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The reversible modulation of acidity using molecular photoswitches enables the remote control of a variety of (bio)chemical processes with light. Herein we investigated the structural features that allow amplifying photoinduced p K a variation in phenol-diarylethene conjugates, which toggle between low- and high-acidity states by switching the conjugation between the ionizable moiety and electron-withdrawing groups upon photoisomerization. By tuning the structure of these conjugates, high p K a modulation amplitudes were accomplished that surpass those previously reported.

Ternary tetrahedral II-III 2 -VI 4 semiconductors, where II is Zn or Cd, III In or Ga, and VI S, Se, or Te, are of interest in UV radiation detectors in medicine and space physics as well as CO 2 photoreduction under visible light. We synthesize colloidal II-III 2 -VI 4 semiconductor nanocrystals from readily available precursors and ascertain their ternary nature by structural and spectroscopic methods, including 77 Se solid-state NMR spectroscopy. The pyramidally shaped nanocrystals range between 2 and 12 nm and exhibit optical gaps of 2-3.9 eV. In the presence of excess anions on the particle surface, treatment with Lewis acidic, Z-type ligands results in better passivation and enhanced photoluminescence. Electronic structure calculations reveal the most stable, lowest energy polymorphs and coloring patterns. This work will pave the way toward more environmentally friendly, ternary semiconductors for optoelectronics and electrocatalysis., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Tin-based semiconductors are highly desirable materials for energy applications due to their low toxicity and biocompatibility relative to analogous lead-based semiconductors. In particular, tin-based chalcohalides possess optoelectronic properties that are ideal for photovoltaic and photocatalytic applications. In addition, they are believed to benefit from increased stability compared with halide perovskites. However, to fully realize their potential, it is first necessary to better understand and predict the synthesis and phase evolution of these complex materials. Here, we describe a versatile solution-phase method for the preparation of the multinary tin chalcohalide semiconductors Sn 2 SbS 2 I 3 , Sn 2 BiS 2 I 3 , Sn 2 BiSI 5 , and Sn 2 SI 2 . We demonstrate how certain thiocyanate precursors are selective toward the synthesis of chalcohalides, thus preventing the formation of binary and other lower order impurities rather than the preferred multinary compositions. Critically, we utilized 119 Sn ssNMR spectroscopy to further assess the phase purity of these materials. Further, we validate that the tin chalcohalides exhibit excellent water stability under ambient conditions, as well as remarkable resistance to heat over time compared to halide perovskites. Together, this work enables the isolation of lead-free, stable, direct band gap chalcohalide compositions that will help engineer more stable and biocompatible semiconductors and devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In biosensor development, silk fibroin is advantageous for providing transparent, flexible, chemically/mechanically stable, biocompatible, and sustainable substrates, where the biorecognition element remains functional for long time periods. These properties are employed here in the production of point-of-care biosensors for resource-limited regions, which are able to display glucose levels without the need for external instrumentation. These biosensors are produced by photopatterning silk films doped with the enzymes glucose oxidase and peroxidase and photoelectrochromic molecules from the dithienylethene family acting as colorimetric mediators of the enzymatic reaction. The photopatterning results from the photoisomerization of dithienylethene molecules in the silk film from its initial uncolored opened form to its pink closed one. The photoisomerization is dose-dependent, and colored patterns with increasing color intensities are obtained by increasing either the irradiation time or the light intensity. In the presence of glucose, the enzymatic cascade reaction is activated, and peroxidase selectively returns closed dithienylethene molecules to their initial uncolored state. Color disappearance in the silk film is proportional to glucose concentration and used to distinguish between hypoglycemic (below 4 mM), normoglycemic (4-6 mM), and hyperglycemic levels (above 6 mM) by visual inspection. After the measurement, the biosensor can be regenerated by irradiation with UV light, enabling up to five measurement cycles. The coupling of peroxidase activity to other oxidoreductases opens the possibility to produce long-life reusable smart biosensors for other analytes such as lactate, cholesterol, or ethanol.

