Optically Transparent Gold Nanoparticles for DSSC Counter-Electrode: An Electrochemical Characterization.

A gold nanoparticles transparent electrode was realized by chemical reduction. This work aims to compare the transparent gold nanoparticles electrode with a more commonly utilized gold-film-coated electrode in order to investigate its potential use as counter-electrode (CE) in dye-sensitized solar cells (DSSCs). A series of DSSC devices, utilizing I-/I3- and Co(III)/(II) polypyridine redox mediators [Co(dtb)3]3+/2+; dtb = 4,4'ditert-butyl-2,2'-bipyridine)], were evaluated. The investigation focused firstly on the structural characterization of the deposited gold layers and then on the electrochemical study. The novelty of the work is the realization of a gold nanoparticles CE that reached 80% of average visible transmittance. We finally examined the performance of the transparent gold nanoparticles CE in DSSC devices. A maximum power conversion efficiency (PCE) of 4.56% was obtained with a commercial I-/I3--based electrolyte, while a maximum 3.1% of PCE was obtained with the homemade Co-based electrolyte.

Transparent Polymeric Formulations Effective against SARS-CoV-2 Infection.

The main route of the transmission of the SARS-CoV-2 virus is through airborne small aerosol particles containing viable virus as well as through droplets transmitted between people within close proximity. Transmission via contaminated surfaces has also been recognized as an important route for the spread of SARS-CoV-2 coronavirus. Among a variety of antimicrobial agents currently in use, polymers represent a class of biocides that have become increasingly important as an alternative to existing biocidal approaches. Two transparent polymeric compounds, containing silver and benzalkonium ions electrostatically bound to a polystyrene sulfonate backbone, were synthesized, through simple procedures, and evaluated for their antimicrobial properties against Gram-positive and Gram-negative bacteria and Candida albicans (ISO EN 1276) and for their antiviral activity toward 229E and SARS-CoV-2 coronaviruses (ISO UNI EN 14476:2019). The results showed that the two tested formulations are able to inhibit the growth of (1.5-5.5) × 1011 CFU of Gram-positive bacteria, Gram-negative bacteria, and of the fungal species Candida albicans. Both compounds were able to control the 229E and SARS-CoV-2 infection of a target cell in a time contact of 5 min, with a virucidal effect from 24 to 72 h postinfection, according to the European Medicines Agency (EMA) guidelines, where a product is considered virucidal upon achieving a reduction of 4 logarithms. This study observed a decrease of more than 5 logarithms, which implies that these formulations are likely ideal candidates for the realization of transparent surface coatings that are capable of maintaining remarkable antibacterial activity and SARS-CoV-2 antiviral properties over time.

A Series of Iron(II)-NHC Sensitizers with Remarkable Power Conversion Efficiency in Photoelectrochemical Cells*.

A series of six new Fe(II)NHC-carboxylic sensitizers with their ancillary ligand decorated with functions of varied electronic properties have been designed with the aim to increase the metal-to- surface charge separation and light harvesting in iron-based dye-sensitized solar cells (DSSCs). ARM130 scored the highest efficiency ever reported for an iron-sensitized solar cell (1.83 %) using Mg2+ and NBu4 I-based electrolyte and a thick 20 µm TiO2 anode. Computational modelling, transient absorption spectroscopy and electrochemical impedance spectroscopy (EIS) revealed that the electronic properties induced by the dimethoxyphenyl-substituted NHC ligand of ARM130 led to the best combination of electron injection yield and spectral sensitivity breadth.

Restarting the Healing Process of Chronic Wounds Using a Novel Desiccant: A Prospective Case Series.

INTRODUCTION: Chronic skin wounds represent a major global health problem and financial burden. The blocked healing process of chronic wounds involves excess inflammatory proteins, persistent microbial burden, and often, drug-resistant biofilm on the wound bed. Wound-bed debridement is considered crucial to restart the healing process. OBJECTIVE: The authors developed a novel desiccant (desiccating agent A) to serve as a new form of chemical debridement. The objective is to establish the working mechanism of desiccating agent A. MATERIALS AND METHODS: Desiccating agent A was exposed to 7 pathogens in vitro and a prospective trial investigation was performed in vivo on 10 cases to establish a timeline to reach granulation. RESULTS: The growth of a pool of the 7 pathogens showed an inhibition ring at 24 hours was 54 mm ± 5 mm. The prospective trial investigating 10 cases (5 females, 5 males) had a median age of 72.5 years (range, 50-90 years). The duration of the ulcers ranged from 6 weeks to 52 weeks (interquartile range, 6-24 weeks). The wound bed (median area, 64 cm2) was rinsed and dried. Desiccating agent A was applied directly to the wound bed with a gloved finger; after 30 to 60 seconds, desiccating agent A was rinsed and the remaining desiccated material was mechanically removed with dry sterile gauze. The wound bed was dried and covered with sterile gauze soaked in fitostimoline; dressings were changed as needed. The only observed side effect, transient pain, graded on a visual analog scale. Pain intensity ranged from 1 to 7 on a scale from 0 to 10. No nodules, welts, or blisters were observed. Median time to full granulation was 20.5 days (range, 7-78 days). CONCLUSIONS: These data support continued development of desiccating agent A as a chemical debridement agent.

