Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry.

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing a plethora of opportunities to synthetic organic chemists. However, performing a photochemical transformation can be quite a challenge because of various issues related to the delivery of photons. These challenges have barred the widespread adoption of photochemical steps in the chemical industry. However, in the past decade, several technological innovations have led to more reproducible, selective, and scalable photoinduced reactions. Herein, we provide a comprehensive overview of these exciting technological advances, including flow chemistry, high-throughput experimentation, reactor design and scale-up, and the combination of photo- and electro-chemistry.

Metoprolol and Its Degradation and Transformation Products Using AOPs-Assessment of Aquatic Ecotoxicity Using QSAR.

Pharmaceuticals are found in waterbodies worldwide. Conventional sewage treatment plants are often not able to eliminate these micropollutants. Hence, Advanced Oxidation Processes (AOPs) have been heavily investigated. Here, metoprolol is exposed to UV irradiation, hydrogen peroxide, and ozonation. Degradation was analyzed using chemical kinetics both for initial and secondary products. Photo-induced irradiation enhanced by hydrogen peroxide addition accelerated degradation more than ozonation, leading to complete elimination. Degradation and transformation products were identified by high-performance liquid-chromatography coupled to high-resolution higher-order mass spectrometry. The proposed structures allowed to apply Quantitative Structure-Activity Relationship (QSAR) analysis to predict ecotoxicity. Degradation products were generally associated with a lower ecotoxicological hazard to the aquatic environment according to OECD QSAR toolbox and VEGA. Comparison of potential structural isomers suggested forecasts may become more reliable with larger databases in the future.

Geographical and temporal assessment of the photochemical decontamination potential of river waters from agrochemicals: A first application to the Piedmont region (NW Italy).

This work shows the potential of using photochemical modelling to assess the river-water ability to photodegrade agrochemicals on a geographic and temporal scale. The case of flowing water requires different data treatment compared to more stationary water bodies (e.g., lakes), but it could allow for the identification of particularly vulnerable environments. Five pesticides were considered here, and the photodegradation rate followed the order bentazon > isoproturon > dimethomorph âˆ¼ chlortoluron > atrazine. The modelled photodegradation kinetics was particularly fast in the river Po, which receives significant input of agricultural nitrate from groundwater and features higher steady-state [•OH] than most other rivers in the region. The fact that the Po eventually collects all river waters in Piedmont is positive, from the point of view of comprehensive photodegradation of pesticides. However, this paradoxical situation of agricultural pollution (nitrate) helping fight pollution from the same source (pesticides) has two important limitations: (i) when compared to the parent compounds, some intermediates deriving from •OH reactions are either more harmful (N-formyl derivatives of phenylureas), or about as harmful (desethyl atrazine); (ii) banned atrazine is no longer sprayed over fields during the plant growth season, but it reaches surface waters from legacy groundwater inputs. The latter are operational also during winter, when photochemistry is least active. Therefore, photochemistry might not ensure considerable attenuation of atrazine during wintertime. Overall, bentazon would be the safest among the studied pesticides because of fast degradation by direct photolysis, and of low ecotoxicological impact of its phototransformation intermediates.

Physiology and yield of piel de sapo melon (Cucumis melo L. ) under water deficit in semi-arid region, Brazil / Fisiologia e rendimento do meloeiro pele-de-sapo (Cucumis melo L. ) cultivado sob diferentes regimes hídricos em região semi-árida, Brasil

