Conjugated singlet ground state diradicals have received remarkable attention owing to their potential applications in optoelectronic devices. A distinctive character of these systems is the location of the double exciton state, a low lying excited state dominated by the doubly excited H,H→L,L configuration, which may influence optical and other photophysical properties. In this contribution we investigate this specific excited state, for a series of recently synthesized conjugated diradicals, employing time dependent density functional theory based on the unrestricted parallel spin reference configuration in the spin-flip formulation (SF-TDDFT) and standard TD calculations based on the unrestricted antiparallel spin reference configuration (TDUDFT). The quality of the computed results is assessed considering diradical and multiradical descriptors and the excited state wavefunction composition.

Coating of organic molecules from the solution phase can result in directional crystal growth under certain conditions, even on a smooth isotropic surface and without the need of any kind of graphoexpitaxial preparation of the substrate. Based on reviewing the results from a variety of coating techniques and conditions, we identify the condition that the coating speed should equal the growth speed of the fastest growing crystal plane as crucial for achieving a high degree of directional crystallization.

Search for appropriate materials with favorable staggered energy band arrangements is important and of great challenge to fabricate Z-scheme photocatalysts with high activity in visible light. In this study, we demonstrated a facile and feasible strategy to construct highly active organic-inorganic Z-scheme hybrids (P-BMO) with linear pyrene-based conjugated polymer (P17-E) and Bi₂MoO₆ via in-situ palladium-catalyzed cross-coupling reaction. Characterization results revealed C-O chemical bond formed at the heterointerface between P17-E and Bi₂MoO₆ after in-situ polycondensation and endowed the hybrids with observably improved photogenerated carries transfer capability. Visible light driven photocatalytic removal of ciprofloxacin and Cr(VI) were significantly enhanced after the incorporation of P17-E into Bi₂MoO₆ whether with the morphology of nanosheets, nanobelts or microspheres. Moreover, this P-BMO hybrids were also found to exhibit sustainable excellent photocatalytic performance after four runs of photocatalytic evaluation test, suggesting its high activity and stability. To better eliminate the redox ability enhancement of P-BMO, a reasonable Z-scheme electrons transferring mechanism between P17-E and Bi₂MoO₆ was proposed and proved by the determination of •O₂^– and •OH and Pt nanoparticles photodeposition experiments. This work might provide a viable source and insight into the design of Z-scheme photocatalysts with excellent redox ability for environmental remediation.

Detecting the presence of explosives is important to protect human lives in military conflicts and peacetime. Gas-phase detection of explosives can make use of the change of material properties, which can be sensitive to environmental conditions such as temperature and humidity. This paper describes a remote-controlled automatic shutter method for environmental impact assessment of photoluminescence (PL) sensors under near-open conditions. Utilizing the remote-sensing method, we obtained environmental effects without being exposed to sensing vapor molecules, and explained how PL intensity was influenced by the temperature, humidity, and exposure time. We also developed a theoretical model including the effect of exciton diffusion for PL quenching, which worked well under limited molecular diffusions. Incomplete recovery of PL intensity, or degradation effect, was considered as an additional factor in the model.

Microorganisms present in fermented foods and beverages play a vital role in enhancing both nutritive and non-nutritive components. During the fermentation, microorganisms can either naturally occur in the food through spontaneous fermentation or be intentionally added as starter cultures with a variety of species and strains. In this review, the focus is placed on micronutrients, such as vitamins and minerals, and three major macromolecules – prebiotics, bioactive peptides, and functional fatty acids. During fermentation, non-digestible carbohydrates like fructooligosaccharides and galactooligosaccharides are synthesized, imparting prebiotic properties that support gut health. Enzymatic hydrolysis of proteins by microorganisms yields bioactive peptides with diverse health benefits. Furthermore, fermentation facilitates the formation of fatty acids, including short-chain fatty acids and conjugated linoleic acid, potentially exerting physiological effects. By harnessing the power of microbial fermentation, nutrient-rich and bioactive compounds can be enhanced, offering a promising approach to address global malnutrition concerns.

The effective treatment for chronic wounds constitute one of the most common worldwide health care problem due to the presence of high levels of proteases, free radicals and exudates in the wound, which constantly activate the inflammatory system avoiding the tissue regeneration. In this study, we describe a multifunctional bioactive and resorbable membrane with in-built antioxidant agent for the continuous quenching of free radicals as well as to control inflammatory response helping to promote the wound healing process. To reach that goal synthesized statistical copolymers of N-vinylcaprolactam (V) and 2-hydroxyethyl methacrylate (H) have been conjugated with catechol bearing hydrocaffeic acid (HCA) molecules. The natural polyphenol (catechol) is the key molecule responsible for the mechanism of adhesion of mussels, and provides the functionalized polymer conjugate a continuous antioxidant response, antiinflammatory effect, UV screen and bioadhesion in the moist environment of the human body, all of them key features in the wound healing process. Therefore, these novel mussel-inspired materials have an enormous potential of application and can act very positively, favoring and promoting the healing effect in chronic wounds.

