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Light-driven modulation of neuronal activity at high spatial-temporal resolution is becoming of high interest in neuroscience. In addition to optogenetics, nongenetic membrane-targeted nanomachines that alter the electrical state of the neuronal membranes are in demand. Here, we engineered and characterized a photoswitchable conjugated compound (BV-1) that spontaneously partitions into the neuronal membrane and undergoes a charge transfer upon light stimulation. The activity of primary neurons is not affected in the dark, whereas millisecond light pulses of cyan light induce a progressive decrease in membrane resistance and an increase in inward current matched to a progressive depolarization and action potential firing. We found that illumination of BV-1 induces oxidation of membrane phospholipids, which is necessary for the electrophysiological effects and is associated with decreased membrane tension and increased membrane fluidity. Time-resolved atomic force microscopy and molecular dynamics simulations performed on planar lipid bilayers revealed that the underlying mechanism is a light-driven formation of pore-like structures across the plasma membrane. Such a phenomenon decreases membrane resistance and increases permeability to monovalent cations, namely, Na+, mimicking the effects of antifungal polyenes. The same effect on membrane resistance was also observed in nonexcitable cells. When sustained light stimulations are applied, neuronal swelling and death occur. The light-controlled pore-forming properties of BV-1 allow performing "on-demand" light-induced membrane poration to rapidly shift from cell-attached to perforated whole-cell patch-clamp configuration. Administration of BV-1 to ex vivo retinal explants or in vivo primary visual cortex elicited neuronal firing in response to short trains of light stimuli, followed by activity silencing upon prolonged light stimulations. BV-1 represents a versatile molecular nanomachine whose properties can be exploit

Perylene dyes are a cornerstone of modern research and technology in fields ranging from printed (opto)electronics to bioimaging. Most known compounds are bisimide derivatives prepared from perylenetetracarboxylic dianhydride (PTCDA), which is essentially a chemical commodity. On the contrary, there are comparatively fewer reports on perylenedicarboxylic monoimide derivatives not due to lack of performance but due to the challenging access to the key intermediate 3,4-perylenedicarboxylic monoanhydride (PDCMA). As we detail, reported synthetic pathways are both costly, resource intensive, and associated with extremely poor green metrics. We show a new two-step straightforward, sustainable, efficient, and organic solvent-free preparation of PDCMA based on a combination of solventless and in-water reactions.

In the context of green chemistry, minimizing waste and energy consumption is crucial in chemical processes. Organic solvents, known for their toxicity and hazards, pose a significant waste issue, prompting the search for non-toxic alternatives like water for organic reactions. Despite the hydrophobic nature of many organic compounds in aqueous environments, self-assembling surfactants enable "micellar catalysis”, overcoming this challenge by hosting reagents in their lipophilic pockets, offering conditions for high-yield, efficient, and sustainable reactions, if appropriately chosen.1 The chemical nature of surfactant-formed interphases significantly influences products distribution in competitive reactions. Within the micelle, an interfacial dipole induces selectivity between the hydrophilic and hydrophobic portions of the surfactant. Introducing selectivity in surfactant-enhanced reactions requires controlling the non-covalent interaction between surfactant and substrates, considering: 1) regioselectivity in competitive transformations induced by the preferential orientation of reaction intermediates due to interface dipoles at the hydrophilic/lipophilic interphase; 2) product selectivity induced by specific surfactant/substrate interactions; and 3) product selectivity due to compartmentalization effects between the water and oil phases. To enhance selectivity, we propose a novel surfactant design with a photochromic compound, specifically a spiropyran. The photochromic residue is incorporated at the boundary between the hydrophilic and the lipophilic portion of the amphiphilic molecule, which consists respectively of a PEG moiety and an alkyl chain. Responsive to UV light, it switches between a neutral-low polarity and a zwitterionic-high polarity state. This tuning ability, rooted in the concept of photostatic equilibrium, determines the relative population of open (polar) and closed (nonpolar) forms of the photochromic molecules.2 Adjusting irradiation conditi

Sonogashira coupling is one of the cornerstone Palladium mediated cross coupling reactions, giving a direct and high yield access to symmetric and non-symmetric alkynes with high tolerance of substituents. The method generally requires the use of CuI as a cocatalyst, an inert atmosphere to protect palladium catalyst, somewhat harsh conditions like prolonged heating and the use of organic solvents due to the hydrophobicity of reagents and products. Leveraging on the opportunities offered by micellar catalysis, we here present a general methodology to perform Sonogashira coupling in water, with moderate or no heating, under air, without copper co-catalysts and at very low catalyst loading. The method offers the same generality and scope of organic solvents based couplings, but strongly improves sustainability while offering excellent yields.