Melon (Cucumis melo L.) is a crop of great socioeconomic importance in regions with semiarid climate, as found in Northeast Brazil. In this region water deficit is a usual condition as well as the main reduction factor of plant productivity. Due to this phenomenon, irrigation techniques are used to make available the amount of water needed for plant production. Therefore, this study evaluated the physiology and fruit production changes of 'Juazeiro' Piel de sapo melon plants under different water replacement rates. 'Juazeiro' melon was grown under four reference evapotranspiration replacement rates (40, 60, 80 and 100% of ETo) distributed randomly in blocks with 5 replicates. The plants were cultivated in the field, in an experimental area located in the Brazilian Northeast region, under hot and dry semiarid climatic conditions, and during the growing cycle the 'Juazeiro' hybrid melon plants were evaluated for leaf area, biomass accumulation, gas exchange, photochemical efficiency of photosystem PSII and production of fruits per plant. Application of water replacement rates of 100% ETo leads to highest growth, net photosynthesis, and fruit yield of 'Juazeiro' melon. Water replacement at 80% ETo can be used for 'Juazeiro" melon under semiarid climatic conditions, but with small losses in fruit yield. Water replacement below 80% ETo leads to drastic reductions in growth, gas exchanges, quantum efficiency of photosystem II and fruit yield, which impairs melon production in semi-arid climate environments. KEYWORDS: Fruits yield. Gas exchange. Photochemical efficiency. INTRODUCTION Melon (Cucumis melo L.) is an important socioeconomic fruit cultivated in the world. Melon fruit production was 29.6 million tons and this production is distributed among China, Turkey, Iran, Egypt, India, United States, and Brazil. These countries account for 70% of the world production (FAO, 2017). In Brazil, cultivated area exceeded 22.000 ha with more than 521.6 thousand tons in 2015. 94.7% of this production was obtained in the semi-arid region of Northeast, mainly in the states of Ceará and Rio Grande do Norte, the largest producers in the country (IBGE, 2014). However, especially due to irregular rainfall, melon fruit production has been dropping in the last few years in this region. According to Pereira Filho et al. (2015), melon plants growth, development, and fruit production are greatly affected by climate conditions, mainly by water stress. Water stress is one of the most complex physiological phenomena because it is a multidimensional component which can considerably limit agricultural crops growth and development (DOGAN et al., 2008; LISAR et al., 2012; SILVA et al., 2015), generally in arid and semi-arid regions, such as in Northeast Brazil. Moreover, plant adaptability to water deficit conditions is related to a range of events occurring at several levels (LISAR et al., 2012), observed as a physiological, biochemical, and molecular adaptations, among others. At plant physiological level, soil water deficit has a significant effect on gas exchange, because it is a result of the limitation of stomatal conductance, and it is considered the primary cause of photosynthetic inhibition due to CO2 influx limitation, as well as water efflux from transpiration Received: 08/04/19 Accepted: 20/12/19

O meloeiro (Cucumis melo L.) é uma cultura de grande importância social e econômica mundial, principalmente em regiões de clima semiárido como o Nordeste brasileiro, onde déficit hídrico é condição comum e considerado o principal fator de redução da produtividade das plantas. Tal fenômeno força a utilização da irrigação como forma de disponibilizar a quantidade de água necessária à produção. Assim, objetivou-se com este trabalho avaliar as variações fisiológicas e produtivas de meloeiro pele-de-sapo submetidos a diferentes taxas de reposição hídrica. O híbrido 'Juazeiro' de melão pele-de-sapo foi cultivado sob quatro taxas de reposição da evapotranspiração de referência (40, 60, 80 e 100% da ETo), distribuídas em blocos ao acaso com 5 repetições. As plantas foram cultivadas em campo, em área experimental situada no Nordeste brasileiro, em condições clima semiárido quente e seco, e durante o ciclo de cultivo as plantas de meloeiro híbrido 'Juazeiro' foram avaliadas quanto a área foliar, o acúmulo de biomassa, as trocas gasosas, eficiência fotoquímica do fotossitesma PSII e produção de frutos por planta. A aplicação de taxas de reposição hídrica a 100% da ETo proporciona o maior crescimento, fotossíntese liquida e produção do meloeiro 'Juazeiro'. A reposição hídrica a 80% da ETo pode ser usada para o cultivo do meloeiro 'Juazeiro' em condições de clima semiárido, admitindo-se pequenas perdas no rendimento. A reposição hídrica com lâminas inferiores a 80% da ETo promove reduções drásticas no crescimento, trocas gasosas, eficiência quântica do fotossistema II e produção, que inviabilizam a produção do meloeiro em ambientes de clima semiáridos.

Decomposition of pharmaceutical micropollutant - diclofenac by photocatalytic nanopowder mixtures in aqueous media: effect of optimization parameters, identification of intermediates and economic considerations.