Titanium Implants Coated with a Bifunctional Molecule with Antimicrobic Activity: A Rabbit Study.

BACKGROUND: Various surface treatments have been tested for titanium implants aiming at increasing their surface biocompatibility and their biological characteristics, but also the efficiency of the implant surface will have to be improved to drastically decrease peri-implantite and mucosite. In fact, the peri-implantitis and peri-implant mucositis have a high incidence in clinical practice. The nanofabrication techniques that offer the possibility to achieve the implant surface that reduces bacterial colonization could influence the osteointegration. The aim of this research was to evaluate the bone response to titanium implants coated with a bifunctional molecule with antimicrobic activity consisting of a combination of silver ions covalently bound to titanium dioxide nanoparticles. METHODS: A total of 36 implants were inserted into 18 older New Zealand white male rabbits. They had two different surfaces. The implants Control group was characterized by an acid-etched and sandblasted surface treatment, and the Test implants had an acid-etched and sandblasted surface coated with a silver ion covalently bound to titanium dioxide nanoparticles in the solution. RESULTS: No statistically significant difference of the bone density was evidenced between Control and Test implants at two weeks (p-value = 0.623), four weeks (p-value = 0.339), and eight weeks (p-value = 0.461). Moreover, no statistically significant difference of the bone-implant contact percentage was evidenced between Control and Test implants at two weeks (p-value = 0.938), four weeks (p-value = 0.307), and eight weeks (p-value = 0.294). The effectiveness of the present investigation demonstrated no adverse effects on osseointegration, and no statistically significant differences were observed in the bone density and percentage of bone-implant contact between Test and Control implants at all the experimental time points (two, four, and eight weeks). CONCLUSIONS: Titanium implants coated with the silver-anatase solution bind very well to the bone and did not have an adverse effect on the bone tissue in a rabbit model. These facts suggest possible clinical applications for the silver composition.

Recombination and regeneration dynamics in FeNHC(ii)-sensitized solar cells.

Recombination and regeneration dynamics in Fe-NHC-sensitized DSSCs revealed incomplete injection and the detrimental effect of photoinjected electron recapture by the I3-form of the redox electrolyte on performance. Importantly, the use of additives in the electrolyte allowed the best efficiency ever recorded for an iron-based DSSC to be reached.

Fluorinated ZnII Porphyrins for Dye-Sensitized Aqueous Photoelectrosynthetic Cells.

Three perfluorinated ZnII porphyrins were evaluated as n-type sensitizers in photoelectrosynthetic cells for HBr and water splitting. All the dyes are featured by the presence of pentafluorophenyl electron-withdrawing groups to increase the ground-state oxidation potential and differ for the nature and position of the π-conjugate linker between the core and anchoring group tasked to bind the metal oxide, in order to assess the best way of coupling with the semiconductor. A phenyl-triazole moiety was used to link the carboxylic anchoring group onto the meso position, while an ethynyl-phenyl linker was chosen to bridge carboxylic and cyanoacrylic groups onto the ß-pyrrolic position. A combination of electrochemical, computational, and spectroscopic investigations confirmed the strong electron-withdrawing effect of the perfluorinated porphyrin core, which assures all the investigated dyes of the high oxidation potential required to the coupling with water oxidation catalysts (WOC). Such an electron-poor core, however, affects the charge separation character of the dyes, as demonstrated by the spatial distribution of the excited states, leading to a nonquantitative charge injection, although tilting of the molecules on the semiconductor surface could bring the porphyrin ring closer to the semiconductor, offering additional charge-transfer pathways. Indeed, all the dyes demonstrated successful in the splitting of both aqueous HBr and water, with the best results found for the SnO2/TiO2 photoanode sensitized with the ß-substituted porphyrin equipped with a cyanoacrylic terminal group, achieving 0.4 and 0.1 mA/cm2 photoanodic currents in HBr and water under visible light, respectively. The faradaic yield for oxygen evolution in the presence of an IrIV catalyst was over 95%, and the photoanode operation was stable for more than 1000 s. Thus, the perfluorinated porphyrins with a cyanoacrylic anchoring group at the ß-position should be considered for further development to improve the charge-transfer character.