Conjugated semiconducting polymers are key active materials for printable electronics, sensors and biosensors, organic photovoltaics, organic light emitting devices, and more. The research in the field developed very efficient materials and sound structure property relationships, thus making a case for a transition from laboratory to industrial environment. At this critical juncture, sustainability, and ease of scaling up are at least as important as performances, to the point that efficient materials on a lab scale could become unpractical for the industry. The development of more efficient synthetic protocols and the complete removal of all organic solvents from both the synthesis and the processing of semiconducting polymers can help tremendously to improve sustainability and reduce costs. It is shown that the use of an aqueous dispersion of the food grade surfactant lecithin as the medium, enables the synthesis and processing of the representative semiconducting alternating copolymer poly (9,9-dioctylfluorene-alt-bithiophene) (PF8T2) in high yield and high quality and with transistor performances comparable with those obtained with reference materials synthetized and processed from volatile organic solvents.

Micellar catalysis is playing a major role in green chemistry with ever increasing applications in the efficient and sustainable preparation of natural compounds, drugs, and more recently organic semiconductors for printed electronics. Most of the contributions in the field focus on the developments of surfactants and suitable formulative conditions capable of reproducing – and often improving – the yield of reactions commonly performed in organic solvents. The real ambition of the micellar catalysis approach goes beyond the improvement in the sustainability of existing methods and aims at mimicking not only the efficiency but also the selectivity of enzymatic catalysis. This review summarizes relevant examples of micellar catalysis enabled, efficient, and selective transformations, and discusses the different kind of processes impacting on the product distribution depending on the details of the formulative state achieved.

Doped organic semiconductors play a central role in the development of several innovative optoelectronic and energy harvesting applications. Currently, the realization of thermoelectric generators, which require both hole- and electron-transporting materials with high electrical conductivity, is strongly hindered by the scarce availability of stable solution-processable n-dopants and their limited efficiency. Herein, the synthesis of 4-(1,3-dimethyl-2,3-dihydro-1H-benzimidazol-2-yl)-dibenzazepine (IStBI), a novel derivative belonging to the well-known family of the benzimidazoline compounds, is presented. The functionalization with the planarized and rigid iminostilbene substituent allows, without significantly affecting the compound electronic structure, an efficient intercalation of the dopant molecules inside the ordered regions of thin films of the benchmark n-type polymer poly(N,N′-bis-2-octyldodecylnaphthalene-1,4,5,8-bis-dicarboximide-2,6-diyl-alt-5,5′-2,2′-bithiophene) P(NDI2OD-T2). Consequently, a maximum electrical conductivity of (1.14 ± 0.13) × 10−2 S cm−1 is recorded, exceeding by one order of magnitude what previously achieved upon solution doping of the reference P(NDI2OD-T2) with benzimidazoline derivatives. The thermoelectric power factor is also simultaneously increased. The findings confirm that tailoring of the dopant chemical structure to improve structural interactions with the host semiconductors can be employed as a successful strategy to achieve more effective n-doping, helping to close the performance gap with p-type materials.

Quadruple addition of phenyl groups to a diphenylpyridylmethane skeleton was achieved. The derived (3,5-difluoro-4-pyridyl)bis(2,6-dichloro-3,4-diphenylphenyl)methyl radical (Ph4-F2PyBTM) displayed superior luminescence properties to the previously reported organic diphenylpyridylmethyl radicals in various organic solutions at room temperature, and it reached 33% photoluminescence quantum efficiency in PMMA film. With the introduction of methoxy groups, quadruple adduct (MeOPh)4-F2PyBTM and triple adduct (MeOPh)3-F2PyBTM were isolated. The excited state of these radicals showed an intramolecular charge transfer character and efficient fluorescence only in nonpolar solvents. The radicals retained not only persistency at the ground state but also durability under photoirradiation, with a 6 to 14 fold improved photostability with respect to the original PyBTM.