This study evaluates application of three different nanopowder mixtures for decomposition of diclofenac (DCF), one of frequently detected pharmaceutical in wastewater. Analyzed three photocatalytic mixtures ZnO/SnO2, ZnO/TiO2 and ZnO/In2O3 are for the first time used for diclofenac degradation. A set of experiments were performed in order to investigate influence of catalyst concentration (0.10-0.60 mg mL-1), initial concentration of diclofenac (0.002-0.010 mg mL-1) and pH value (5-9). The increase in the catalyst concentration leads to a decrease in the degradation rate constant, which is the most pronounced in the ZnO/TiO2 and ranges from 0.47 (6) min-1 to 0.25 (3) min-1. The influence of pH on efficacy shows completely different effects: ZnO/In2O3 is most effective in alkaline environments, ZnO/TiO2 in neutral environments, while ZnO/SnO2 efficiency is good in both alkaline and acidic environments. Initial concentrations of diclofenac showed a complex effect on the degradation rate. The four dominant intermediates were detected by LC MS/MS technique. In case of all three nanomaterials, intensive degradation was achieved in first 30 minutes. The economical analysis of photocatalytic treatment was provided where the preparation of nanomaterials does not demand high costs and with the highest diclofenac concentration, total operation costs are the lowest (77.14 US$/kWh).

The importance of synthetic chemistry in the pharmaceutical industry.

Innovations in synthetic chemistry have enabled the discovery of many breakthrough therapies that have improved human health over the past century. In the face of increasing challenges in the pharmaceutical sector, continued innovation in chemistry is required to drive the discovery of the next wave of medicines. Novel synthetic methods not only unlock access to previously unattainable chemical matter, but also inspire new concepts as to how we design and build chemical matter. We identify some of the most important recent advances in synthetic chemistry as well as opportunities at the interface with partner disciplines that are poised to transform the practice of drug discovery and development.

Photothermal treatment of port-wine stains using erythrocyte-derived particles doped with indocyanine green: a theoretical study.

Pulsed dye laser irradiation in the wavelength range of 585 to 600 nm is currently the gold standard for treatment of port-wine stains (PWSs). However, this treatment method is often ineffective for deeply seated blood vessels and in individuals with moderate to heavy pigmentation. Use of optical particles doped with the FDA-approved near-infrared (NIR) absorber, indocyanine green (ICG), can potentially provide an effective method to overcome these limitations. Herein, we theoretically investigate the effectiveness of particles derived from erythrocytes, which contain ICG, in mediating photothermal destruction of PWS blood vessels. We refer to these particles as NIR erythrocyte-derived transducers (NETs). Our theoretical model consists of a Monte Carlo algorithm to estimate the volumetric energy deposition, a finite elements approach to solve the heat diffusion equation, and a damage integral based on an Arrhenius relationship to quantify tissue damage. The model geometries include simulated PWS blood vessels as well as actual human PWS blood vessels plexus obtained by the optical coherence tomography. Our simulation results indicate that blood vessels containing micron- or nano-sized NETs and irradiated at 755 nm have higher levels of photothermal damage as compared to blood vessels without NETs irradiated at 585 nm. Blood vessels containing micron-sized NETs also showed higher photothermal damage than blood vessels containing nano-sized NETs. The theoretical model presented can be used in guiding the fabrication of NETs with patient-specific optical properties to allow for personalized treatment based on the depth and size of blood vessels as well as the pigmentation of the individual's skin.

Toxicity assessment of arsenate and arsenite on growth, chlorophyll a fluorescence and antioxidant machinery in Nostoc muscorum.

The present study deals with impact of varied doses of arsenite (AsIII; 50, 100 and 150 µM) and arsenate (AsV; 50, 100 and 150 mM) on growth, photosynthetic pigments, photochemistry of photosystem II, oxidative biomarkers, (O2•¯, H2O2 and MDA equivalents contents) and activity of antioxidant enzymes in diazotrophic cyanobacterium Nostoc muscorum after 48 and 96 h of the treatments. The reduction in growth, pigment contents (Chl a, Phy and Car) and PS II photochemistry was found to increase with enhanced accumulation of test metal in cells, and the damaging effect on photosynthetic pigments showed the order (Phy > chl a> Car). The negative effect on PS II photochemistry was due to significant decrease in the value of JIP kinetics ϕP0, FV/F0, ϕE0,Ψ0 and PIABS except F0/FV and significant rise in values of energy flux parameters such as ABS/RC, TR0/RC, ET0/RC and DI0/RC. Both the species of arsenic caused significant rise in oxidative biomarkers as evident by in vitro and in vivo analysis of (O2•¯, H2O2 and MDA equivalents contents) despite of appreciable rise in the activity antioxidative enzymes such as SOD, POD, CAT and GST. The study concludes that in among both forms of arsenic, arsenite effect was more dominant on growth, photosynthetic pigments; oxidative stress biomarkers as evident by weak induction of anti-oxidative defense system to overcome the stress as compared to arsenate.

