with IEC of 1.54 mequiv/g showed σ values of 81 and 11 mS/cm in water and 70% RH, respectively, at 60 °C.     

新型表面活性剂对酞菁蓝颜料的表面处理及表面性质的研究

本文自行设计并合成出新型颜料分散剂RSJ,用于酞菁蓝颜料的表面改性处理。分别研究在不同RSJ加量条件下酞菁蓝颜料临界润湿表面张力、表面自由能、流动性以及水相中分散稳定性的改善效果,并从中发现:经RSJ0.5％～3.0％添加量改性处理后,颜料临界润湿表面能γ_c由23mN/m变为34.8mN/m,提高了51％;对水的接触角由82.4°变为47°,减小了47％。表面自由能中的色散成分γ_s~d变化不大,可以认为保持不变,但是γ_s~p却由18.9mN/m变大为27.2mN/m,使得γ_s整体提高13％。此外,流动性提高2.5倍,水中分散稳定性提高了29％。     

Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.     

Drug self-assembly: A phenomenon at the nanometer scale with major impact in the structure–biological properties relationship and the treatment of disease

Under water-rich conditions, small amphiphilic and hydrophobic drug molecules self-assemble into supramolecular nanostructures. Thus, substantial modifications in their interaction with cellular structures and the ability to reach intracellular targets could happen. Additionally, drug aggregates could be more toxic than the non-aggregated counterparts, or vice versa. Moreover, since self-aggregation reduces the number of effective “monomeric” molecules that interact with the target, the drug potency could be underestimated. In other cases, the activity could be ascribed to the non-aggregated molecule while it stems from its aggregates. Thus, drug self-assembly could mislead from drug throughput screening assays to advanced preclinical and clinical trials. Finally, aggregates could serve as crystallization nuclei. The impact that this phenomenon has on the biological performance of active compounds, the inconsistent and often controversial nature of the published data and the need for recommendations/guidelines as preamble of more harmonized research protocols to characterize drug self-aggregation were main motivations for this review. First, the key molecular and environmental parameters governing drug self-aggregation, the main drug families for which this phenomenon and the methods used for its characterization are described. Then, promising nanotechnology platforms investigated to prevent/control it towards a more efficient drug development process are briefly discussed.     

酞青钴-Fe_3O_4纳米复合粒子的化学稳定性研究

制备了酞菁钴（CoPc）－Fe3O4纳米复合粒子,研究了其化学稳定性．结果表明．CoPc与Fe3O4纳米粒子通过一定程度的化学键作用形成了有效的复合．在Fe3O4纳米粒子表面形成了包覆层,有效地保护其不被空气氧化。其抗氧化能力与CoPc包裹层的数目有很强的依赖关系。     

Selective voltammetric determination of electroactive neuromodulating species in biological samples using iron(II) phthalocyanine modified multi-wall carbon nanotubes paste electrode

Iron(II) phthalocyanine (FePc) modified multi-wall carbon nanotubes paste electrodes (MWCNTPEs) were used as voltammetric sensors to selectively detect dopamine (DA) in the presence of serotonin (5-HT). The electrochemical behavior of DA at the new modified electrode was investigated using CV. The enhanced current response of DA indicates that FePc modification of the MWCNTPE surface results in a high catalytic activity for the redox reaction of DA. Differential pulse voltammetry was applied in detection of DA and 5-HT at FePc-MWCNTPE. The method parameters were optimized. Detection limit of 2.05 × 10⁻⁷ M was obtained for DA by using the electrocatalytic oxidation signal corresponding to the Fe^II/Fe^III redox process. The separation between the peak potentials of DA and 5-HT is 170 mV which is large enough for the simultaneously, selective determination of the two chemical species in their mixtures. There was no electrochemical response for ascorbic acid (AA) added in the sample. The monoamine neurotransmitter measuring method has been tested in analyzing deproteinized serum samples.     

Polypyrrole functionalized with FePcTSA for NO2 sensor application

The nitrogen dioxide (NO₂) sensing capability of polypyrrole (PPy) was enhanced dramatically after functionalized with iron(III)phthalocyanine-4,4′,4″,4-tetrasulfonic acid monosodium salt (FePcTSA). The incorporated phthalocyanine was confirmed by different characterization techniques such as UV–vis spectroscopy, FTIR, GFAAS, EDAX, etc. The resistance of the functionalized PPy decreased spontaneously during exposure to NO₂ gas at room temperature. This material exhibited excellent stability, reversibility, and reproducibility. The lowest response time (t₅₀) thus obtained is 47 s with a highest response factor (ΔR/R₀ × 100) of 50.25.     

Interaction of Langmuir–Blodgett and spin-coated films of μ-carbido-bridged ironphthalocyanine with NO2: Optical and conductimetric behaviour

The present study investigates the interaction of NO₂ gas and μ-carbido-bridged iron phthalocyanine (PcFeCFePc) films obtained by Langmuir–Blodgett (LB) and spin-coating (SC) techniques. The phthalocyanine bridged dimer under study belongs to the polynuclear unsubstituted phthalocyanines class and presents poor solubility: in contrast the corresponding N-base bis-adducts are soluble enough in organic solvents to be deposited by Langmuir–Blodgett and spin-coating techniques. The reaction with NO₂ is monitored by visible spectra variation that shows identical behaviour for both kinds of films, indicating that the chemical reaction between the gas and the films is independent of the deposition method. The electrical conductivity change as a function of time with NO₂ is instead dissimilar: for spin-coated films it shows a behaviour already observed for sandwich-type phthalocyanine whereas for LB films it resembles that of monomeric phthalocyanine. Such a response implies that the charges (holes) generated in the oxidation/reduction process are carried differently through the material, and we attempt to explain this behaviour taking into account the two different structural and morphological features induced by the two techniques.     

增效超分散剂对铜酞菁颜料表面改性的研究

本文合成了几种增效超分散剂，并用于β-型铜酞菁的表面改性，其分散性、流动性和色光均有提高。结果表明，以聚酯为溶剂化链，胺或多胺类为锚基，通过砜基连接到铜酞菁分子上制成增效超分散剂。当超分散剂的用量由0％增加至8％时，体系的流动度由29增加到45；溶剂化链的分子量在1800-8000时，体系的分散性提高明显：在不同的脂肪胺中，多乙烯多胺效果最佳。这类分散剂都具有很好的抗絮凝性能，所制成的油墨长时间置放不分层。