A New Strategy Against Peri-Implantitis: Antibacterial Internal Coating.

The bacterial biofilm formation in the oral cavity and the microbial activity around the implant tissue represent a potential factor on the interface between bone and implant fixture that could induce an inflammatory phenomenon and generate an increased risk for mucositis and peri-implantitis. The aim of the present clinical trial was to investigate the bacterial quality of a new antibacterial coating of the internal chamber of the implant in vivo at six months. The PIXIT implant (Edierre srl, Genova Italy) is prepared by coating the implant with an alcoholic solution containing polysiloxane oligomers and chlorhexidine gluconate at 1%. A total of 15 healthy patients (60 implants) with non-contributory past medical history (nine women and six men, all non-smokers, mean age of 53 years, ranging from 45-61 years) were scheduled to receive bilateral fixed prostheses or crown restorations supported by an implant fixture. No adverse effects and no implant failure were reported at four months. All experimental sites showed a good soft tissue healing at the experimental point times and no local evidence of inflammation was observed. Real-Time Polymerase Chain Reaction (PCR) analysis on coated and uncoated implants showed a decrease of the bacterial count in the internal part of the implant chamber. The mean of total bacteria loading (TBL) detected in each PCR reaction was lower in treated implants (81038 units/reaction) compared to untreated implants (90057 units/reaction) (p < 0.01). The polymeric chlorhexydine coating of the internal chamber of the implant showed the ability to control the bacterial loading at the level of the peri-implant tissue. Moreover, the investigation demonstrated that the coating is able to influence also the quality of the microbiota, in particular on the species involved in the pathogenesis of peri-implantitis that are involved with a higher risk of long-term failure of the dental implant restoration.

Photoelectrocatalytic degradation of emerging contaminants at WO3/BiVO4 photoanodes in aqueous solution.

WO3/BiVO4 films obtained by electrochemical deposition of BiVO4 over mesoporous WO3 were applied to the photoelectrochemical degradation of selected emerging contaminants (ketoprofen and levofloxacine) in aqueous solutions. The WO3/BiVO4 films in this work are characterized by a mesoporous morphology with a maximum photoconversion efficiency >40% extending beyond 500 nm in Na2SO4 electrolytes. Oxygen was found to be the dominant water oxidation product (ca. 90% faradaic yield) and no evidence for the photogeneration of OH radicals was obtained. Nevertheless, both 10 ppm levofloxacine and ketoprofen could be degraded at WO3/BiVO4 junctions upon a few hours of illumination under visible light. However, while levofloxacine degradation intermediates were progressively consumed by further oxidation at the WO3/BiVO4 interface, ketoprofen oxidation byproducts, being stable aromatic species, were found to be persistent in aqueous solution even after 15 hours of solar simulated illumination. This indicates that, due to the lower oxidizing power of photogenerated holes in BiVO4 and a different water oxidation mechanism, the employment of WO3/BiVO4 in photoelectrochemical environmental remediation processes is much less universal than that possible with wider band gap semiconductors such as TiO2 and WO3.

Publisher Correction: Hierarchical organization of perylene bisimides and polyoxometalates for photo-assisted water oxidation.

In the version of this Article originally published, in the graphical abstract the y-axis units of the plot read 'mA cm-2', but should have read 'µA cm-2'. Additionally, an erroneous gap appeared in the red trace. These errors have now been corrected.

Hierarchical organization of perylene bisimides and polyoxometalates for photo-assisted water oxidation.

The oxygen in Earth's atmosphere is there primarily because of water oxidation performed by photosynthetic organisms using solar light and one specialized protein complex, photosystem II (PSII). High-resolution imaging of the PSII 'core' complex shows the ideal co-localization of multi-chromophore light-harvesting antennas with the functional reaction centre. Man-made systems are still far from replicating the complexity of PSII, as the majority of PSII mimetics have been limited to photocatalytic dyads based on a 1:1 ratio of a light absorber, generally a Ru-polypyridine complex, with a water oxidation catalyst. Here we report the self-assembly of multi-perylene-bisimide chromophores (PBI) shaped to function by interaction with a polyoxometalate water-oxidation catalyst (Ru4POM). The resulting [PBI]5Ru4POM complex shows a robust amphiphilic structure and dynamic aggregation into large two-dimensional paracrystalline domains, a redshifted light-harvesting efficiency of >40% and favourable exciton accumulation, with a peak quantum efficiency using 'green' photons (λ > 500 nm). The modularity of the building blocks and the simplicity of the non-covalent chemistry offer opportunities for innovation in artificial photosynthesis.

