Electron Spin Dynamics of the Intersystem Crossing in Aminoanthraquinone Derivatives: The Spectral Telltale of Short Triplet Excited States.

We studied the excited state dynamics of two bis-amino substituted anthraquinone (AQ) derivatives, with absorption in the visible spectral region, which results from the attachment of a electron-donating group to the electron-deficient AQ chromophore. Femtosecond transient absorption spectra show that intersystem crossing (ISC) takes place in 190-320 ps, and nanosecond transient absorption spectra demonstrated an unusually short triplet state lifetime (2.06-5.

Computational Exploration of the Mechanism of Action of a Sorafenib-Containing Ruthenium Complex as an Anticancer Agent for Photoactivated Chemotherapy.

Ruthenium(II) polypyridyl complexes are being tested as potential anticancer agents in different therapies, which include conventional chemotherapy and light-activated approaches. A mechanistic study on a recently synthesized dual-action Ru(II) complex [Ru(bpy)(sora)Cl] is described here. It is characterized by two mono-dentate leaving ligands, namely, chloride and sorafenib ligands, which make it possible to form a di-aquo complex able to bind DNA.

Self-Sensing Cavitation Detection for Pulsed Cavitational Ultrasound Therapy.

Objectives: Monitoring cavitation during ultrasound therapy is crucial for assessing the procedure safety and efficacy. This work aims to develop a self-sensing and low-complexity approach for robust cavitation detection in moving organs such as the heart.

Methods: An analog-to-digital converter was connected onto one channel of the therapeutic transducer from a clinical system dedicated to cardiac therapy, allowing to record signals on a computer.

Benzo-Fused BOPAM Fluorophores: Synthesis, Post-functionalization, Photophysical Properties and Acid sensing Applications.

A novel category of asymmetric boron chromophores with the attachment of two BF moieties denoted as BOPAM has been successfully synthesized via a one-pot three-step reaction starting from N-phenylbenzothioamide. This synthetic route results in the production of [a] and [b]benzo-fused BOPAMs along with post-functionalization of the [a]benzo-fused BOPAMs. The photophysical properties of these compounds have been systematically investigated through steady-state absorption and fluorescence emission measurements in solvents at both ambient and cryogenic temperatures, as well as in the solid state.

Assessing Predictive Value of SARS-CoV-2 Epitope-Specific CD8 T-Cell Response in Patients with Severe Symptoms.

Specific T cell responses against SARS-CoV-2 provided an overview of acquired immunity during the pandemic. Anti-SARS-CoV-2 immunity determines the severity of acute illness, but also might be related to the possible persistence of symptoms (long COVID). We retrospectively analyzed ex vivo longitudinal CD8 T cell responses in 26 COVID-19 patients diagnosed with severe disease, initially (1 month) and long-term (10 months), and in a cohort of 32 vaccinated healthcare workers without previous SARS-CoV-2 infection.

The C1s core levels of polycyclic aromatic hydrocarbons and styrenic polymers: A first-principles study.

Understanding core level shifts in aromatic compounds is crucial for the correct interpretation of x-ray photoelectron spectroscopy (XPS) of polycyclic aromatic hydrocarbons (PAHs), including acenes, as well as of styrenic polymers, which are increasingly relevant for the microelectronic industry, among other applications. The effect of delocalization through π aromatic systems on the stabilization of valence molecular orbitals has been widely investigated in the past. However, little has been reported on the impact on the deeper C1s core energy levels.

Histotripsy and Catheter-Directed Lytic: Efficacy in Highly Retracted Porcine Clots In Vitro.

Objective: Standard treatment for deep vein thrombosis (DVT) involves catheter-directed anticoagulants or thrombolytics, but the chronic thrombi present in many DVT cases are often resistant to this therapy. Histotripsy has been found to be a promising adjuvant treatment, using the mechanical action of cavitating bubble clouds to enhance thrombolytic activity. The objective of this study was to determine if histotripsy enhanced recombinant tissue plasminogen activator (rt-PA) thrombolysis in highly retracted porcine clots in vitro in a flow model of occlusive DVT.

Hydrocortisone cardioprotection in ischaemia/reperfusion injury involves antioxidant mechanisms.

Background: Glucocorticoid (GR) and mineralocorticoid (MR) receptors are highly expressed in cardiac tissue, and both can be activated by corticosteroids. MR activation, in acute myocardial infarction (AMI), worsens cardiac function, and increase NHE activity contributing to the deleterious process. In contrast, effects of GR activation are not fully understood, probably because of the controversial scenario generated by using different doses or potencies of corticosteroids.

Peak Broadening in Photoelectron Spectroscopy of Amorphous Polymers: The Leading Role of the Electrostatic Landscape.

The broadening in photoelectron spectra of polymers can be attributed to several factors, such as light source spread, spectrometer resolution, the finite lifetime of the hole state, and solid-state effects. Here, for the first time, we set up a computational protocol to assess the peak broadening induced for both core and valence levels by solid-state effects in four amorphous polymers by using a combination of density functional theory, many-body perturbation theory, and classical polarizable embedding. We show that intrinsic local inhomogeneities in the electrostatic environment induce a Gaussian broadening of 0.

Modeling the Fluorescence Quantum Yields of Aromatic Compounds: Benchmarking the Machinery to Compute Intersystem Crossing Rates.

The calculation of fluorescence quantum yields (FQYs) and lifetimes of organic dyes remains very challenging. In this article, we extensively test the machinery to calculate FQYs. Specifically, we perform an extensive analysis on the parameters influencing the intersystem crossing (ISC), internal conversion (IC), and fluorescence rate constants calculations.

First-Principles Calculations of Excited-State Decay Rate Constants in Organic Fluorophores.

