LASU: An efficient and stable phthalocyanine dye with tolerable safety profile for self-disinfecting anti-COVID textiles activated by ambient light.

BACKGROUND: Recent COVID crisis has demonstrated that modern society urgently needs an accessible protection against mass infections, especially viruses, as the new strains are appearing at an ever-increasing pace and cause severe harm to the population and the world economy. METHODS: We have developed an efficient phthalocyanine photosensitizer LASU, that is suitable for dyeing textiles and allows to prepare reusable self-disinfecting fabrics with strong antiviral properties. The safety profile of LASU was evaluated in accredited laboratories by several in vitro assays according to the OECD-guidelines. RESULTS: The textiles impregnated with LASU phthalocyanine showed a significant antiviral photodynamic effect even under moderate indoor and outdoor light. The dye did not show any genotoxic potential in human lymphocyte micronucleus assay. It showed a possible indication for eye irritation in human EpiOcular™ model and was phototoxic when tested in mouse BALB/c 3T3 cell test in the presence and absence of UVA-irradiation. CONCLUSION: Novel phthalocyanine-dyed textiles are suitable for general use as self-disinfecting antiviral barriers and materials in hospitals, households, and public places. The safety profile of LASU is the phototoxic effect which is related to LASU´s mode of action.

Review: chitosan-based biopolymers for anion-exchange membrane fuel cell application.

Chitosan (CS)-based anion exchange membranes (AEMs) have gained significant attention in fuel cell applications owing to their numerous benefits, such as environmental friendliness, flexibility for structural alteration, and improved mechanical, thermal and chemical durability. This study aims to enhance the cell performance of CS-based AEMs by addressing key factors including mechanical stability, ionic conductivity, water absorption and expansion rate. While previous reviews have predominantly focused on CS as a proton-conducting membrane, the present mini-review highlights the advancements of CS-based AEMs. Furthermore, the study investigates the stability of cationic head groups grafted to CS through simulations. Understanding the chemical properties of CS, including the behaviour of grafted head groups, provides valuable insights into the membrane's overall stability and performance. Additionally, the study mentions the potential of modern cellulose membranes for alkaline environments as promising biopolymers. While the primary focus is on CS-based AEMs, the inclusion of cellulose membranes underscores the broader exploration of biopolymer materials for fuel cell applications.

Development of Quaternized Chitosan Integrated with Nanofibrous Polyacrylonitrile Mat as an Anion-Exchange Membrane.

A two-phase anion-exchange membrane was prepared from quaternized chitosan (QCS) integrated with an electrospun polyacrylonitrile (PAN) scaffold by spin coating. To synthesize QCS, glycidyltrimethylammonium chloride in various amounts was introduced into the structure of CS. The characterization of the cast cross-linked QCS (CQCS) membranes by impedance spectroscopy revealed the ionic conductivity (IC) in the range of 2.8 × 10-4 to 8.2 × 10-4 S cm-1 and the degree of quaternization (DQ) of 26.4-51.0%, where the CQCS film with the DQ of 51.0% showed excellent performance. When CQCS was reinforced with a PAN fiber mat, the newly developed composite membrane demonstrated the highest IC of 34 × 10-4 S cm-1 at 80 °C, low swelling, and an almost eightfold increase in tensile strength at a fully hydrated state compared to pristine materials. Moreover, the CQCS/PAN membrane was chemically stable and revealed increasing hydroxide transport during 1 month immersion in alkaline media.

Lipophilicity prediction of three photosensitizers by liquid-liquid extraction, HPLC, and DFT methods.

Photodynamic therapy (PDT) is a method of treating precancerous diseases and malignant neoplasms. The efficacy of PDT depends on different parameters such as light dosimetry, oxygen availability, and photophysical and physical-chemical properties of the photosensitizer. In PDT, a photosensitizer is activated using light to promote oxygen photosensitization and cellular transport plays a key role in the reach of it to the desired tissue. In particular, to know the effectiveness of the drug delivery in PDT and its dosage forms to target damaged organs, along with such characteristics as water solubility, it is important to know the ability of a substance to penetrate through cell membrane or accumulate in it. Lipophilicity is used to quantify the earlier-described abilities. We evaluated the lipophilicity of three selected photosensitizers (PS) (protoporphyrin IX, pyropheophorbide-a and photofrin) by means of three different methods: octanol-water distribution methods (shake-flask), reversed-phase high-performance liquid chromatography (HPLC) and theoretical calculations based on density functional theory (DFT). We describe and compare the results of these various methods.

Binding and Degradation Reaction of Hydroxide Ions with Several Quaternary Ammonium Head Groups of Anion Exchange Membranes Investigated by the DFT Method.