Silver-Based Chemical Device as an Adjunct of Domestic Oral Hygiene: A Study on Periodontal Patients.

The use of chemical devices for periodontitis treatment has led to new strategies aiming primarily to control infections. Over the last few years, new chemical devices have been subjected to many scientific and medical studies. The purpose of the present study was to assess the effect of a new silver based chemical devices gel named "Hydrosilver Plus Gel", abbreviated here as Hydrosilver, on the pathogenic microorganisms, using Polymerase Chain Reaction (PCR) for microbiological analysis. Materials and methods: Ten patients with a diagnosis of chronic periodontitis in the age group >25 years were selected. None of these patients had received any surgical or non-surgical periodontal therapy, and demonstrated radiographic evidence of moderate bone loss. After scaling and root planning, patients received Hydrosilver to be used at home. Four non-adjacent sites in separate quadrants were selected in each patient for monitoring, based on criteria that the sites localise chronic periodontitis. Microbial analysis was analysed at baseline and at Day 15. SPSS program was used for statistical purposes and a paired samples correlation was performed at the end of the observation period. Results: Mean amounts of bacterial loading before and after Hydrosilver treatment reduced statistically significantly (p = 0.002). Conclusions: The present study demonstrated that Hydrosilver has a good impact on oral biofilm. Additional studies are needed to detect the efficacy of this chemical device.

Coupling of Zinc Porphyrin Dyes and Copper Electrolytes: A Springboard for Novel Sustainable Dye-Sensitized Solar Cells.

The combination of ß-substituted Zn2+ porphyrin dyes and copper-based electrolytes represents a sustainable route for economic and environmentally friendly dye-sensitized solar cells. Remarkably, a new copper electrolyte, [Cu(2-mesityl-1,10-phenanthroline)2]+/2+, exceeds the performance reached by Co2+/3+ and I-/I3- reference electrolytes.

Electronic and charge transfer properties of bio-inspired flavylium ions for applications in TiO2-based dye-sensitized solar cells.

We present here a complete study on four synthetic environmentally friendly flavylium salts employed as sensitizers for dye-sensitized solar cells (DSSCs). The effect of several donor groups on the molecular structure of flavylium ions was investigated by combining electrochemical, spectroscopic and computational means. The computational investigation indicated that these molecules can interact strongly with the TiO2 surface by a single OH group of the dihydroxybenzene moiety, and can efficiently inject electrons into the TiO2 following the excitation of their lowest singlet states exhibiting charge transfer (CT) character. In general, all dyes within the explored series exhibited quite good regeneration efficiencies, often ≥70%, in the presence of an iodide electron donor, explaining the high IPCEs and photocurrents recorded in the presence of high lithium content electrolytes. The combination of molecular orbital calculations and electrochemical measurements has also revealed that the introduction of donor groups on the benzopyrylium ring has a generally positive effect resulting in an extended low energy light harvesting and in a potential improvement of the photoinduced charge separation at the semiconductor/dye/electrolyte interface. It also increases the reversibility of the oxidative redox processes of these bio-inspired species, a feature in favour of their long-term stability. At present the best dye within the explored series is 7-(N,N-diethylamino)-3',4'-dihydroxyflavylium chloride based on a dialkylamine donor which is capable of delivering, under optimized conditions, a short-circuit current density of 15 mA cm-2. This is the highest value so far obtained for synthetic analogues of anthocyanins.

Photoelectrochemical Behavior of Electrophoretically Deposited Hematite Thin Films Modified with Ti(IV).

Doping hematite with different elements is a common strategy to improve the electrocatalytic activity towards the water oxidation reaction, although the exact effect of these external agents is not yet clearly understood. Using a feasible electrophoretic procedure, we prepared modified hematite films by introducing in the deposition solution Ti(IV) butoxide. Photoelectrochemical performances of all the modified electrodes were superior to the unmodified one, with a 4-fold increase in the photocurrent at 0.65 V vs. SCE in 0.1 M NaOH (pH 13.3) for the 5% Ti-modified electrode, which was the best performing electrode. Subsequent functionalization with an iron-based catalyst led, at the same potential, to a photocurrent of ca. 1.5 mA·cm(-2), one of the highest achieved with materials based on solution processing in the absence of precious elements. AFM, XPS, TEM and XANES analyses revealed the formation of different Ti(IV) oxide phases on the hematite surface, that can reduce surface state recombination and enhance hole injection through local surface field effects, as confirmed by electrochemical impedance analysis.