A highly crystalline, highly emissive, and wide-bandgap polymer AC174 with an extremely small Stokes shift is designed and synthesized in water, and is used to reduce system energetic disorder and increase the exciton diffusion length of the classical PM6:Y6 blend system. AC174 is incompatible with PM6 and Y6, improves molecular packing, and reduces system energetic disorder. The long-range Förster resonance energy transfer between the donor and acceptor is enhanced, and the exciton diffusion constant and exciton lifetime are increased, leading to a longer exciton diffusion length and more efficient exciton dissociation and charge generation. The addition of AC174 simultaneously improves the open-circuit voltage, short-circuit current density (JSC) and fill factor of PM6:Y6 devices; especially the highest internal quantum efficiency approaches 100%, and the highest JSC is 28.4 mA cm−2. Ternary devices with 5% AC174 in the donors achieve a power conversion efficiency of 17.2%, higher than those of the parent binary devices based on PM6:Y6 (15.9%) and AC174:Y6 (3.24%).

Micellar catalysis is having a dramatic impact in improving the sustainability of a wide variety of chemical transformations, including most of the popular palladium mediated carbon–carbon and carbon–nitrogen bond forming reactions. The Suzuki-Miyaura coupling is one of the earliest examples of micellar catalyzed reactions and it is still a very much active research field even at industrial scale. So far, micellar catalysis proved particularly efficient in enabling the high yield, low catalyst loading and mild reaction condition coupling of hydrophobic reagents in a water solution of selected surfactants. In this paper we show that the use of aqueous solutions of a mixture of food grade lecithin and the industrial surfactant Tween 80 not only enables efficient coupling in water of hydrophobic chemicals, but also provides a very resourceful tool for the functionalization of water and organic solvent insoluble pigments of interest for the dye and printed electronic industries.

Molecular doping of conjugated polymers is extremely desirable to control charge density gradients and shape the electric field across polymer electronic devices, including highly efficient organic solar cells. It is also a fundamental requirement for organic thermoelectrics and a powerful strategy to boost charge injection and transport properties in transistors. Yet, currently available doping approaches are far from offering a suitable level of control, particularly in the case of n-type doping. We here reveal that part of this limitation lies in the lack of understanding of dominant factors in doping efficiency. In particular, we highlight the key role played by very small amounts of a specific decomposition product formed during processing of the widely used molecular dopant 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (DMBI-H) in influencing the n-type conductivity in polymer blends. We show that such an overlooked decomposition product acts as a nucleating agent for a new crystalline phase of DMBI-H, with the overall effect of boosting the electrical conductivity of the final doped polymer films. Such results, confirmed by control experiments performed with a different nucleating agent, focus on the crucial role played by the solid-state microstructure in molecular doped semiconductors and offer ground for a significant change in design guidelines for molecular doping strategies.

The impact on chiral aggregation in solution processed and thermally annealed thin films of two indolenine and one anilino squaraines with chiral (S)-citronellyl functionalization at the nitrogen of the squaraine backbone is investigated. A pseudo polymorphic crystal structure is obtained for one of the indolenine squaraines, but thin films of both compounds are basically non-aggregated and truly isotropic as evidenced by spectroscopic ellipsometry. The anilino squaraine coalesces and readily aggregates to circular dichroic but discontinuous thin films. The extent of circular dichroism correlates with the morphology of the samples, which is quantified by Mueller matrix polarimetry in combination with atomic force microscopy. The shape of the CD spectra reinforces the hybrid Frenkel and charge-transfer excitonic nature of the characteristic double hump signatures within unpolarized absorbance spectra of previously investigated non-chiral anilino squaraines with linear alkyl chain functionalization. Such excitonic CD offers an additional design parameter for next-generation opto-electronic devices.

Innovative sustainable synthetic methods for the production of perylenemonoimide derivatives and their application in retinal photosensitisation

Molecular doping can increase the conductivity of organic semiconductors and plays an increasingly important role in emerging and established plastic electronics applications. 4-(1,3-Dimethyl-2,3-dihydro-1H-benzimidazol-2-yl)-N,N-dimethylaniline (N-DMBI-H) and tris(pentafluorophenyl)borane (BCF) are established n- and p-dopants, respectively, but neither functions as a simple one-electron redox agent. Molecular hydrogen has been suggested to be a byproduct in several proposed mechanisms for doping using both N-DMBI-H and BCF. In this paper we show for the first time the direct detection of molecular hydrogen in the uncatalysed doping of a variety of polymeric and molecular semiconductors using these dopants. Our results provide insight into the doping mechanism, providing information complementary to that obtained from more commonly applied methods such as optical, electron spin resonance, and electrical measurements.