In this study, two donor-acceptor (D-A) type conjugated polymers namely PQSeCz and PQSeFl were designed and synthesized. Selenophene was incorporated as a π -bridge, quinoxaline as an acceptor unit while carbazole and fluorene were used as the donor units. Polymers were synthesized via palladium catalyzed Suzuki polymerization reaction. All molecules were characterized by 1H and 13C NMR Spectroscopy. The weight and number average molecular weights of the two polymers were determined by gel permeation chromatography (GPC). Electrochemical and spectroelectrochemical characterizations of the polymers were performed to investigate their optoelectronic properties. Oxidation potentials were 1.15 V/ 0.82 V and 1.11 V/ 0.82 V for PQSeCz and PQSeFl respectively, while reduction potentials were -1.26 V /-1.14 V and -1.48 V/ -1.23 V, respectively. In the visible region, maximum absorption wavelengths for the two polymers were 551 nm and 560 nm, respectively. Optical band gaps (Egop) were found from the lowest energy π – π∗ transition onsets as 1.71 eV and 1.58 eV, respectively. Both polymers showed good solubility in common solvents.

The probiotic bacterial strain Lactobacillus plantarum ZS2058 has been proved to manifest comprehensive functions, which were due to ability to synthesise conjugated fatty acids (CFAs). To investigate the specific functions of CFAs produced by this probiotic bacterium, α-linolenic acid was isomerized by Lactobacillus plantarum strain ZS2058, and two different conjugated α-linolenic acid (CLNA) isomers were successfully isolated. These isoforms, CLNA1 (c9, t11, c15-CLNA, purity 97.48%) and CLNA2 (c9, t11, t15-CLNA, purity 99.00%), both showed the ability to inhibit the growth of three types of colon cancer cells in a time- and concentration-dependent manner. In addition, the expression of MDA in Caco-2 cells was increased by CLNA1 or CLNA2, which indicated lipid peroxidation was related to the antiproliferation activity of CLNAs. Examination of the key protein of pyroptosis showed that CLNA1 induced the cleavage of caspase-1 and gasdermin-D, while CLNA2 induced the cleavage of caspase-4, 5 and gasdermin-D. The addition of relative inhibitors could alleviate the pyroptosis by CLNAs. CLNA1 and CLNA2 showed no effect on caspase-3, 7, 9 and PARP-1, which were key proteins associated with apoptosis. And no sub-diploid apoptotic peak appeared in the result of PI single staining test. In conclusion, CLNA1 activated caspase-1 and induced Caco-2 cell pyroptosis, whereas CLNA2 induced pyroptosis through the caspase-4/5-mediated pathway. The inhibition of Caco-2 cells by the two isomers was not related to apoptosis. This is the first report showing the ability of CLNAs to activate antioxidant defenses resulting in pyroptosis.

Benign recurrent intrahepatic cholestasis (BRIC) is a rare genetic cause of cholestasis. It is considered as part of inherited intrahepatic cholestasis syndromes, such as progressive familial intrahepatic cholestasis (PFIC), and intrahepatic cholestasis of pregnancy. BRIC is presented in infancy or in early adulthood. It is characterized by exacerbations and remissions of jaundice with accompanying intense itching, lasting from weeks to years throughout lifetime. Normal gamma-glutamyl transferase (GGT) is a characteristic laboratory finding. Contrary to PFIC, which may progress to cirrhosis, BRIC does not progress to chronic liver disease or cirrhosis. However, incessant episodes of cholestasis result in marked reduction in quality of life and distinct mutations increase the risk of hepatobiliary malignancy. In intervals between the exacerbations, the histological findings of centrilobular cholestasis together with the abnormal laboratory parameters return to normal. In this context, liver biopsy might be avoided. In this review, we will focus on the genetic aspects of BRIC, its pathophysiology, clinical presentation, and prognosis of this autosomal recessive genetically determined cholestatic disorder. Moreover, triggering factors as well as treatment options will be further elucidated.