Photocatalytic Degradation of Oxytetracycline by Ternary Mixed Catalyst and Toxicity Assessment Using Boar Sperm.

Response surface methodology was adopted to obtain ternary mixed catalysts of TiO2-loaded ZSM-5 zeolite and graphene. Oxytetracycline was used as challenged toxicant to evaluate the photocatalytic degradation efficiency of the composites. The optimal weight ratio of graphene, TiO2, and ZSM-5 was 1:8:1. The composites were characterized by ultraviolet-visible spectroscopy, X-ray diffraction, fourier transform infrared, N2 adsorption-desorption isotherms, and transmission electron microscope with an energy-dispersive spectroscopy system, etc. Synthesized samples showed high stability and strong visible-light absorption efficiency. The optimal operating conditions of oxytetracycline photocatalytic degradation were achieved over a wide range of pH and temperature. With 0.1 g/L of optimal ternary mixed composite, the photocatalytic degradation of oxytetracycline was nearly reached completion within 150 min at all treatment temperatures at pH 7. Toxicity of degraded oxytetracycline solution was assayed by a boar sperm quality model using fluorescent staining and flow cytometry. During 180 min of photocatalytic treatment, the degraded oxytetracycline solution showed increasing biotoxicity and changed the morphology and function of boar sperm, despite not killing them.

Water-Soluble Polymers with Strong Photoluminescence through an Eco-Friendly and Low-Cost Route.

Photoluminescence (PL) of nonconjugated polymers brings a favorable opportunity for low-cost and nontoxic luminescent materials, while most of them still exhibit relatively weak emission. Strong PL from poly[(maleic anhydride)-alt-(vinyl acetate)] (PMV) from low-cost monomer has been found in organic solvents, yet the necessity of noxious solvents would hinder its practical applications. Herein, through a novel, eco-friendly, and one-step route, PMV-derived PL polymers can be fabricated with the highest quantum yield of 87% among water-soluble nonconjugated PL polymers ever reported. These PMV-derived polymers emit strong blue emission in both solutions and solids, and can be transformed into red-emission agents easily. These PL polymers exhibit application potentials in light-conversion agricultural films. It is assumed that this work not only puts forward a convenient preparation routine for nonconjugated polymers with high PL, but also provides an industrial application possibility for them.

Photolytic and photocatalytic degradation of the antipsychotic agent tiapride: Kinetics, transformation pathways and computational toxicity assessment.

The photolytic and photocatalytic transformation of tiapride with the use of TiO2 and H2O2 was investigated. A novel micro-scale method for simultaneous irradiation with simulated full solar spectrum of multiple samples in photostability chamber was proposed. RP-UHPLC-DAD coupled with ESI-Q-TOF mass spectrometer was used for the quantitative and qualitative analysis of the processes. Quantitative method was fully validated, and kinetic parameters of tiapride photodegradation were compared. Structures of twenty-one photoproducts as well as phototransformation pathways were proposed. Based on the elucidated structures, computational toxicity assessment with the use of various software was performed and some of transformation products were found as a potentially highly mutagenic and carcinogenic compounds. The multivariate statistical method (principal component analysis) was used to compare toxicity of phototransformation products as well as toxicity assessment.

Quantification and human health risk assessment of by-products of photo catalytic oxidation of ethylbenzene, xylene and toluene in indoor air of analytical laboratories.

The by-products of TiO2-based photocatalytic oxidation (PCO) of ethylbenze, p,m-xylene, o-xylene and toluene (EXT) in vapour phase and those adsorbed on the catalyst surface (solid phase) were identified and quantified on GC/GC-MS. A factor was developed in terms of µg of by-product produced per mg of EXT removed per sq-meter surface area of catalyst for estimating the mass of by-products produced. The by-products quantified were: acetone, hexane, cyclohexane, benzene, crotonaldehyde, toulene, 1,4-benzoquinone, benzaldehyde, phenol, benzylalcohol, cresol, hydroquinone and benzoic acid. The by-products accounted for 2.3-4.2% of the total mass of EXT treated. For treating concentrations of 220µg/m(3) (ethylbenzene), 260µg/m(3) (p,m-xylene), 260µg/m(3) (o-xylene) and 320µg/m(3) (toluene), at a flow rate of 7L/min for 12h in a laboratory of volume 195m(3), the estimated cancer risks of by-products to the occupants were 1.51×10(-6), 1.06×10(-6), 4.69×10(-7), and 1.58×10(-9) respectively. The overall hazard index (HI) of the by-products for EXT was of the order 10(-4); which is much less than desired level of 1.0. The estimated risks were within the acceptable level. This study has also suggested the photocatalytic degradation pathways for EX which are through formation of toluene.

