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tert -Amines were harnessed to afford arenesulfonyl hydrazides and arenesulfonyl chlorides via a metal-, oxidant- and halogen-free electrochemical oxidative coupling in an undivided cell at RT. This environmentally benign approach afforded a wide spectrum of sulfonamides in satisfactory yields using cheap and renewable Pencil Graphite Electrodes (PGEs).

This paper describes an atom-economical strategy for the direct conversion of Baylis–Hillman alcohols to β-chloro aldehydes under metal free conditions with excellent functional group tolerance. The use of stable-nontoxic Oxone as a terminal oxidant along with an inexpensive salt (sodium chloride) as a halogen source and water as the reaction medium makes this chemical synthetic process more viable and environmentally benign contributing towards green chemistry.

An amorphous Cu–In–S nanoparticle-based precursor ink with improved atom economy was developed in which a large amount of bulky organic ligands was replaced with metal salt–organic ligand complexes. This change resulted in a reduction of the required amount of organic ligands in the ink, meaning that additional spaces in the green layer were occupied by constituent metal atoms rather than organic ligands. Using modified amorphous Cu–In–S nanoparticle inks containing metal salt–organic ligand complexes, improvement of the morphologies of selenized CuInSe 2 thin films was observed in terms of greater compactness, better flatness, and larger grains, which led to an increase in the device efficiency to 10.85%. This result demonstrates that even with low-quality precursor materials, such as amorphous Cu–In–S nanoparticles, proper control of the atom economy of the precursor inks enables the facile fabrication of high-quality inorganic semiconductor films and devices at low cost.

In this work, a novel IL-based synergistic extraction system utilizing the ionic liquid tricaprylmethylammonium nitrate ([A336][NO 3 ]) and the commercial extractant di(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP) was developed for the extraction of rare earth (RE) nitrates. Pr( III ) was used as a model RE and the effects of key factors, i.e. the ratio of [A336][NO 3 ] to DEHEHP, the acidity of feed solutions, and the concentration of a salting-out reagent, were systematically studied. Our results demonstrate that the mixture of [A336][NO 3 ] and DEHEHP had an obviously synergistic extraction effect for the extraction of Pr( III ). The maximum synergistic enhancement coefficient of 3.44 was attained at X A = 0.4 (v%). Alternatively, a mixture of [A336][Cl] and DEHEHP hardly extracted Pr( III ) from chloride media. Moreover, we investigated the Pr( III ) extraction mechanism and demonstrated that Pr( III ) can be extracted as the neutral complexation species Pr(NO 3 ) 3 · x DEHEHP and the ion-type species [A336] y ·Pr(NO 3 ) 3+ y . These extraction processes can effectively hamper the release of organic cation-ligands into the aqueous phase. The synergistic extraction effect is mainly derived from the enhanced solubility of the extracted species in the ionic liquid phase. The extraction behaviors of Pr( III ) could be properly described by Langmuir and pseudo-second-order rate equations. An increase in temperature was unfavorable for the extraction reaction but greatly improved the extraction rate. Interestingly, the mixed IL extraction system has an obviously synergistic extraction effect for light REs (LREs, La–Eu), but an anti-synergistic effect for heavy REs (HREs, Gd–Lu, Y), thus indicating that our synergistic extraction system is helpful for the separation of LREs from HREs. In addition, the high selectivity between REs and non-REs suggested that the recovery of REs from a complicated high-salt leachate could be highly possible. It demonstrates that the IL-based synergistic extraction strategy developed in this work is promising and sustainable, and as a result the development of an IL-based synergistic extraction process for the recovery of REs is straightforwardly envisaged.

We have investigated an economical green route for the synthesis of a p-type N-doped ZnO photocatalyst by a wet chemical method. Significantly, hazardous H 2 S waste was converted into eco-friendly hydrogen energy using the p-type N-doped ZnO photocatalyst under solar light, which has previously been unattempted. The as-synthesized p-type N-doped ZnO shows a hexagonal wurtzite structure. The optical study shows a drastic shift in the band gap of the doped ZnO in the visible region (3.19–2.3 eV). The doping of nitrogen into the ZnO lattice is conclusively proved from X-ray photoelectron spectroscopy analysis and Raman scattering. The morphological features of the N-doped ZnO are studied from FESEM , TEM and reveal particle sizes to be in the range of ～4–5 nm. The N-doped ZnO exhibits enhanced photocatalytic hydrogen generation (～3957 μmol h ?1 ) by photodecomposition of hydrogen sulfide under visible light irradiation, which is much higher as compared to semiconductor metal oxides reported so far. It is noteworthy that a green catalyst is investigated to curtail H 2 S pollution along with production of hydrogen (green fuel ) using solar light, i.e. , a renewable energy source. The green process investigated will have the potential to synthesize other N-doped metal oxides .