Single Walled Carbon Nanohorns as Catalytic Counter Electrodes for Co(III)/(II) Electron Mediators in Dye Sensitized Cells.

The electrochemical properties of both pristine single walled carbon nanohorns (SWCNHS) and their chemically oxidized form (ox-SWCNHS) spray coated onto fluorine doped SnO2 (FTO) were investigated in the framework of the fabrication of cobalt based transparent dye sensitized solar cells (DSSCs). These new nanocarbon substrates, evaluated in conjunction with the Co(bpy)3(2+/3+) (bpy = 2,2'-bipyridine) redox mediator, are endowed with excellent electrocatalytic properties, ease of fabrication, and very promising stability and display a great potential for replacing the best noble metal and conductive polymer catalytic materials in the building of semitransparent counter electrodes in new generation photoelectrochemical devices.

Correction: On the stability of manganese tris(ß-diketonate) complexes as redox mediators in DSSCs.

Correction for 'On the stability of manganese tris(ß-diketonate) complexes as redox mediators in DSSCs' by Stefano Carli et al., Phys. Chem. Chem. Phys., 2016, 18, 5949-5956.

Tetracoordinated Bis-phenanthroline Copper-Complex Couple as Efficient Redox Mediators for Dye Solar Cells.

A tetracoordinated redox couple, made by [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)2][PF6], 1, and its Cu(II) form [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)2][PF6]2, 2, has been synthesized, and its electrochemical and photochemical features have been investigated and compared with those of a previously published Cu(2+)/Cu(+) redox shuttle, namely, [Cu(2,9-dimethyl-1,10-phenanthroline)2][PF6], 3, and its pentacoordinated oxidized form [Cu(2,9-dimethyl-1,10-phenanthroline)2Cl][PF6], 4. The detrimental effect of the fifth Cl(-) ancillary ligand on the charge transfer kinetics of the redox shuttles has been exhaustively demonstrated. Appropriately balanced Cu-based electrolytes have been then formulated and tested in dye solar cells in combination with a π-extended benzothiadiazole dye. The bis-phenanthroline Cu-complexes, 1 and 2, have been found to provide an overall 4.4% solar energy conversion efficiency, which is more than twice that of the literature benchmark couple, 3 and 4, employing a Cl-coordinated oxidized species and even comparable with the performances of a I(-)/I3(-) electrolyte of analogous concentration. A fast counter-electrode reaction, due to the excellent electrochemical reversibility of 2, and a high electron collection efficiency, allowed through the efficient dye regeneration kinetics exerted by 1, represents two major characteristics of these copper-based electron mediators and may constitute a pivotal step toward the development of a next generation of copper-based efficient iodine-free redox shuttles.

A New 1,3,4-Oxadiazole-Based Hole-Transport Material for Efficient CH3 NH3 PbBr3 Perovskite Solar Cells.

A new hole-transport material (HTM) based on the 1,3,4-oxadiazole moiety (H1) was prepared through a single-step synthetic pathway starting from commercially available products. Thanks to a deep HOMO level, H1 was used as HTM in CH3 NH3 PbBr3 perovskite solar cells yielding an efficiency of 5.8%. The reference HTM (Spiro-OMeTAD), under the same testing conditions, furnished a lower efficiency of 5.1%. Steady-state and time-resolved photoluminescence of the thin films showed good charge-extraction dynamics for H1 devices. In addition, H1 shows a large thermal stability and completely amorphous behavior (as evaluated by thermal gravimetric analysis and differential scanning calorimetry).

On the stability of manganese tris(ß-diketonate) complexes as redox mediators in DSSCs.

The photoelectrochemical properties and stability of dye sensitized solar cells containing Mn(ß-diketonato)3 complexes, [Mn(III)(acac)3] () (acac = acetylacetonate), [Mn(III)(CF2)3] () (CF2 = 4,4-difluoro-1-phenylbutanate-1,3-dione), [Mn(III)(DBM)3] () (DBM = dibenzoylmethanate), [Mn(II)(CF2)3]TBA (TBA = tetrabutylammonium) () and [Mn(II)(DBM)3]TBA (), have been evaluated. At room temperature, the complexes undergo ligand exchange with 4-tert-butyl-pyridine, an additive commonly used in the solar device to reduce charge recombination at the photoanode. An increased device stability was achieved by using the Z907 dye and passivating the photoanode with short chain siloxanes. It was also found that the Mn(ii)/(iii) couple is involved in the dye regeneration process, instead of Mn(iii)/(iv) (E1/2 > 1 V vs. SCE) previously indicated in the literature.