The early detection of very low bacterial concentrations is key to minimize the healthcare and safety issues associated with microbial infections, food poisoning or water pollution. In amperometric integrated circuits for electrochemical sensors, flicker noise is still the main bottleneck to achieve ultrasensitive detection with small footprint, cost-effective and ultra-low power instrumentation. Current strategies rely on autozeroing or chopper stabilization causing negative impacts on chip size and power consumption. This work presents a 27-μW potentiostatic-amperometric Delta-Sigma modulator able to cancel its own flicker noise and provide a 4-fold improvement in the limit of detection. The 2.3-mm 2 all-in-one CMOS integrated circuit is glued to an inkjet-printed electrochemical sensor. Measurements show that the limit of detection is 15 pA rms , the extended dynamic range reaches 110 dB and linearity is R 2  = 0.998. The disposable device is able to detect, in less than 1h, live bacterial concentrations as low as 10 2  CFU/mL from a 50-μL droplet sample, which is equivalent to 5 microorganisms., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Michele Dei reports financial support was provided by European Commission REA grant agreement no. 600388 (TECNIOspring programme). Xavier Munoz-Berbel reports financial support was provided by European Commission project PROTECT (H2020-NMBP-PILOT-720851)., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

By enabling rapid, cost-effective, user-friendly and in situ detection of carbon dioxide, colorimetric CO 2 sensors are of relevance for a variety of fields. However, it still remains a challenge the development of optical chemosensors for CO 2 that combine high sensitivity, selectivity and reusability with facile integration into solid materials. Herein we pursued this goal by preparing hydrogels functionalized with spiropyrans, a well-known class of molecular switches that undergo different color changes upon application of light and acid stimuli. By varying the nature of the substituents of the spiropyran core, different acidochromic responses are obtained in aqueous media that allow discriminating CO 2 from other acid gases (e.g., HCl). Interestingly, this behavior can be transferred to functional solid materials by synthesizing polymerizable spiropyran derivatives, which are used to prepare hydrogels. These materials preserve the acidochromic properties of the incorporated spiropyrans, thus leading to selective, reversible and quantifiable color changes upon exposure to different CO 2 amounts. In addition, CO 2 desorption and, therefore, recovery of the initial state of the chemosensor is favored by irradiation with visible light. This makes spiropyran-based chromic hydrogels promising systems for the colorimetric monitorization of carbon dioxide in a diversity of applications., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Marco, Guirado, Sebastián and Hernando.)

The detection of living organisms at very low concentrations is necessary for the early diagnosis of bacterial infections, but it is still challenging as there is a need for signal amplification. Cell culture, nucleic acid amplification, or nanostructure-based signal enhancement are the most common amplification methods, relying on long, tedious, complex, or expensive procedures. Here, we present a cyanotype-based photochemical amplification reaction enabling the detection of low bacterial concentrations up to a single-cell level. Photocatalysis is induced with visible light and requires bacterial metabolism of iron-based compounds to produce Prussian Blue. Bacterial activity is thus detected through the formation of an observable blue precipitate within 3 h of the reaction, which corresponds to the concentration of living organisms. The short time-to-result and simplicity of the reaction are expected to strongly impact the clinical diagnosis of infectious diseases.

Microbial detection is crucial for the control and prevention of infectious diseases, being one of the leading causes of mortality worldwide. Among the techniques developed for bacterial detection, those based on metabolic indicators are progressively gaining interest due to their simplicity, adaptability, and, most importantly, their capacity to differentiate between live and dead bacteria. Prussian blue (PB) may act as a metabolic indicator, being reduced by bacterial metabolism, producing a visible color change from blue to colorless. This molecule can be present in two main forms, namely, the soluble and the insoluble, having different properties and structures. In the current work, the bacterial-sensing capacity of soluble and insoluble PB will be tested and compared both in suspensions as PB-NPs and after deposition on transparent indium tin oxide-poly(ethylene terephthalate) (ITO-PET) electrodes. In the presence of live bacteria, PB-NPs are metabolized and completely reduced to the Prussian white state in less than 10 h for soluble and insoluble forms. However, when electrodeposited on ITO-PET substrates, less than 1 h of incubation with bacteria is required for both forms, although the soluble one presents faster metabolic reduction kinetics. This study paves the way to the use of Prussian blue as a metabolic indicator for the early detection of bacterial infection in fields like microbial diagnostics, surface sterilization, food and beverage contamination, and environmental pollution, among others., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Sepsis is a serious bloodstream infection where the immunity of the host body is compromised, leading to organ failure and death of the patient. In early sepsis, the concentration of bacteria is very low and the time of diagnosis is very critical since mortality increases exponentially with every hour after infection. Common culture-based methods fail in fast bacteria determination, while recent rapid diagnostic methods are expensive and prone to false positives. In this work, we present a sepsis kit for fast detection of bacteria in whole blood, here achieved by combining selective cell lysis and a sensitive colorimetric approach detecting as low as 10 3 CFU/mL bacteria in less than 5 h. Homemade selective cell lysis buffer (combination of saponin and sodium cholate) allows fast processing of whole blood in 5 min while maintaining bacteria alive (100% viability). After filtration, retained bacteria on filter paper are incubated under constant illumination with the electrochromic precursors, i.e., ferricyanide and ferric ammonium citrate. Viable bacteria metabolically reduce iron(III) complexes, initiating a photocatalytic cascade toward Prussian blue formation. As a proof of concept, we combine this method with antibiotic susceptibility testing to determine the minimum inhibitory concentration (MIC) using two antibiotics (ampicillin and gentamicin). Although this kit is used to demonstrate its applicability to sepsis, this approach is expected to impact other key sectors such as hygiene evaluation, microbial contaminated food/beverage, or UTI, among others.

