Role of the Radical Character in Singlet Fission: An Ab Initio and Quantum Chemical Topology Analysis.

The radical character of molecules exhibiting singlet fission is related to the energy level matching relationships that facilitate this process. Using a linear H model molecule, we employ quantum chemical topology descriptors based on full configuration interaction calculations to rationalize singlet fission. In this context, the influence of the closed-shell to diradical and diradical to tetraradical character on the singlet fission energy matching conditions is analyzed.

Spin Mixing in Intramolecular Singlet Fission: A First-Principles-Based Quantum Dynamical Study.

We investigate the dynamical interplay between the different triplet-pair spin states that are formed in the intramolecular singlet fission process in a series of pentacene-based dimers covalently bonded to a phenylene linker in ortho, meta, and para positions. Using first-principles calculations and a density matrix quantum dynamical approach we show that the spin dipole-dipole interaction leads to significant population of the quintet spin manifold in these regioisomers when the singlet, triplet and quintet triplet-pair states are quasidegenerate. Furthermore, we also show that the relative arrangement of the pentacene-like moieties has a profound impact on the dynamics of the spin-mixing process, affecting both the relative population of the different spin-states involved in the dynamics and the time scale of the process.

Non-adiabatic electronic relaxation of tetracene from its brightest singlet excited state.

The ultrafast relaxation dynamics of tetracene following UV excitation to the bright singlet state S6 has been studied with time-resolved photoelectron spectroscopy. With the help of high-level ab initio multireference perturbation theory calculations, we assign photoelectron signals to intermediate dark electronic states S3, S4, and S5 as well as to a low-lying electronic state S2. The energetic structure of these dark states has not been determined experimentally previously.

Defining well-being in psoriasis: A Delphi consensus among healthcare professionals and patients.

Psoriasis is a chronic skin disease that negatively impacts on patient's life. A holistic approach integrating well-being assessment could improve disease management. Since a consensus definition of well-being in psoriasis is not available, we aim to achieve a multidisciplinary consensus on well-being definition and its components.

Intramolecular singlet fission: Quantum dynamical simulations including the effect of the laser field.

In the previous work [Reddy et al., J. Chem.

Parallel versus Twisted Pentacenes: Conformational Impact on Singlet Fission.

We placed two pentacene chromophores at the termini of a diacetylene linker to investigate the impact of excitation wavelength, conformational flexibility, and vibronic coupling on singlet fission. Photoexcitation of the low-energy absorption results in a superposed mixture of states, which transform on an ultrafast time-scale into a spin-correlated and vibronically coupled/hot delocalized triplet pair (TT). Regardless of temperature, the lifetime for (TT) is less than 2 ps.

Genetic Variants of the NF-κB Pathway: Unraveling the Genetic Architecture of Psoriatic Disease.

Psoriasis is a multifactorial genetic disease for which the genetic factors explain about 70% of disease susceptibility. Up to 30-40% of psoriasis patients develop psoriatic arthritis (PsA). However, PsA can be considered as a "disease within a disease", since in most cases psoriasis is already present when joint complaints begin.

Molecular Transistor Controlled through Proton Transfer.

The potential of proton transfer reactions as a fundamental mechanism to realize a nanoscale molecular transistor is investigated. Employing density functional theory and the nonequilibrium Green's function formalism, we identify molecule-graphene nanojunctions, which exhibit high- and low-conducting states depending on the specific location of protons in the molecular bridge. In addition, we show that an electrostatic gate field can control the proton transfer process and thus allow specific conductance states to be selected.

Improving the standard of care for patients with spondyloarthritis-related immune inflammatory conditions: results of a Delphi study and proposal for early detection.

Background: Our objective was to provide consensus recommendations on the optimal management of the immune-mediated inflammatory diseases (IMIDs) seen in patients with spondyloarthritis (SpA) using a multidisciplinary approach, and to develop a simple tool to help earlier recognition and referral of coexisting IMIDs in patients who already have one type of IMID.

Methods: A total of 28 experts in the multidisciplinary management of the SpA-associated IMIDs assessed two questionnaires: one with statements focused on the multidisciplinary management of IMIDs, and a second questionnaire focused on questions useful for early recognition and referral. Panelists assessed the statements with a 9-point ordinal scale (1 = strongly disagree, 9 = strongly agree) using a modified Delphi methodology.

Long-living and highly efficient bio-hybrid light-emitting diodes with zero-thermal-quenching biophosphors.

Bio-hybrid light-emitting diodes (Bio-HLEDs) based on color down-converting filters with fluorescent proteins (FPs) have achieved moderate efficiencies (50 lm/W) and stabilities (300 h) due to both thermal- and photo-degradation. Here, we present a significant enhancement in efficiency (~130 lm/W) and stability (>150 days) using a zero-thermal-quenching bio-phosphor design. This is achieved shielding the FP surface with a hydrophilic polymer allowing their homogenous integration into the network of a light-guiding and hydrophobic host polymer.

Single-Component Biohybrid Light-Emitting Diodes Using a White-Emitting Fused Protein.

