Role of the Benzothiadiazole Unit in Organic Polymers on Photocatalytic Hydrogen Production.

Organic polymers based on the donor-acceptor structure are a promising class of efficient photocatalysts for solar fuel production. Among these polymers, poly(9,9-dioctylfluorene-alt-1,2,3-benzothiadiazole) (PFBT) consisting of fluorene donor and benzothiadiazole acceptor units has shown good photocatalytic activity when it is prepared into polymer dots (Pdots) in water. In this work, we investigate the effect of the chemical environment on the activity of photocatalysis from PFBT Pdots for hydrogen production. This is carried out by comparing the samples with various concentrations of palladium under different pH conditions and with different sacrificial electron donors (SDs). Moreover, a model compound 1,2,3-benzothiadiazole di-9,9-dioctylfluorene (BTDF) is synthesized to investigate the mechanism for protonation of benzothiadiazole and its kinetics in the presence of an organic acid-salicylic acid by cyclic voltammetry. We experimentally show that benzothiadiazole in BTDF can rapidly react with protons with a fitted value of 0.1-5 × 1010 M-1 s-1 which should play a crucial role in the photocatalytic reaction with a polymer photocatalyst containing benzothiadiazole such as PFBT Pdots for hydrogen production in acidic conditions. This work gives insights into why organic polymers with benzothiadiazole work efficiently for photocatalytic hydrogen production.

Small Organic Molecular Electrocatalysts for Fuels Production.

In recent years, heterocyclic organic compounds have been explored as molecular electrocatalysts in relevant reactions for energy conversion and storage. Merging mimetics of biological systems that perform hydride transfer with rational synthetic chemical design has opened many opportunities for organic molecules to be tuned at the atomic level conferring them interesting reactivities. These molecular electrocatalysts represent an alternative to traditional metallic materials and metal complexes employed for water oxidation, hydrogen production, and carbon dioxide reduction. This minireview describes recent reports concerning design, catalytic activity and the mechanism of synthetic molecular electrocatalysts towards solar fuels production.

Organic Polymer Dots Photocatalyze CO2 Reduction in Aqueous Solution.

Developing low-cost and efficient photocatalysts to convert CO2 into valuable fuels is desirable to realize a carbon-neutral society. In this work, we report that polymer dots (Pdots) of poly[(9,9'-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-thiadiazole)] (PFBT), without adding any extra co-catalyst, can photocatalyze reduction of CO2 into CO in aqueous solution, rendering a CO production rate of 57 µmol g-1 h-1 with a detectable selectivity of up to 100 %. After 5 cycles of CO2 re-purging experiments, no distinct decline in CO amount and reaction rate was observed, indicating the promising photocatalytic stability of PFBT Pdots in the photocatalytic CO2 reduction reaction. A mechanistic study reveals that photoexcited PFBT Pdots are reduced by sacrificial donor first, then the reduced PFBT Pdots can bind CO2 and reduce it into CO via their intrinsic active sites. This work highlights the application of organic Pdots for CO2 reduction in aqueous solution, which therefore provides a strategy to develop highly efficient and environmentally friendly nanoparticulate photocatalysts for CO2 reduction.

Preparation, characterization, evaluation and mechanistic study of organic polymer nano-photocatalysts for solar fuel production.

Production of renewable fuels from solar energy and abundant resourses, such as water and carbon dioxide, via photocatalytic reactions is seen as a promising strategy to adequately address the climate challenge. Photocatalytic systems based on organic polymer nanoparticles (PNPs) are seen as one avenue to transform solar energy into hydrogen and other solar fuels. Semiconducting PNPs are light-harvesting materials with exceptional optical properties, photostability, low cost and low cytotoxity, whose performance surpasses conventional organic dyes and inorganic semiconductors. This review introduces the optimization strategies for the preparation methods of PNP via cocatalyst loading and morphology tuning. We present an analysis on how the preparative methods will impact the physico-chemical properties of these materials, and thus the catalytic activity. A list of experimental techniques is presented for characterization of the physico-chemical properties (optical, morphological, electrochemical and catalytic properties) of PNPs. We provide detailed analysis of PNP photochemistry during photocatalysis with focus on the mechanistic understanding of processes of internal charge generation and transport to the catalyst. This tutorial review provides the reader with the guidelines on current strategies used to optimize PNP performance highlighting the future directions of polymer nano-photocatalysts development.

Small Organic Molecule Based on Benzothiadiazole for Electrocatalytic Hydrogen Production.