The application of molecular switches for the fabrication of multistimuli-responsive chromic materials and devices still remains a challenge because of the restrictions imposed by the supporting solid matrices where these compounds must be incorporated: they often critically affect the chromic response as well as limit the type and nature of external stimuli that can be applied. In this work, we propose the use of ionogels to overcome these constraints, as they provide a soft, fluidic, transparent, thermally stable, and ionic-conductive environment where molecular switches preserve their solution-like properties and can be exposed to a number of different stimuli. By exploiting this strategy, we herein pioneer the preparation of nitrospiropyran-based materials using a single solid platform that exhibit optimal photo-, halo-, thermo-, and electrochromic switching behaviors.

The control of chemical functionalization with orthogonal light stimuli paves the way toward manipulating materials with unprecedented spatiotemporal resolution. To reach this goal, we herein introduce a photochemical reaction system that enables two-color control of covalent ligation via an oxo -Diels-Alder cycloaddition between two separate light-responsive molecular entities: a UV-activated photocaged diene based on ortho -quinodimethanes and a carbonyl dienophile appended to a diarylethene photoswitch, whose reactivity can be modulated upon illumination with UV and visible light.

One of the limitations of many skin-patch wearable sensors today is their dependence on silicon-based electronics, increasing their complexity and unit cost. Self-powered sensors, in combination with electrochromic materials, allow simplifying the construction of these devices, leading to powerful analytical tools that remove the need for external detection systems. This work describes the construction, by screen-printing, of a self-powered electrochromic device that can be adapted for the determination of metabolites in sweat by the naked eye in the form of a 3 × 15 mm colour bar. The device comprises a lactate oxidase and osmium-polymer -based anode connected to a coplanar 3 × 15 mm Prussian Blue, PB, cathode printed over a transparent poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, PEDOT:PSS electrode. An ion-gel composed of Poly(vinylidene fluoride-co-hexafluoropropylene), PVDF-co-HFP, a gelling agent, and ionic liquid 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate, EMIM-Tf, effectively separates the cathode display from the biosensing anode, protecting it from the sample. Despite its cathodic electrochromism, the PEDOT:PSS has a transmission above 90% and does not mask the Prussian Blue colour change because the cathode does not operate below 0 V vs Ag/AgCl at any time. The sensor displays lactate concentrations in the range of 0-10 mM over the length of the electrochromic display, which has a contrast ratio of 1.43. Although full response takes up to 24 min, 85% of the colour change is displayed within 10 min., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In optical biosensing, silk fibroin (SF) appears as a promising alternative where other materials, such as paper, find limitations. Besides its excellent optical properties and unmet capacity to stabilize biomacromolecules, SF in test strips exhibits additional functions, i.e. capillary pumping activity of 1.5 mm s -1 , capacity to filter blood cells thanks to its small, but tuneable, porosity and enhanced biosensing sensitivity. The bulk functionalization of SF with the enzymes glucose oxidase and peroxidase and the mediator ABTS produces colourless and transparent SF films that respond to blood glucose increasing 2.5 times the sensitivity of conventional ABTS-based assays. This enhanced sensitivity results from the formation of SF-ABTS complexes, where SF becomes part of the bioassay. Additionally, SF films triple the durability of most stable cellulose-based sensors. Although demonstrated for glucose, SF microfluidic test strips may incorporate other optical bioassays, e.g. immunoassays, with the aim of transferring them from central laboratories to the place of patient's care.

Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C 2 B 9 H 11 ) 2 ] - , whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C 2 B 9 H 11 ) 2 ] - very appealing to participate in electron-transfer processes. In this work, [Co(C 2 B 9 H 11 ) 2 ] - is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C 2 B 9 H 11 ) 2 ] - with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state., (© 2020 Wiley-VCH GmbH.)

In healthcare facilities, environmental microbes are responsible for numerous infections leading to patient's health complications and even death. The detection of the pathogens present on contaminated surfaces is crucial, although not always possible with current microbial detection technologies requiring sample collection and transfer to the laboratory. Based on a simple sonochemical coating process, smart hospital fabrics with the capacity to detect live bacteria by a simple change of colour are presented here. Prussian Blue nanoparticles (PB-NPs) are sonochemically coated on polyester-cotton textiles in a single-step requiring 15 min. The presence of PB-NPs confers the textile with an intensive blue colour and with bacterial-sensing capacity. Live bacteria in the textile metabolize PB-NPs and reduce them to colourless Prussian White (PW), enabling in situ detection of bacterial presence in less than 6 h with the bare eye (complete colour change requires 40 h). The smart textile is sensitive to both Gram-positive and Gram-negative bacteria, responsible for most nosocomial infections. The redox reaction is completely reversible and the textile recovers its initial blue colour by re-oxidation with environmental oxygen, enabling its re-use. Due to its simplicity and versatility, the current technology can be employed in different types of materials for control and prevention of microbial infections in hospitals, industries, schools and at home., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In the development of colorimetric biosensors, the use of electrochromic mediators has been accepted and widely used during decades. The main drawback of these types of enzymatic substrates is the difficult recovery of the initial redox state of the molecule, which can be done electrochemically or by antioxidants addition, complicating the initially simple structure of the biosensor. those strategies are rarely followed Actually, being the disposable biosensor configuration the most extended for this detection mechanisms. Alternatively, we propose the first reported use of a diacid dithienylethene 1,2-bis(5-carboxy-2-methylthien-3-yl)cyclopentene (DTE) photoelectrochromic compound as a substrate of the horseradish peroxidase (HRP). The photoisomerization between the open (DTEo) and closed (DTEc) forms of the molecule and the respective shift in the redox potential allowed the light-induced enzymatic detection of glucose in the glucose oxidase [(GOx)]-HRP cascade system. This fast and easy control over the enzymatic substrate availability by light pulses permits a gradually consumption and the light-regeneration of the biosensor for a number of cycles. We consider the presented results transcendent in the development of reusable and light-controlled photonic biosensing systems., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Sensor arrays used to detect electrophysiological signals from the brain are paramount in neuroscience. However, the number of sensors that can be interfaced with macroscopic data acquisition systems currently limits their bandwidth. This bottleneck originates in the fact that, typically, sensors are addressed individually, requiring a connection for each of them. Herein, we present the concept of frequency-division multiplexing (FDM) of neural signals by graphene sensors. We demonstrate the high performance of graphene transistors as mixers to perform amplitude modulation (AM) of neural signals in situ , which is used to transmit multiple signals through a shared metal line. This technology eliminates the need for switches, remarkably simplifying the technical complexity of state-of-the-art multiplexed neural probes. Besides, the scalability of FDM graphene neural probes has been thoroughly evaluated and their sensitivity demonstrated in vivo. Using this technology, we envision a new generation of high-count conformal neural probes for high bandwidth brain machine interfaces.

The use of CO 2 as a C1 carbon source for synthesis is raising increasing attention both as a strategy to bring value to carbon dioxide capture technologies and a sustainable approach towards chemicals and energy. The presented results focus on the application of electrochemical methods to incorporate CO 2 into organic compounds using ionic liquids as electrolytes, which provides a green alternative to the formation of C-C bonds. In this sense, the current manuscript shows that Naproxen (6-Methoxy-α-methyl-2-naphthaleneacetic acid) can be synthetizing in high yield (89%) and conversion rates (90%) through an electrocarboxylation process using CO 2 and ionic liquids. The role of the cathode and solvent, which can potentially enhance the synthesis, is also discussed. The "green" route described in the current work would open a new sustainable strategy for the electrochemical production of pharmaceutical compounds., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Two azo dyes, acid red 1 (AR1) and acid red 18 (AR18), were used alone or in combination with sodium dodecyl sulfate (SDS) for the electropolymerization of a pyrrole monomer. Polypyrrole (PPy) showed higher redox capacity when SDS and AR18 were used simultaneously as dopant agents (PPy/AR18-SDS) than when the conducting polymer was produced in the presence of SDS, AR18, AR1, or an AR1/SDS mixture. Moreover, PPy/AR18-SDS is a self-stabilizing material that exhibits increasing electrochemical activity with the number of oxidation-reduction cycles. A mechanism supported by scanning electron microscopy and X-ray diffraction structural observations was proposed to explain the synergy between the SDS surfactant and the AR18 dye. On the other hand, the Bordeaux red color of PPy/AR18-SDS, which exhibits an optical band gap of 1.9 eV, rapidly changed to orange-yellow and blue colors when films were reduced and oxidized, respectively, by applying linear or step potential ramps. Overall, the results indicate that the synergistic utilization of AR18 and SDS as dopant agents in the same polymerization reaction is a very successful and advantageous strategy for the preparation of PPy films with cutting-edge electrochemical and electrochromic properties.