Eco-friendly synthesis of core-shell structured (TiO2/Li2CO3) nanomaterials for low cost dye-sensitized solar cells.

Core-shell structured TiO2/Li2CO3 electrode was successfully synthesized by eco-friendly solution growth technique. TiO2/Li2CO3 electrodes were characterized using X-ray Diffractometer (XRD), Scanning electron microscopy (SEM) and photocurrent-voltage measurements. The synthesized core-shell electrode material was sensitized with tetrabutylammonium cis-di(thiocyanato)-N,N'-bis(4-carboxylato-4'-carboxylic acid-2,2'-bipyridine)ruthenate(II) (N-719). The performance of dye-sensitized solar cells (DSCs) based on N719 dye modified TiO2/Li2CO3 electrodes was investigated. The effect of various shell thickness on the photovoltaic performance of the core-shell structured electrode is also investigated. We found that Li2CO3 shells of all thicknesses perform as inert barriers which improve open-circuit voltage (Voc) of the DSCs. The energy conversion efficiency was greatly dependent on the thickness of Li2CO3 on TiO2 film, and the highest efficiency of 3.7% was achieved at the optimum Li2CO3 shell layer.

Membrane bioreactor: A mini review on recent R&D works.

Membrane bioreactor (MBR) has been widely applied worldwide in full scale. Recent research and development trends of MBR technology has been shifted from process optimization and economic evaluation to installation of new process architecture to enrich functional strains like nitrifiers or providing assisted field for performance enhancement, to incorporation of affordable adsorbents or scouring agent for membrane fouling mitigation, and to applying MBR hybrid systems for achieving simultaneous removals of nutrients and other pollutants. This mini-review summarized the recent works, principally in 2014-2015, on the above aspects, and provided a discussion on the osmotic MBR based on forward osmosis on its use of high-osmotic-pressure draw solution and the pre-treatment needed, and the reverse solute leakage that affects the MBR efficiency.

Tracking diurnal variation in photosynthetic down-regulation using low cost spectroscopic instrumentation.

Photosynthetic light-use efficiency (LUE) has gained wide interest as an input to modeling forest gross primary productivity (GPP). The photochemical reflectance index (PRI) has been identified as a principle means to inform LUE-based models, using airborne and satellite-based observations of canopy reflectance. More recently, low-cost electronics have become available with the potential to provide for dense in situ time-series measurements of PRI. A recent design makes use of interference filters to record light transmission within narrow wavebands. Uncertainty remains as to the dynamic range of these sensors and performance under low light conditions, the placement of the reference band, and methodology for reflectance calibration. This paper presents a low-cost sensor design and is tested in a laboratory set-up, as well in the field. The results demonstrate an excellent performance against a calibration standard (R2 = 0.9999) and at low light conditions. Radiance measurements over vegetation demonstrate a reversible reduction in green reflectance that was, however, seen in both the reference and signal wavebands. Time-series field measurements of PRI in a Douglas-fir canopy showed a weak correlation with eddy-covariance-derived LUE and a significant decline in PRI over the season. Effects of light quality, bidirectional scattering effects, and possible sensor artifacts on PRI are discussed.

Effects of photodemethylation on the methylmercury budget of boreal Norwegian lakes.