This work presents a pioneering multidisciplinary approach toward enhancing biohybrid light-emitting diodes (BioHLEDs), merging synthetic biology tools, polymer chemistry, and device engineering to design a thin color down-converting coating with a single white-emitting fluorescent protein (WFP). In particular, the WFP consists of fused red-, green-, and blue-emitting FPs following the so-called protein superglue approach. This WFP shows an efficient and stable white emission originated from a Förster resonance energy transfer between FP moieties.

Quantum dynamical simulation of intramolecular singlet fission in covalently coupled pentacene dimers.

We analyze the dynamics of intramolecular singlet fission in a series of pentacene-based dimers consisting of two pentacene-like chromophores covalently bonded to a phenylene linker in ortho, meta, and para positions. The study uses a quantum dynamical approach that employs a model vibronic Hamiltonian whose parameters are obtained using multireference perturbation theory methods. The results highlight the different role of the direct and mediated mechanism in these systems, showing that the population of the multiexcitonic state, corresponding to the first step of the intramolecular singlet fission process, occurs mainly through a superexchange-like mechanism involving doubly excited or charge transfer states that participate in the process in a virtual way.

Obesity in psoriatic arthritis: Comparative prevalence and associated factors.

Obesity is a common cardiovascular risk factor in psoriatic disease. Although the prevalence of obesity is high, the factors associated with it in patients with psoriatic arthritis (PsA) are poorly understood. We aimed to analyze the frequency and obesity-associated factors in a cohort of PsA.

Hypertension is associated with increased age at the onset of psoriasis and a higher body mass index in psoriatic disease.

Background And Aims: High blood pressure (HBP) is a common comorbidity in psoriatic disease. Some studies indicate a higher prevalence of HBP among arthritis patients, in relation to psoriasis alone, within the psoriatic spectrum. Our objective was to study the prevalence of HBP in both types of patients as well as to analyse the factors associated with it.

Polyarticular evolution and late-onset psoriasis may be associated with cardiovascular disease in psoriatic arthritis.

Background And Aims: Patients with psoriatic arthritis (PsA) have high prevalence of cardiovascular risk factors (CVRF), and they also show higher rates of cardiovascular disease (CVD). We aimed to corroborate these findings and identify factors associated with these events in our clinical setting.

Methods: This cross-sectional study included 340 consecutive patients seen in a tertiary care hospital.

Intramolecular Singlet Fission: Insights from Quantum Dynamical Simulations.

We investigate the dynamics of intramolecular singlet fission in a dimer consisting of two pentacene-based chromophores covalently bonded to a phenylene spacer using an approach that combines high-level ab initio multireference perturbation theory methods and quantum dynamical simulations. The results show that the population of the multiexcitonic state, corresponding to the first step of singlet fission, is facilitated by the existence of higher-lying doubly excited and charge transfer states that participate in a superexchange-like way. The important role played by high-frequency ring-breathing molecular vibrations in the process is also discussed.

Dynamical simulation of electron transfer processes in self-assembled monolayers at metal surfaces using a density matrix approach.

A single-particle density matrix approach is introduced to simulate the dynamics of heterogeneous electron transfer (ET) processes at interfaces. The characterization of the systems is based on a model Hamiltonian parametrized by electronic structure calculations and a partitioning method. The method is applied to investigate ET in a series of nitrile-substituted (poly)(p-phenylene)thiolate self-assembled monolayers adsorbed at the Au(111) surface.

New Materials and Approaches for Advanced Optoelectronics.

An optoelectronic odyssey: ChemPlusChem presents its special issue on "New Materials and Approaches for Advanced Optoelectronics", guest-edited by Pedro Coto and Rubén Costa. This issue features top-quality contributions covering new blue-emitting coordination complexes, perovskites, nanocarbon-based hybrids, metal-organic frameworks, hybrid metal oxides, and small molecules.

Minimal Disease Activity and Patient-Acceptable Symptom State in Psoriatic Arthritis: A Real-World Evidence Study With Ustekinumab.

Background/aims: Ustekinumab (UST) is a fully human immunoglobulin G1 monoclonal antibody approved for treating moderate to severe psoriasis and, more recently, psoriatic arthritis (PsA) as well. However, information regarding its clinical usefulness in a real-world setting is scarce. We aimed to evaluate the effectiveness and safety of UST in a real-world clinical setting.

Prevalence and type II diabetes-associated factors in psoriatic arthritis.

Diabetes is a common cardiovascular risk factor in psoriatic arthritis (PsA). Although the prevalence of diabetes is high, the factors associated with it in PsA are poorly understood. We aimed to analyse the prevalence of type II diabetes and diabetes-associated factors in a hospital-based population with PsA.

Standards of care and quality indicators for multidisciplinary care models for psoriatic arthritis in Spain.

To define and give priority to standards of care and quality indicators of multidisciplinary care for patients with psoriatic arthritis (PsA). A systematic literature review on PsA standards of care and quality indicators was performed. An expert panel of rheumatologists and dermatologists who provide multidisciplinary care was established.

When Fluorescent Proteins Meet White Light-Emitting Diodes.

Over the last decades, fluorescent proteins (FPs) have been extensively employed for imaging and tracing in cell biology and medicine. However, their application for lighting devices like light-emitting diodes (LEDs) and lasers has recently started. The interest of FPs is the result of their good photoluminescence features (high emission efficiency with a narrow spectrum and a high photon-flux saturation), good photostability, sustainable production by bacteria, and eco-friendly recycling.