On-command changes in the emission color of functional materials is a sought-after property in many contexts. Of particular interest are systems using light as the external trigger to induce the color changes. Here we report on a tri-component cocktail consisting of a fluorescent donor molecule and two photochromic acceptor molecules encapsulated in polymer micelles and we show that the color of the emitted fluorescence can be continuously changed from blue-to-green and from blue-to-red upon selective light-induced isomerization of the photochromic acceptors to the fluorescent forms. Interestingly, isomerization of both acceptors to different degrees allows for the generation of all emission colors within the red-green-blue (RGB) color system. The function relies on orthogonally controlled FRET reactions between the blue emitting donor and the green and red emitting acceptors, respectively.

Color-tunable white-light-emitting materials are currently attracting much attention because of their potential applications in artificial lighting, sensing, and imaging. However, preparation of these systems from organic emitters is often cumbersome due to the interchromophoric interactions occurring upon solvent drying in the final solid materials, which can be hardly predicted and may lead to detrimental effects. To circumvent these obstacles, we have developed a new fabrication methodology that relies on dye encapsulation within liquid-filled capsules, thus enabling direct transfer of the luminescent properties from solution to the solid state and as such, rational design of miniaturized white-light-emitting materials. By introducing a thermally responsive chromophore into the capsules, these materials are further endowed with color tunability, which does not only allow ample modulation of the emitted color but also facilitate external fine control of the system so as to ensure precise realization of white light at the desired temperature and excitation wavelength.

Electrocarboxylation of organic halides is one of the most widely used approaches for valorising CO 2 . In this manuscript, we report a new greener synthetic route for synthesising 2-(4-isobutylphenyl)propanoic acid, Ibuprofen, one of the most popular non-steroidal anti-inflammatory drugs (NSAIDs). The joint use of electrochemical techniques and ionic liquids (ILs) allows CO 2 to be used as a C 1 -organic building block for synthesising Ibuprofen in high yields, with conversion ratios close to 100%, and under mild conditions. Furthermore, the determination of the reduction peak potential values of 1-chloro-(4-isobutylphenyl)ethane in several electrolytes (DMF, and ionic liquids) and with different cathodes (carbon and silver) makes it possible to evaluate the most "energetically" favourable conditions for performing the electrocarboxylation reaction. Hence, the use of ILs not only makes the electrolytic media greener, but they also act as catalysts enabling the electrochemical reduction of 1-chloro-(4-isobutylphenyl)ethane to be decreased by up to 1.0 V., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Fluorescent switches based on spirocyclic zwitterionic Meisenheimer (SZMC) complexes are stimuli-responsive organic molecules with application in a variety of areas. To expand their functionality, novel switching mechanisms are herein reported for these systems: (a) acid- and redox-triggered formation of an additional protonation state with distinct optical properties, and (b) solvent-induced fluorescence modulation. We demonstrate that these new features, which enable both multistimuli and multistate operation of SZMC switches, can be exploited in the preparation of smart organic materials: wide-range pH optical probes, electrochromic and electrofluorochromic films, and polymer-based fluorescent detectors of organic liquids.