Methylmercury (MeHg) concentrations in freshwater fish from southeastern Norway continue to increase, highlighting the need for a comprehensive understanding of MeHg sources, cycling, and degradation in the aquatic environment. The authors assessed the importance of photodemethylation in the MeHg budget of 4 Norwegian lakes. Photodemethylation rates were determined using incubation experiments with MeHg-spiked natural lake water. The authors determined full-spectrum exposure rates at all study sites and waveband-specific rates (photosynthetically active radiation, ultraviolet-A radiation, and ultraviolet-B radiation) at 1 clear-water (Sognsvann) and 1 humic (Langtjern) site. No significant differences in photodemethylation rates between the sites were found, and the authors' observed rates agreed with available literature for lake and wetland waters. The authors paired experimentally derived photodemethylation rates with lake-specific incident irradiation, light attenuation, and MeHg concentrations to estimate MeHg loss through photodemethylation for the study sites. For Langtjern, losses through photodemethylation equalled 27% of total annual inputs, highlighting the importance of photodemethylation in the MeHg budget. Furthermore, the authors assessed how changes in terrestrial dissolved organic carbon (DOC) exported to freshwaters and climate-driven reductions in ice cover duration may affect MeHg losses through photodemethylation. Results suggest that future increases in DOC may lead to higher aqueous MeHg concentrations in boreal lakes due to increased DOC-associated MeHg inputs paired with significant decreases in the loss of MeHg through photodemethylation due to increased light attenuation.

Comparison between solar utilization of a closed microalgae-based bio-loop and that of a stand-alone photovoltaic system.

This study compared the solar energy utilization of a closed microalgae-based bio-loop for energy efficient production of biogas with fertilizer recovery against that of a stand-alone photovoltaic (PV) system. The comparison was made from the perspective of broad life cycle assessment, simultaneously taking exergy to be the functional unit. The results indicated that the bio-loop was more environmentally competitive than an equivalent stand-alone PV system, but had higher economic cost due to high energy consumption during the operational phase. To fix the problem, a patented, interior pressurization scheduling method was used to operate the bio-loop, with microalgae and aerobic bacterial placed together in the same reactor. As a result, the overall environmental impact and total investment were respectively reduced by more than 75% and 84%, a vast improvement on the bio-loop.

Recycling of indium from CIGS photovoltaic cells: potential of combining acid-resistant nanofiltration with liquid-liquid extraction.

Electronic consumer products such as smartphones, TV, computers, light-emitting diodes, and photovoltaic cells crucially depend on metals and metalloids. So-called "urban mining" considers them as secondary resources since they may contain precious elements at concentrations many times higher than their primary ores. Indium is of foremost interest being widely used, expensive, scarce and prone to supply risk. This study first investigated the capability of different nanofiltration membranes of extracting indium from copper-indium-gallium- selenide photovoltaic cell (CIGS) leachates under low pH conditions and low transmembrane pressure differences (<3 bar). Retentates were then subjected to a further selective liquid-liquid extraction (LLE). Even at very acidic pH indium was retained to >98% by nanofiltration, separating it from parts of the Ag, Sb, Se, and Zn present. LLE using di-(2-ethylhexyl)phosphoric acid (D2EHPA) extracted 97% of the indium from the retentates, separating it from all other elements except for Mo, Al, and Sn. Overall, 95% (2.4 g m(-2) CIGS) of the indium could be extracted to the D2EHPA phase. Simultaneously, by nanofiltration the consumption of D2EHPA was reduced by >60% due to the metal concentration in the reduced retentate volume. These results show clearly the potential for efficient scarce metal recovery from secondary resources. Furthermore, since nanofiltration was applicable at very low pH (≥ 0.6), it may be applied in hydrometallurgy typically using acidic conditions.

Optical fluence modelling for ultraviolet light emitting diode-based water treatment systems.

This work presents a validated optical fluence rate model optimised for ultraviolet light-emitting diodes (UV-LEDs), which allow a very wide range of emission wavelengths and source geometries to be used in water treatment units. The model is based on a Monte Carlo approach, in which an incremental ray-tracing algorithm is used to calculate the local volumetric rate of energy absorption and subsequently convert it to the local fluence rate distribution for an UV-LED water treatment chamber of arbitrary design. The model includes contributions from optical reflections and scattering by treatment chamber walls and from scattering due to particulates and/or microorganisms. The model successfully predicts optical fluence rates in point-of-use water treatment units, as verified using biodosimetry with MS-2 bacteriophage at a UV-LED emission wavelength of 254 nm. The effects of chamber geometry are also modelled effectively and are consistent with the inactivation data for E. coli at 254 nm. The data indicate that this model is suitable for application in the design and optimisation of UV-LED-based water treatment systems.

Batch versus flow photochemistry: a revealing comparison of yield and productivity.

The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20% lower than that of batch, whereas three-layer reactors were 20% more productive. Finally, the utility of flow chemistry was demonstrated in the scale-up of the ring-opening reaction of a potentially explosive [1.1.1] propellane with butane-2,3-dione.