This account summarizes the impact that the quest for sustainability is having on the field of organic polyconjugate molecules and polymers for plastic (opto)electronics. While at the proof-of-concept level, the design criteria as well as the preferred synthetic strategies to access new and improved materials, have been dominated by the need of performance. The ongoing transition from the lab environment to the industrial scale imposes strict limitations to the cost and overall environmental impact of new materials. We here summarize our efforts devoted to the development of new design criteria and synthetic strategies aimed at improving sustainability - without compromising performances - in organic polyconjugated molecules. The article is composed of three sections: Introduction and motivation, sustainability through improved synthetic methods and through improved design. Outline 1 Introduction and motivation 2 Sustainable reaction methods 2.1 The new tools: reactions in aqueous solution of surfactants 2.2 Intrinsically more sustainable reactions: direct arylation 2.3 Sustainable multistep protocols: combining micellar, solventless and mechanochemical methods. 3 Sustainability as a design criterion: de novo design 4 Conclusion.

Perovskite materials research has received unprecedented recognition due to its applications in photovoltaics, LEDs, and other large area low-cost electronics. The exceptional improvement in the photovoltaic conversion efficiency of Perovskite solar cells (PSCs) achieved over the last decade has prompted efforts to develop and optimize device fabrication technologies for the industrial and commercial space. However, unstable operation in outdoor environments and toxicity of the employed materials and solvents have hindered this proposition. While their optoelectronic properties are extensively studied, the environmental impacts of the materials and manufacturing methods require further attention. This review summarizes and discusses green and environment-friendly methods for fabricating PSCs, particularly non-toxic solvents, and lead-free alternatives. Greener solvent choices are surveyed for all the solar cell films, (i.e. electron and hole transport, semiconductor, and electrode layers) and their impact on thin film quality, morphology and device performance is explored. We also discuss lead content in perovskites, its environmental impact and sequestration routes, and progress in replacing lead with greener alternatives. This review provides an analysis of sustainable green routes in perovskite solar cell fabrication, discussing the impact of each layer in the device stack, via life cycle analysis.

Photodynamic inhibition (PDI) of bacteria represents a powerful strategy for dealing with multidrug-resistant pathogens and infections, as it exhibits minimal development of antibiotic resistance. The PDI action stems from the generation of a triplet state in the photosensitizer (PS), which subsequently transfers energy or electrons to molecular oxygen, resulting in the formation of reactive oxygen species (ROS). These ROS are then able to damage cells, eventually causing bacterial eradication. Enhancing the efficacy of PDI includes the introduction of heavy atoms to augment triplet generation in the PS, as well as membrane intercalation to circumvent the problem of the short lifetime of ROS. However, the former approach can pose safety and environmental concerns, while achieving stable membrane partitioning remains challenging due to the complex outer envelope of bacteria. Here, we introduce a novel PS, consisting of a metal-free donor-acceptor thiophene-based conjugate molecule (BV-1). It presents several advantageous features for achieving effective PDI, namely: (i) it exhibits strong light absorption due to the conjugated donor-acceptor moieties; (ii) it exhibits spontaneous and stable membrane partitioning thanks to its amphiphilicity, accompanied by a strong fluorescence turn-on; (iii) it undergoes metal-free intersystem crossing, which occurs preferentially when the molecule resides in the membrane. All these properties, which we rationalized via optical spectroscopies and calculations, enable the effective eradication of Escherichia coli, with an inhibition concentration that is below that of current state-of-the-art treatments. Our approach holds significant potential for the development of new PS for controlling bacterial infections, particularly those caused by Gram-negative bacteria.

Cesium lead halide perovskite nanocrystals of general formula CsPbX3 are having tremendous impact on a vast array of technologies requiring strong and tunable luminescence across the visible range and solutions processing. The development of plastic scintillators is just one of the many relevant applications. The syntheses are relatively simple but generally unsuitable to produce a large amount of material of reproducible quality required when moving from proof-of-concept scale to industrial applications. Wastes, particularly large amounts of lead-contaminated toxic and flammable organic solvents, are also an open issue. We describe a simple and reproducible procedure enabling the synthesis of luminescent CsPbX3 nanobricks of constant quality on a scale going from 0.12 to 8 g in a single batch. We also show complete recycling of the reaction wastes, leading to dramatically improved efficiency and sustainability.