The binding and electrochemical properties of the complexes Cu II -HAH, Cu II -HWH, Cu II -Ac-HWH, Cu II -HHW, and Cu II -WHH have been studied by using NMR and UV/Vis spectroscopies, CV, and density functional calculations. The results obtained highlight the importance of the peptidic sequence on the coordination properties and, consequently, on the redox properties of their Cu II complexes. For Cu II -HAH and Cu II -HWH, no cathodic processes are observed up to -1.2 V; that is, the complexes exhibit very high stability towards copper reduction. This behaviour is associated with the formation of very stable square-planar (5,5,6)-membered chelate rings (ATCUN motif), which enclose two deprotonated amides. In contrast, for non-ATCUN Cu II -Ac-HWH, Cu II -HHW complexes, simulations seem to indicate that only one deprotonated amide is enclosed in the coordination sphere. In these cases, the main electrochemical feature is a reductive irreversible one electron-transfer process from Cu II to Cu I , accompanied with structural changes of the metal coordination sphere and reprotonation of the amide. Finally, for Cu II -WHH, two major species have been detected: one at low pH (<5), with no deprotonated amides, and another one at high pH (>10) with an ATCUN motif, both species coexisting at intermediate pH. The present study shows that the use of CV, using glassy carbon as a working electrode, is an ideal and rapid tool for the determination of the redox properties of Cu II metallopeptides., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Stable zwitterionic spirocyclic Meisenheimer compounds were synthesized using a one-step reaction between picric acid and diisopropyl (ZW1) or dicyclohexyl (ZW3) carbodiimide. A solution of these compounds displays intense orange fluorescence upon UV or visible light excitation, which can be quenched or "turned-off" by adding a mole equivalent amount of F - or CN - ions in acetonitrile. Fluorescence is not quenched in the presence of other ions such as Cl - , Br - , I - , NO₂ - , NO₃ - , or H₂PO₄ - . These compounds can therefore be utilized as practical colorimetric and fluorescent probes for monitoring the presence of F - or CN - anions., Competing Interests: The authors declare no conflict of interest.

Functionalization of gold nanoparticles with supramolecular hosts allows their plasmon-based photocatalytic activity to be enhanced. This is mainly ascribed to the formation of labile host-guest complexes with the reagent molecules on the metal surface, thus promoting nanoparticle-substrate approximation without interfering with the light-induced catalytic process.

A Ru II -pentadentate polypyridyl complex [Ru II (κ-N 5 -bpy2PYMe)Cl] + (1 + , bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6-2,2'-bipyridyl)ethane) and its aqua derivative [Ru II (κ-N 5 -bpy2PYMe)(H 2 O)] 2+ (2 2+ ) were synthesized and characterized by experimental and computational methods. In MeOH, 1 + exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-1 2+ generates a [Ru III (κ-N 4 -bpy2PYMe)Cl 2 ] + intermediate after the exchange of a pyridyl ligand by a Cl - counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-1 2+ is in direct equilibrium with trans-1 2+ , with absence of the κ-N 4 -bis-chlorido Ru III -intermediate. All these equilibria were modeled by density functional theory calculations. Interestingly, the aqua derivative is obtained as a pure trans-[Ru II (κ-N 5 -bpy2PYMe)(H 2 O)] 2+ isomer (trans-2 2+ ), while the addition of a methyl substituent to a single bpy of the pentadentate ligand leads to the formation of a single cis isomer for both chlorido and aqua derivatives [Ru II (κ-N 5 -bpy(bpyMe)PYMe)Cl] + (3 + ) and [Ru II (κ-N 5 -bpy(bpyMe)PYMe)(H 2 O)] 2+ (4 2+ ) due to the steric constraints imposed by the modified ligand. This system was also structurally and electrochemically compared to the previously reported [Ru II (PY5Me 2 )X] n+ system (X = Cl, n = 1 (5 + ); X = H 2 O, n = 2 (6 2+ )), which also contains a κ-N 5 -Ru II coordination environment, and to the newly synthesized [Ru II (PY4Im)X] n+ complexes (X = Cl, n = 1 (7 + ); X = H 2 O, n = 2 (8 2+ )), which possess an electron-rich κ-N 4 C-Ru II site due to the replacement of a pyridyl group by an imidazolic carbene.

We encapsulate a fluorescent donor molecule and a photochromic acceptor unit (photoswitch) in polymer micelles and show that the color of the emitted fluorescence is continuously changed from blue to yellow upon light-induced isomerization of the acceptor. Interestingly, white-light generation is achieved in between. With the photoswitch in the colorless form, intense blue emission from the donor is observed, while UV-induced isomerization to the colored form induces an energy transfer reaction that quenches the donor emission and sensitizes the yellow emission from the colored photoswitch. The process is reversed by exposure to visible light, triggering isomerization to the colorless form.