Commercialization of anion exchange membrane fuel cells (AEMFCs) has been limited due to the chemical degradation of various quaternary ammonium (QA) head groups, which affects the transportation of hydroxide (OH−) ions in AEMs. Understanding how various QA head groups bind and interact with hydroxide ions at the molecular level is of fundamental importance to developing high-performance AEMs. In this work, the binding and degradation reaction of hydroxide ions with several QA head groups­(a) pyridinium, (b) 1,4-diazabicyclo [2.2.2] octane (DABCO), (c) benzyltrimethylammonium (BTMA), (d) n-methyl piperidinium, (e) guanidium, and (f) trimethylhexylammonium (TMHA)­are investigated using the density functional theory (DFT) method. Results of binding energies ("∆" EBinding) show the following order of the binding strength of hydroxide ions with the six QA head groups: (a) > (c) > (f) > (d) > (e) > (b), suggesting that the group (b) has a high transportation rate of hydroxide ions via QA head groups of the AEM. This trend is in good agreement with the trend of ion exchange capacity from experimental data. Further analysis of the absolute values of the LUMO energies for the six QA head groups suggests the following order for chemical stability: (a) < (b)~(c) < (d) < (e) < (f). Considering the comprehensive studies of the nucleophilic substitution (SN2) degradation reactions for QA head groups (c) and (f), the chemical stability of QA (f) is found to be higher than that of QA (c), because the activation energy ("∆" EA) of QA (c) is lower than that of QA (f), while the reaction energies ("∆" ER) for QA (c) and QA (f) are similar at the different hydration levels (HLs). These results are also in line with the trends of LUMO energies and available chemical stability data found through experiments.

Photophysical Properties of Protoporphyrin IX, Pyropheophorbide-a and Photofrin® in Different Conditions.

Photodynamic therapy (PDT) is an innovative treatment of malignant or diseased tissues. The effectiveness of PDT depends on light dosimetry, oxygen availability, and properties of the photosensitizer (PS). Depending on the medium, photophysical properties of the PS can change leading to increase or decrease in fluorescence emission and formation of reactive oxygen species (ROS) especially singlet oxygen (1O2). In this study, the influence of solvent polarity, viscosity, concentration, temperature, and pH medium on the photophysical properties of protoporphyrin IX, pyropheophorbide-a, and Photofrin® were investigated by UV-visible absorption, fluorescence emission, singlet oxygen emission, and time-resolved fluorescence spectroscopies.

New Phenalenone Derivatives: Synthesis and Evaluation of Their Singlet Oxygen Quantum Yield.

1H-Phenalen-1-one is a very efficient and easy-to-synthesize photosensitizer. Many substitutions have been previously described, but most of them significantly reduce the singlet oxygen quantum yield. The chloromethyl derivative described elsewhere is a good starting point for the synthesis of many useful derivatives because of the methylene bridge that saves its unique photosensitizing properties. Eighteen new phenalenone derivatives have been synthesized, bearing amine, carboxylic acid, alcohol, azide, and other major functional groups in organic chemistry. These reactions were carried out in good-to-excellent yields, and most of these new compounds retained the singlet oxygen quantum yield of the parent molecule. These new derivatives are very promising precursors for a number of applications such as the development of photosensitive antimicrobial agents or materials.

Polythiophenes with Cationic Phosphonium Groups as Vectors for Imaging, siRNA Delivery, and Photodynamic Therapy.

In this work, we exploit the versatile function of cationic phosphonium-conjugated polythiophenes to develop multifunctional platforms for imaging and combined therapy (siRNA delivery and photodynamic therapy). The photophysical properties (absorption, emission and light-induced generation of singlet oxygen) of these cationic polythiophenes were found to be sensitive to molecular weight. Upon light irradiation, low molecular weight cationic polythiophenes were able to light-sensitize surrounding oxygen into reactive oxygen species (ROS) while the highest were not due to its aggregation in aqueous media. These polymers are also fluorescent, allowing one to visualize their intracellular location through confocal microscopy. The most promising polymers were then used as vectors for siRNA delivery. Due to their cationic and amphipathic features, these polymers were found to effectively self-assemble with siRNA targeting the luciferase gene and deliver it in MDA-MB-231 cancer cells expressing luciferase, leading to 30-50% of the gene-silencing effect. In parallel, the photodynamic therapy (PDT) activity of these cationic polymers was restored after siRNA delivery, demonstrating their potential for combined PDT and gene therapy.

Fighting Hypoxia to Improve PDT.

Photodynamic therapy (PDT) has drawn great interest in recent years mainly due to its low side effects and few drug resistances. Nevertheless, one of the issues of PDT is the need for oxygen to induce a photodynamic effect. Tumours often have low oxygen concentrations, related to the abnormal structure of the microvessels leading to an ineffective blood distribution. Moreover, PDT consumes O2. In order to improve the oxygenation of tumour or decrease hypoxia, different strategies are developed and are described in this review: 1) The use of O2 vehicle; 2) the modification of the tumour microenvironment (TME); 3) combining other therapies with PDT; 4) hypoxia-independent PDT; 5) hypoxia-dependent PDT and 6) fractional PDT.