A small organic molecule 2,1,3-benzothiadiazole-4, 7-dicarbonitrile (BTDN) is assessed for electrocatalytic hydrogen evolution on glassy carbon electrode and shows a hydrogen production Faradaic efficiency of 82% in the presence of salicylic acid. The key catalytic intermediates of reduced species BTDN-• and protonated intermediates are characterized or hypothesized by using various spectroscopic methods and density functional theory (DFT)-based calculations. With the experimental and theoretical results, a catalytic mechanism of BTDN for electrocatalytic H2 evolution is proposed.

Panchromatic Ternary Polymer Dots Involving Sub-Picosecond Energy and Charge Transfer for Efficient and Stable Photocatalytic Hydrogen Evolution.

Panchromatic ternary polymer dots (Pdots) consisting of two conjugated polymers (PFBT and PFODTBT) based on fluorene and benzothiadiazole groups, and one small molecular acceptor (ITIC) have been prepared and assessed for photocatalytic hydrogen production with the assistance of a Pt cocatalyst. Femtosecond transient absorption spectroscopic studies of the ternary Pdots have revealed both energy and charge transfer processes that occur on the time scale of sub-picosecond between the different components. They result in photogenerated electrons being located mainly at ITIC, which acts as both electron and energy acceptor. Results from cryo-transmission electron microscopy suggest that ITIC forms crystalline phases in the ternary Pdots, facilitating electron transfer from ITIC to the Pt cocatalyst and promoting the final photocatalytic reaction yield. Enhanced light absorption, efficient charge separation, and the ideal morphology of the ternary Pdots have rendered an external quantum efficiency up to 7% at 600 nm. Moreover, the system has shown a high stability over 120 h without obvious degradation of the photocatalysts.

A single-step method for rapid extraction of total lipids from green microalgae.

Microalgae produce a wide range of lipid compounds of potential commercial interest. Total lipid extraction performed by conventional extraction methods, relying on the chloroform-methanol solvent system are too laborious and time consuming for screening large numbers of samples. In this study, three previous extraction methods devised by Folch et al. (1957), Bligh and Dyer (1959) and Selstam and Öquist (1985) were compared and a faster single-step procedure was developed for extraction of total lipids from green microalgae. In the single-step procedure, 8 ml of a 2∶1 chloroform-methanol (v/v) mixture was added to fresh or frozen microalgal paste or pulverized dry algal biomass contained in a glass centrifuge tube. The biomass was manually suspended by vigorously shaking the tube for a few seconds and 2 ml of a 0.73% NaCl water solution was added. Phase separation was facilitated by 2 min of centrifugation at 350 g and the lower phase was recovered for analysis. An uncharacterized microalgal polyculture and the green microalgae Scenedesmus dimorphus, Selenastrum minutum, and Chlorella protothecoides were subjected to the different extraction methods and various techniques of biomass homogenization. The less labour intensive single-step procedure presented here allowed simultaneous recovery of total lipid extracts from multiple samples of green microalgae with quantitative yields and fatty acid profiles comparable to those of the previous methods. While the single-step procedure is highly correlated in lipid extractability (r²â€Š= 0.985) to the previous method of Folch et al. (1957), it allowed at least five times higher sample throughput.

Specific impairments in instrumental learning following chronic intermittent toluene inhalation in adolescent rats.

RATIONALE: Inhalant abuse is prevalent in adolescent populations, with chronic use resulting in neurobiological and cognitive abnormalities in adulthood. However, the nature and persistence of cognitive dysfunction, particularly following adolescent inhalant abuse, remain equivocal. OBJECTIVE: The present study assessed specific cognitive processes beginning in late adolescence and adulthood following adolescent inhalation of toluene, a main component of many compounds readily abused. METHODS: Adolescent male Wistar rats (postnatal day (PN) 27) were exposed to chronic intermittent inhaled toluene (10,000 ppm) for 1 h/day, 3 days/week for 4 weeks (PN 27-52) to mimic the patterns observed in human adolescent inhalant abusers. Following toluene exposure, motor and cognitive function was assessed. RESULTS: Adolescent toluene exposure did not alter motor learning in the Rotarod task (PN 58) or acquisition, reversal, or retention of spatial learning in the Morris water maze (PN 55-64). In contrast, it delayed acquisition of instrumental responding for sucrose (5 % w/v) and impaired operant reversal learning and cue-induced reinstatement of sucrose seeking in adulthood (PN 57-100). CONCLUSION: This study demonstrates that exposure to toluene at an abuse concentration during adolescence results in specific impairments in aspects of instrumental learning, without altering motor function and spatial learning in late adolescence/early adulthood. Our data imply that persistent alterations in reward processing may occur following adolescent inhalant misuse.