Although the quantum nature of molecules makes them specially suitable for mimicking the operation of digital electronic elements, molecular compounds can also be envisioned to emulate the behavior of analog devices. In this work we report a novel fluorescent three-state switch capable of reproducing the analog response of transistors, an ubiquitous device in modern electronics. Exploiting the redox and thermal sensitivity of this compound, the amplitude of its fluorescence emission can be continuously modulated, in a similar way as the output current in a transistor is amplified by the gate-to-source voltage.

Primary alkyl amines are one of the most commonly used and effective reagents in CO2 capture. Most of the amines used for CO2 capture are recycled, but a minor portion of the amines are degraded after one electron oxidation process, leading to highly toxic substances. The combination of the complementary information obtained from photoinduced electron transfer (flash photolysis) and heterogeneous electron transfer (electrochemistry) appears to be very attractive to fully characterize the electron transfer reaction mechanism of reactive species in general, as well as for determining important thermodynamic properties, such as standard potentials (E°) or pKa values. It is particularly difficult to determine these crucial data accurately in the cases of alkyl primary amines. Hence, in this manuscript we focus on the establishment of the several alkyl primary amines oxidation mechanism in organic aprotic solvents. In order to achieve this, this work combines information provided by flash photolysis (nanosecond), cyclic voltammetry (millisecond), and digital simulation (nanomile-second). Moreover, the accuracy of the E° values calculated using the nanosecond equilibrium method allows not only revising them, but also estimating new important thermodynamic data concerning the bond dissociation energies (BDEs) of ammonium cations (N(+)-H) and of the amine cation radicals (α-C-H), as well as their corresponding pKa values.

A report is presented on the use of cyclic voltammetry using silver as a working electrode. The combined electrocatalytic properties of silver and ionic liquids allow cyclic voltammetry to be turned into an ideal tool for the rapid and accurate access to diffusion coefficient values and solubility values of carbon dioxide in ionic liquids under standard conditions.

The redox equilibrium method was used to determine accurate oxidation potentials in acetonitrile for 40 heteroatom-substituted compounds. These include methoxy-substituted benzenes and biphenyls, aromatic amines, and substituted acetanilides. The redox equilibrium method allowed oxidation potentials to be determined with high precision (≤ ±6 mV). Whereas most of the relative oxidation potentials follow well-established chemical trends, interestingly, the oxidation potentials of substituted N-methylacetanilides were found to be higher than those of the corresponding acetanilides. Density functional theory calculations provided insight into the origin of these surprising results in terms of the preferred conformations of the amides versus their cation radicals.

A thermally irreversible dithienylethene (DTE) photochrom can be turned into a thermally reversible one in presence of Cu(II) triflate. A ring opening (DTEC closed→DTEO open) occurs through the formation of a copper-containing fast transient intermediate. Stopped-flow experiments monitored at 410 and 780 nm have allowed to show that the stoichiometry of this intermediate is DTE/Cu=1:1. At longer monitoring times (i.e., several seconds after mixing), the intermediate undergoes a slow decay while the residual DTEC closed form opens. A joint detailed kinetic and electrochemical analysis has unveiled a proton catalysis scenario in which electron transfer between DTEC and Cu(II), ligand exchange, protonation-deprotonation equilibria of the cation radicals and ring opening are embedded into two main reaction cycles. At the beginning of the reaction, Cu(II) is reduced into Cu(I) and DTE is degraded without ring opening. Then, as the reaction progresses, the triflic acid released from the Cu(II) reduction switches-on a propagation cycle during which ring opens without any more Cu(II) consumption. Cyclic voltammetry, spectro-electrochemical measurements, delayed photocoloration experiments in presence of Cu(II) and acid-base additions have confirmed the main features of the proton catalysis., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The present study quantitatively analyses the gated photochromism and the acidity photomodulation properties of a diacid dithienylethene compound. Photoisomerisation between the open and closed isomers was investigated by UV/visible and (1)H NMR spectroscopy. It was found that the photocyclisation quantum yield of the diacid form was remarkably high (around 90%). Partial neutralisation of the open isomer revealed a gated photochromism as the photocyclisation quantum yield of the mono- and dianion were 50 and 67%, respectively. A considerable photomodulation of the acidity was observed: the closed isomer is more acid than the open one by more than one pK(a) unit. This effect has been shown to be exploitable for a reversible photo-acid generation. This is the first time that a complete quantitative investigation that allows for the determination of the main photochromic, spectral and thermodynamic parameters of a base-sensitive photochromic diarylethene has been carried out., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