New photodynamic molecular beacons (PMB) as potential cancer-targeted agents in PDT.

Further improvements in Photodynamic therapy (PDT) necessitate that the dye targets more selectively tumour tissues or neovascularization than healthy cells. Different enzymes such as matrix metalloproteinases (MMPs) are overexpressed in tumour areas. Among these MMPs, gelatinases (MMP-2 and MMP-9) and its activator MMP-14 are known to play a key role in tumour angiogenesis and the growth of many cancers such as glioblastoma multiforme (GBM), an aggressive malignant tumour of the brain. These last years, the concept of photodynamic molecular beacons (PMB) became interesting for controlling the photosensitizer's ability to generate singlet oxygen (1O2) close to target biomolecules as MMPs. We report herein novel PMBs triggered by MMP-2 and/or MMP-9 and/or MMP-14, comprising a photosensitizer and a singlet oxygen quencher linked by MMP cleavable peptide linker (H-GRIGFLRTAKGG-OH). First of all, we focused on the synthesis and the photophysical study of different derivatives photosensitizer-peptide. This preliminary work concluded on an influence of the nature and the distance from the peptide, but not of the position of the photosensitizer in these derivatives on the proteolytic enzymatic action. The nature of the quencher used (a blackberry quencher (BBQ-650) or a black hole quencher (BHQ3)) does not influence the enzymatic action. We also studied the influence of an additional PEG spacer. Finally, the synthesis, the singlet oxygen quenching efficiency and the enzymatic activation of these new MMP- cleavable-PMBs were compared.

Extraction, Identification and Photo-Physical Characterization of Persimmon (Diospyros kaki L.) Carotenoids.

Carotenoid pigments were extracted and purified from persimmon fruits using accelerated solvent extraction (ASE). Eleven pigments were isolated and five of them were clearly identified as all-trans-violaxanthine, all-trans-lutein, all-trans-zeaxanthin all-trans-cryptoxanthin and all-trans-ß-carotene. Absorption and fluorescence spectra were recorded. To evaluate the potential of ¹O2 quenching of the purified carotenoids, we used a monocarboxylic porphyrin (P1COOH) as the photosensitizer to produce ¹O2. The rate constants of singlet oxygen quenching (Kq) were determined by monitoring the near-infrared (1270 nm) luminescence of ¹O2 produced by photosensitizer excitation. The lifetime of singlet oxygen was measured in the presence of increasing concentrations of carotenoids in hexane. Recorded Kq values show that all-trans-ß-cryptoxanthin, all-trans-ß-carotene, all-trans-lycopene and all-trans-zeaxanthin quench singlet oxygen in hexane efficiently (associated Kq values of 1.6 × 108, 1.3 × 108, 1.1 × 108 and 1.1 × 108 M-1·s-1, respectively). The efficiency of singlet oxygen quenching of ß-cryptoxanthin can thus change the consideration that ß-carotene and lycopene are the most efficient singlet oxygen quenchers acting as catalysts for deactivation of the harmful ¹O2.

Folic acid conjugates with photosensitizers for cancer targeting in photodynamic therapy: Synthesis and photophysical properties.

Recent researches in photodynamic therapy have focused on novel techniques to enhance tumour targeting of anticancer drugs and photosensitizers. Coupling a photosensitizer with folic acid could allow more effective targeting of folate receptors which are over-expressed on the surface of many tumour cells. In this study, different folic acid-OEG-conjugated photosensitizers were synthesized, characterized and their photophysical properties were evaluated. The introduction of an OEG does not significantly improve the hydrophilicity of the FA-porphyrin. All the FA-targeted photosensitizers present good to very good photophysical properties. The best one appears to be Ce6. Molar extinction coefficient, fluorescence and singlet oxygen quantum yields were determined and were compared to the corresponding photosensitizer alone.

The Interest of Folic Acid in Targeted Photodynamic Therapy.

Photodynamic therapy is an alternative to chemotherapy and radiotherapy for cancer treatment. PDT is clinically applied to treat age-related macular degeneration and several types of cancer. Most of the time, the selectivity of the treatment is brought about by the application of light. Another strategy to improve selectivity is to design and synthesize targeted photosensitizers or nanoparticles, which can identify and selectively accumulate within tumor tissues. This review presents our inventory of all the data concerning the use of folic acid as a promising targeting unit to improve the selectivity of photosensitizers to folic acid receptors. We will discuss the strategies that are developed to couple folic acid to photosensitizers or nanoparticles as well as the influence of the presence of folic acid on the objects' photophysical properties and their effects on selectivity and phototoxicity in vitro and in vivo.