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Our studies demonstrate how the interplay of changes in the reorganization energy and the damping factor of the molecular bridges, in addition to variation in the solvent polarity, affect the outcome of charge-transfer and the corresponding rate constants. The different regions of the Marcus parabola are highly relevant The charge-recombination of, for example, the adjacent C60•‒ ZnP•+ Fc charge-separated state is located in the inverted region, while that of the distant C60•‒ ZnP Fc•+ charge-separated state lies in the normal region. Here, the larger reorganization energy of Fc relative to ZnP makes the difference.Diagnostics and therapeutics are generally separate entities in medicine. Theranostics, agents that provide for both modalities, are being developed. However, they often require complex syntheses so as to incorporate within one molecular structure both diagnostic and therapeutic elements. Moreover, their use is often complicated by the disparate dosage requirements for diagnosis and therapy. Herein, we report that closely related porphyrinoid regioisomers produced from the same 1,3-dipolar cycloaddition reaction give rise to products that as their corresponding ytterbium(III) complexes may be split and used for the separate biological functions that are required for theranostics. Specifically, the cis isomer is luminescent and suitable for NIR imaging, while the trans isomer produces singlet oxygen with a good quantum yield and is thus attractive for use in photodynamic therapy (PDT). Both in vitro and in vivo experiments provide support for the complementary biological functions of the two regioisomers. The present study reveals how ostensibly related regioisomers may be used to switch between diagnosis and therapy. More broadly, it serves to highlight a new approach to creating paired sets of molecules that may be used in combination as effective theranostics.The utilization of photodynamic therapy (PDT) for the treatment of various types of cancer has gained increasing attention over the last decades. Despite the clinical success of approved photosensitizers (PSs), their application is sometimes limited due to poor water solubility, aggregation, photodegradation, and slow clearance from the body. To overcome these drawbacks, research efforts are devoted toward the development of metal complexes and especially Ru(II) polypyridine complexes based on their attractive photophysical and biological properties. Despite the recent research developments, the vast majority of complexes utilize blue or UV-A light to obtain a PDT effect, limiting the penetration depth inside tissues and, therefore, the possibility to treat deep-seated or large tumors. To circumvent these drawbacks, we present the first example of a DFT guided search for efficient PDT PSs with a substantial spectral red shift toward the biological spectral window. Thanks to this design, we have unveiled a Ru(II) polypyridine complex that causes phototoxicity in the very low micromolar to nanomolar range at clinically relevant 595 nm, in monolayer cells as well as in 3D multicellular tumor spheroids.In recent times, deep eutectic solvents (DESs) have emerged as an environment-friendly alternative to both common organic solvents and ionic liquids (ILs). The present study has been undertaken with an objective to understand the intermolecular interaction, structural organization, and dynamics of two DES systems in the absence and presence of lithium salt so that the potential of these mixtures in electrochemical application is realized. For this purpose, the steady-state, time-resolved fluorescence, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) behavior of two DESs (ethaline and glyceline) and their mixture with lithium bis(trifluoromethylsulfonyl) imide (LiNTf2) has been investigated. Measurements of polarity through EPR technique have revealed that the polarities of DESs are close to aliphatic polyhydroxy alcohol and the polarities of the medium increase with the increase in lithium salt concentration. Studies on solvation dynamics have indicated that there is an increase in average solvation time with the increase in lithium salt concentration. Investigation of rotational dynamics of some selected fluorophore in these media has shown that addition of lithium salt significantly alters the nano/microstructural organization of both DESs. Further, measurements of the self-diffusion coefficient through NMR have also supported the perturbation of the nanostructural organization of the solvent systems by addition of lithium salts. Essentially, all of these investigations have suggested that addition of lithium salt significantly alters the microscopic behavior of DESs. The outcome of this study is expected to be helpful in realizing the potential of these media for various electrochemical applications including application in lithium-ion battery.To study the contribution of yeasts to the formation of terpene derivatives during winemaking, a dispersive liquid-liquid microextraction gas chromatography mass spectrometry method was developed for the quantitation of terpenes in white wines, synthetic wine, and a fermented synthetic medium. A mixture of acetone (disperser solvent) and dichloromethane (extraction solvent) was added to 5 mL of sample. The proposed method showed no matrix effect, good linearity in the enological range (from 10 to 200 μg/L), good recovery, and satisfactory inter- and intraday reproducibilities (below 20 and 15% of the relative standard deviation). This sample preparation technique is very interesting for high-throughput studies and economic and environmental reasons because it is fast and easy to operate with high enrichment and consumes a low volume of organic solvents. find more This method was applied to explore the capacities of 40 yeast strains to produce terpene compounds during fermentation of Chardonnay and Ugni Blanc musts as well as in a synthetic medium. Interestingly, most of the studied compounds were detected and quantified in the resulting wines. This study shows that yeast strains can intrinsically produce terpene derivatives under enological conditions and also highlights the differences between the de novo biosynthesis of terpenes and their precursor-linked production.
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