On the route to single (large) molecule unimolecular chemistry, the adsorption of a photochromic dithienylethene dye on Cu(111) at a submonolayer level has been studied by Ultra High Vacuum-Scanning Tunneling Microscopy at Low Temperature. This technique has shown that the observed adsorbed molecule's shape is compatible with an helical conformation but has also revealed a surrounding electronic corrugation due to the perturbed surface states. Careful examination of the standing wave pattern indicated that only a part of the molecule is indeed interacting with the metallic substrate. Geometric considerations were used to infer that the bridging ethene moiety could be responsible for the electronic scattering. Scanning Tunneling Spectroscopy has shown a substantial amount of charge transfer from the surface to the adsorbate. The hypothesis that this precise double bond is a reactive locus toward charge transfer processes is confirmed by the electrochemical results: this double bond is indeed reduced upon coulometric reduction on glassy carbon. Furthermore, the use of a copper cathode strongly facilitates the reduction since a +0.6 V shift was recorded.

In a landmark publication over 40 years ago, Rehm and Weller (RW) showed that the electron transfer quenching constants for excited-state molecules in acetonitrile could be correlated with the excited-state energies and the redox potentials of the electron donors and acceptors. The correlation was interpreted in terms of electron transfer between the molecules in the encounter pair (A*/D ⇌ A(•-)/D(•+) for acceptor A and donor D) and expressed by a semiempirical formula relating the quenching constant, k(q), to the free energy of reaction, ΔG. We have reinvestigated the mechanism for many Rehm and Weller reactions in the endergonic or weakly exergonic regions. We find they are not simple electron transfer processes. Rather, they involve exciplexes as the dominant, kinetically and spectroscopically observable intermediate. Thus, the Rehm-Weller formula rests on an incorrect mechanism. We have remeasured k(q) for many of these reactions and also reevaluated the ΔG values using accurately determined redox potentials and revised excitation energies. We found significant discrepancies in both ΔG and k(q), including A*/D pairs at high endergonicity that did not exhibit any quenching. The revised data were found to obey the Sandros-Boltzmann (SB) equation k(q) = k(lim)/[1 + exp[(ΔG + s)/RT]]. This behavior is attributed to rapid interconversion among the encounter pairs and the exciplex (A*/D ⇌ exciplex ⇌ A(•-)/D(•+)). The quantity k(lim) represents approximately the diffusion-limited rate constant, and s the free energy difference between the radical ion encounter pair and the free radical ions (A(•-)/D(•+) vs A(•-) + D(•+)). The shift relative to ΔG for the overall reaction is positive, s = 0.06 eV, rather than the negative value of -0.06 eV assumed by RW. The positive value of s involves the poorer solvation of A(•-)/D(•+) relative to the free A(•-) + D(•+), which opposes the Coulombic stabilization of A(•-)/D(•+). The SB equation does not involve the microscopic rate constants for interconversion among the encounter pairs and the exciplex. Data that fit this equation contain no information about such rate constants except that they are faster than dissociation of the encounter pairs to (re-)form the corresponding free species (A* + D or A(•-) + D(•+)). All of the present conclusions agree with our recent results for quenching of excited cyanoaromatic acceptors by aromatic donors, with the two data sets showing indistinguishable dependencies of k(q) on ΔG.

Nanosecond laser flash photolysis methods were used to generate and spectrally characterize the cation radicals of 1,2-diaryl-1,1,2,2,-tetramethyldisilanes (Ar = p-X-Ph, X = H, CH(3), OCH(3)) in hexafluoroisopropanol (HFIP) at room temperature. The disilane cation radicals rapidly reacted with methanol, with bimolecular rate constants ranging from 0.63 to 2.1 x 10(8) M(-1) s(-1). The cation radicals were found to react with tert-butanol 4-5 times more slowly than methanol, consistent with a small steric effect for nucleophile-assisted fragmentation of the Si-Si bond. The standard potentials for oxidation of the disilanes in HFIP were determined by two different methods: first, by measuring equilibrium constants for electron exchange between the disilanes and the cation radical of hexaethylbenzene and, second, by combining electrochemical data from cyclic voltammetry with the lifetimes of the disilane cation radicals measured by laser flash photolysis in the same media. Agreement between the two methods was excellent (