Controlling supramolecular structures in iron tetrasulfonated phthalocyanine films through pH variation: implications for thin-film device performance.

Improving the performance of thin film-based devices is a crucial factor for their successful application, mainly for organic electronic semiconductors. The adjustment of supramolecular structuring of thin films plays a role in the optical and electrical properties. In this sense, we investigated how various pH values, such as 2.5, 6.0, and 9.0, of the solutions influenced the growth of iron tetrasulfonated phthalocyanine (FeTsPc) Layer-by-Layer (LbL) films and their respective supramolecular structures as well as their electrochemical properties. The supramolecular structures were evaluated via UV-vis absorption spectroscopy, quartz crystal microbalance (QCM), micro-Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and cyclic voltammetry. The different pH values of the solution induce different degrees of molecular aggregation for FeTsPc (monomer, dimer, and aggregate formation). For instance, the higher the pH, the higher the aggregation. Films produced at pH 2.5 were organized preferentially with the molecules perpendicular to the substrate, while films at pH 6.0 and 9.0 were organized preferentially with the molecules parallel to the substrate. Besides, the film produced at pH 2.5 results in higher film thickness, higher stability, and better electrocatalytic behavior for the electrochemical detection of catechol. The results presented here enhance the understanding of nanostructured films, helping to harness supramolecular organization to improve the performance of thin-film devices.

Lipid-matrix effects on tyrosinase immobilization in Langmuir and Langmuir-Blodgett films.

The immobilization of the enzyme tyrosinase (Tyr) in lipid matrices can be explored to produce biosensors for detecting polyphenols, which is relevant for the food industry. Herein, we shall demonstrate the importance of the lipid composition to immobilize the enzyme tyrosinase in Langmuir-Blodgett (LB) films. Tyr could be incorporated into Langmuir monolayers of arachidic acid (AA), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (sodium salt) (DPPG), having as the main effect an expansion in the monolayers. Results from polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) pointed to electrostatic interactions between the charged residues of Try and the lipid headgroups, in addition to changes in the order of lipid chains. The interaction between Tyr and DPPC in Langmuir monolayers can be correlated with the superior performance of DPPC/Tyr LB films used as biosensors to detect catechol by cyclic voltammetry. The molecular-level interactions assessed via PM-IRRAS are therefore believed to drive an immobilization process for Tyr in the lipid LB matrix and may serve as a general criterion to identify matrices that preserve enzyme activity.

Supramolecular architecture and electrical conductivity in organic semiconducting thin films.

Organic thin films are an essential component of the structure of optical and electronic devices. However, the optical and electrical properties of these films depend on their supramolecular architecture, which may vary according to the techniques used to manufacture them. Here, the correlation between conductivity and supramolecular architecture was investigated. The supramolecular architecture was analyzed in terms of the molecular organization and J- or H-aggregation established during the fabrication of perylene tetracarboxylic diimide (PTCD) nanometric films. Three deposition techniques, Langmuir-Schaefer (LS), Langmuir-Blodgett (LB), and Physical Vapor Deposition (PVD), were evaluated. The UV-vis absorption spectra indicated that LS, LB, and PVD films grow homogeneously. Also, the presence of J and H aggregates was observed for all films, the H aggregates prevailing for the LB film. The FTIR measurements suggested that the molecular organization is similar for LS and LB films, with a tendency to form head-on organization onto a solid substrate. For the PVD film, the perylene macrocycles are inclined approximately 45° relative to the substrate. AFM measurements indicated a homogenous surface for all films. In terms of electrical conductivity, the highest conductivity was found for LS, followed by LB and PVD. The conductivity values were interpreted in terms of molecular organization and J- or H-aggregate formation.

Metallic Phthalocyanines: impact of the film deposition method on its supramolecular arrangement and sensor performance.

This short review gives a concise overview of the impact of deposition methods on the supramolecular arrangement of metallic phthalocyanine films and their applications. Primarily, an introduction about the possible phthalocyanine molecular structures and derivatives obtained from modification on the phthalocyanine rings was presented. The possibility of perfecting/improving the supramolecular arrangement of metallic phthalocyanine (MPcs) films by using different deposition techniques such as Langmuir-Blodgett (LB), Langmuir-Schaefer (LS), Layer-by-Layer (LbL), physical vapor deposition (PVD) and electrodeposition was discussed in further details. Herein, we highlighted some techniques used on the characterization of supramolecular arrangement (morphology, optical properties, and molecular organization), including the impact on sensing applications. The main scope of this short review is focused on the advances made in this research field in the last five years.

Angiosarcoma of small intestine: case report and literature review / Angiossarcoma de intestino delgado: relato de caso e revisão da literatura

ABSTRACT Introduction: Angiosarcomas are rare pathologies, and their appearance in the small intestine is extremely unusual. Case report: Female patient presenting vomiting, colic, abdominal distension and peritoneal irritation. An exploratory laparotomy and an enterectomy were performed. Histopathology revealed vascular neoplasm; immunohistochemistry, markers CD31, p53 and cell proliferation antigen Ki-67. The patient developed diffuse sarcomatosis and died two months after the onset of symptoms. Conclusion: This case demonstrates the difficulty in early diagnosing this pathology, due to its nonspecific clinical presentation. The disease aggressiveness, its unestablished predisposing factors and the controversy around the adequate treatment engender the poor prognosis.

RESUMO Introdução: Angiossarcomas são patologias raras, e o aparecimento deles no intestino delgado é extremamente incomum. Relato de caso: Paciente do sexo feminino apresentando vômitos, cólica, distensão abdominal e irritação peritoneal. Foram realizadas laparotomia exploratória e enterectomia, evidenciando-se neoplasia vascular ao anatomopatológico e marcadores CD31, p53 e antígeno de proliferação celular Ki-67 à imuno-histoquímica. A paciente evoluiu com sarcomatose difusa e faleceu dois meses após o início dos sintomas. Conclusão: Demonstra-se a dificuldade em diagnosticar precocemente essa patologia devido à sua clínica inespecífica. A agressividade da doença, seus fatores predisponentes indeterminados e a controvérsia referente ao tratamento adequado suscitam seu péssimo prognóstico.