In this study, we investigate the structural changes, electronic properties, and charge redistribution within azo-bithiophene (Azo-BT) chemisorbed monolayers under different light stimuli using density functional theory and molecular dynamics simulations. We consider two types of switches, Azo-BT and BT-Azo, with different arrangements of the Azo and BT blocks counting from the anchor thiol group. The chemisorbed monolayers of pure cis- and trans-isomers with a surface concentration of approximately 2.7 molecules per nm2 are modeled on a gold surface using classical all-atom molecular dynamics. Our results reveal significant shrinkage of the BT-Azo layer under UV illumination, whereas the thicknesses of the Azo-BT layer remain comparable for both isomers. This difference in behavior is attributed to the ordering of the trans-molecules in the layers, which is more pronounced for Azo-BT, leading to a narrow distribution of the inclination angle to the gold surface. Conversely, both layers consisting of cis-switches exhibit disorder, resulting in similar brush heights. To study charge transfer within the immobilized layers, we analyze each snapshot of the layer and calculate mean charge transfer integrals using Nelsen’s algorithm for a number of interacting neighboring molecules. Combining these integrals with reorganization energies defined for the isolated molecules, we evaluate the charge transfer rates and mobilities for electron and hole hopping within the layers at room temperature based on Marcus’ theory. This research offers new perspectives for the innovative design of electrode surface modifications and provides insights into controlling charge transfer within immobilized layers using light triggers. Additionally, we identify molecular properties that are enhanced through specific molecular design, which contributes to the development of more efficient molecular switches for various electronic applications.

Load transfer through orthopaedic joint implants is poorly understood. The longer-term outcomes of these implants are just starting to be studied, making it imperative to monitor contact loads across the entire joint implant interface to elucidate the force transmission and distribution mechanisms exhibited by these implants in service. This study proposes and demonstrates the design, implementation, and characterization of a 3D-printed smart polymer sensor array using conductive polyaniline (PANI) structures embedded within a polymeric parent phase. The piezoresistive characteristics of PANI were studied to characterize the sensing behaviours inherent to these embedded pressure sensor arrays. PANI's stable response to a continuous load, its stability throughout loading and unloading cycles, and its repeatable and linear response to incremental loading cycles together with the accuracy of these measurements were investigated. It is demonstrated that this specially developed multi-material additive manufacturing process for polyaniline is an attractive approach for the fabrication of implant components having embedded smart-polymer sensors for the measurement and analysis of joint loads in orthopaedic implants.

Photophysics properties such as fluorescence quenching, and photoexcitation dynamics of bimolecular non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and anionic graphene carboxylate (GC) have been discovered for the first time by the steady state and time-resolved femtosecond transient absorption (TA) spectroscopy with broadband capabilities. The steady-state fluorescence of PFN is quenched with high efficiency by GC acceptor. Fluorescence lifetime measurements revealed that the quenching mechanism of PFN by GC is static. Here, the quenching mechanisms are well proven by TA spectra of PFN/GC systems. For PFN/GC systems, the photo electron transfer (PET) and charge recombination (CR) processes are ultrafast (within few tens of ps) related to static interactions whereas for PFN/DCB systems the PET takes place in few hundreds ps (217.50 ps)1 suggesting diffusion-controlled PET process. In the latter case, the PFN+•-DCB-• radical ion pairs as the result of PET from the PFN to DCB are clearly resolved and they are long-lived. The slow CR process (in 30 ns time scales)1 suggest PFN+• and DCB-• may already form separated radical ion pairs through charge separation (CS) process, which recombined back to the initial state with a characteristic time constant of 30 ns. The advantage of the present positively charged polyfluorene used in this work is the control over the electrostatic interactions and electron transfers in non-covalent polyfluorene/quencher systems in DMSO solution.

Macromolecules with well-defined structures in terms of molar mass and monomer sequence became interesting building blocks for modern materials. The precision of the macromolecular structure makes fine-tuning of the properties of resulting materials possible. Conjugated macromolecules exhibit excellent optoelectronic properties that make them exceptional candidates for sensors construction. The importance of chain length and monomer sequence is particularly important in conjugated systems. The sequence lengths, monomer sequence and structural modification often influence the energy bang gap between HOMO and LUMO orbitals of the molecules that reflect in their properties. Moreover, the supramolecular aggregation that is often observed in oligo-conjugated systems is usually strongly affected by even minor structural changes that are used for sensor designs. This review summarizes the examples of well-defined conjugated macromolecules based on oligo(arylene ethynylene)s skeleton used for sensor applications. The sensing mechanisms and importance of uniformity of structure are discussed.

The seasonal variation in fatty acids and minerals concentrations was investigated through the analysis of Pecorino Romano cheese samples collected in January, April, and June. A fraction of samples contained missing values in their fatty acid profile. Probabilistic Principal component analysis coupled with Linear Discriminant Analysis was employed to classify cheese samples on a production season basis while accounting for missing data and quantifying the missing Fatty acids concentration for the sample in which they were absent. The levels of rumenic acid, vac-cenic acid and omega-3 compounds were positively correlated with the spring season, while the length of the saturated fatty acids increased throughout the production seasons. Concerning the classification performances, the optimal number of principal components (i.e., 5) achieved an ac-curacy in cross-validation equal to 98 %. Then, when the model was tasked to impute the lacking Fatty acid concentration values, the optimal number of principal components resulted in an R2 value in cross-validation of 99.53%