An efficient and environmentally benign amidation of aldehydes with N -chloroamines has been developed using AIBN as an initiator. This methodology offers a metal free and base free approach and is endowed with mild reaction conditions, high yields, and good functional group tolerance.

The efficient production of biodiesel in hydrophobic ionic liquids using immobilized lipase was demonstrated. The use of ionic liquids containing long alkyl chains on the cation has the important advantage of producing homogeneous systems at the start of the reaction but, when the reaction is complete, a three-phase system is created that allows selective extraction of the products using straightforward separation techniques, while the ionic liquid and the enzyme can be reused. Fifteen ionic liquids based on different alkyl chain length of the methyl imidazolium cation ([C 10 MIM], [C 12 MIM], [C 14 MIM], [C 16 MIM] and [C 18 MIM]) combined with [BF 4 ], [PF 6 ] or [NTf 2 ] anions were assayed as reaction media for two immobilized lipases ( Candida antarctica lipase B and Pseudomonas fluorescens lipase AK) for biodiesel production. The highest synthetic activity was obtained in [C 16 MIM] [NTf 2 ] using Novozym 435 (immobilized Candida antarctica lipase with 245.13 U g ?1 IME), its activity being more than three times higher than in a solvent -free system. Additionally, in this IL the fatty acid methyl esters production was 90.29% after 3 h, while in the solvent -free system it was 27.3%. The influence of several reaction parameters, such as temperature, methanol-to-oil molar ratio, alkyl-chain length of the alcohols , IL?:?substrate volume ratios, amount of enzyme, and oils feedstock were studied and optimized.

Green and efficient catalysts for the production of biodiesel are highly important. In this study, a Pickering magnetic interface biocatalyst (Fe 3 O 4 @PS-NH-lipase) was prepared, which can effectively stabilize the soybean oil-in-methanol emulsion and achieve static transesterification. When the appropriate methanol/soybean oil molar ratio and catalyst loading were chosen, the Pickering interface biocatalyst exhibited outstanding enzymatic activity, reaching a conversion rate of 89.3% after 30 h. Pickering interfacial catalysis (PIC, immobilizing catalytic centers on a carrier and combining it with a Pickering emulsion) shows more significant specific activity, leading to a 1.2-fold improvement in catalytic performance as compared to Pickering assisted catalysis (PAC, relying on the use of nanoparticles for stabilizing Pickering emulsions together with a homogeneous catalyst). Moreover, the recycled catalyst still possesses significant catalytic activity after 5 cycles. This article provides a green and efficient strategy for the effective recovery of biologically active substances and the enhancement of biphasic reactions.

Structural alerts are widely accepted in chemical toxicology and regulatory decision support as a simple and transparent means to flag potential chemical hazards or group compounds into categories for read-across. However, there has been a growing concern that alerts disproportionally flag chemicals as toxic, which questions their reliability as toxicity markers. Conversely, rigorously developed and properly validated statistical QSAR models can accurately and reliably predict the toxicity of a chemical; however, their use in regulatory toxicology has been hampered by a lack of transparency and interpretability. We demonstrate that contrary to the common perception of QSAR models as “black boxes” they can be used to identify statistically significant chemical substructures (QSAR-based alerts) that influence toxicity. We show through several case studies, however, that the mere presence of structural alerts in a chemical, irrespective of the derivation method (expert-based or QSAR-based), should be perceived only as hypotheses of possible toxicological effect. We propose a new approach that synergistically integrates structural alerts and rigorously validated QSAR models for a more transparent and accurate safety assessment of new chemicals.

Algae are being explored as a sustainable energy feedstock, having potential to reduce dependence on petrofuels and offset greenhouse gas emissions. Economic considerations and principles of green design suggest that if algae-to- fuel technology is to be successful, biofuels must be produced simultaneously with value-added co-products. At present, the algae industry is centered around a limited number of products, such as low-volume/high-value speciality nutrients . New products for medium- and high-volume markets will be needed as biomass production increases in scale. This Perspective highlights non-fuel applications of algal biomass that have received relatively little attention to date but are promising for future development. It is our goal to draw attention to some of the unique opportunities that algae present with respect to biochemical composition as compared to lignocellulosic energy crops.