In this Perspective, we discuss recent advances made to evaluate from first-principles the excited-state decay rate constants of organic fluorophores, focusing on the so-called strategy. In this strategy, one essentially takes advantage of Fermi's golden rule (FGR) to evaluate rate constants at key points of the potential energy surfaces, a procedure that can be refined in a variety of ways. In this way, the radiative rate constant can be straightforwardly obtained by integrating the fluorescence line shape, itself determined from vibronic calculations.

Postoperative Staphylococcus aureus Infections in Patients With and Without Preoperative Colonization.

Importance: Staphylococcus aureus surgical site infections (SSIs) and bloodstream infections (BSIs) are important complications of surgical procedures for which prevention remains suboptimal. Contemporary data on the incidence of and etiologic factors for these infections are needed to support the development of improved preventive strategies.

Objectives: To assess the occurrence of postoperative S aureus SSIs and BSIs and quantify its association with patient-related and contextual factors.

The impact of free antiretroviral therapy for pregnant non-citizens and their infants in Botswana.

Introduction: In December 2019, the Botswana government expanded free antiretroviral therapy (ART) to include non-citizens. We evaluated the impact of this policy change on antenatal care (ANC), antiretroviral therapy coverage and adverse birth outcomes.

Methods: The Tsepamo Surveillance study collects data at up to 18 delivery sites in Botswana.

mRNA COVID-19 Vaccination Does Not Exacerbate Symptoms or Trigger Neural Antibody Responses in Multiple Sclerosis.

Background And Objective: In people with multiple sclerosis (pwMS), concern for potential disease exacerbation or triggering of other autoimmune disorders contributes to vaccine hesitancy. We assessed the humoral and T-cell responses to SARS-CoV-2 after mRNA vaccination, changes in disease activity, and development of antibodies against central or peripheral nervous system antigens.

Methods: This was a prospective 1-year longitudinal observational study of pwMS and a control group of patients with other inflammatory neurologic disorders (OIND) who received an mRNA vaccine.

Photophysical Properties of Silver Clusters in Faujasite Zeolites: Does the Crystal Size Matter?

Electrostatic interactions between the zeolite cavity and confined noble-metal nanoparticles govern the photophysical properties of these materials. A better understanding of these interactions can afford new perspectives in optoelectronics applications. We investigated this interplay by revealing the peculiar photophysical properties of Ag clusters embedded in nanosized faujasite zeolite structures.

Phosphorescent Properties of Heteroleptic Ir(III) Complexes: Uncovering Their Emissive Species.

In this contribution, we assess the computational machinery to calculate the phosphorescence properties of a large pool of heteroleptic [Ir(C^N)(N^N)] complexes (where N^N is an ancillary ligand and C^N is a cyclometalating ligand) including their phosphorescent rates and their emission spectra. Efficient computational protocols are next proposed. Specifically, different flavors of DFT functionals were benchmarked against DLPNO-CCSD(T) for the phosphorescence energies.

Extensive Analysis of the Parameters Influencing Radiative Rates Obtained through Vibronic Calculations.

Defining a theoretical model systematically delivering accurate predictions of the fluorescence quantum yields of organic dyes is highly desirable for designing improved fluorophores in a systematic rather than trial-and-error way. To this end, the first required step is to obtain reliable radiative rates (), as low typically precludes effective emission. In the present contribution, using a series of 10 substituted phenyls with known experimental , we analyze the impact of the computational protocol on the determined through the thermal vibration correlation function (TVCF) approach on the basis of time-dependent density functional theory (TD-DFT) calculations of the energies, structures, and vibrational parameters.

Initiating and imaging cavitation from infused echo contrast agents through the EkoSonic catheter.

Ultrasound-enhanced delivery of therapeutic-loaded echogenic liposomes is under development for vascular applications using the EkoSonic Endovascular System. In this study, fibrin-targeted echogenic liposomes loaded with an anti-inflammatory agent were characterized before and after infusion through an EkoSonic catheter. Cavitation activity was nucleated by Definity or fibrin-targeted, drug-loaded echogenic liposomes infused and insonified with EkoSonic catheters.

Passive Cavitation Imaging Artifact Reduction Using Data-Adaptive Spatial Filtering.

Passive cavitation imaging (PCI) with a clinical diagnostic array results in poor axial localization of bubble activity due to the size of the point spread function (PSF). The objective of this study was to determine if data-adaptive spatial filtering improved PCI beamforming performance relative to standard frequency-domain delay, sum, and integrate (DSI) or robust Capon beamforming (RCB). The overall goal was to improve source localization and image quality without sacrificing computation time.

The radiative surface hopping (RSH) algorithm: Capturing fluorescence events in molecular systems within a semi-classical non-adiabatic molecular dynamics framework.

In this article, we present the radiative surface hopping algorithm, which enables modeling fluorescence within a semi-classical non-adiabatic molecular dynamics framework. The algorithm has been tested for the photodeactivation dynamics of trans-4-dimethylamino-4'-cyanostilbene (DCS). By treating on equal footing the radiative and non-radiative processes, our method allows us to attain a complete molecular movie of the excited-state deactivation.

Evaluation and Clinical Impact of Biofire FilmArray Pneumonia Panel Plus in ICU-Hospitalized COVID-19 Patients.

Microbiological diagnosis by using commercial multiplex quantitative PCR systems provides great advantages over the conventional culture. In this work, the Biofire FilmArray Pneumonia Panel Plus (FAPP+) was used to test 144 low respiratory tract samples from 105 COVID-19 patients admitted to an Intensive Care Unit (ICU), detecting 78 pathogens in 59 (41%) samples. The molecular panel was evaluated by using the conventional culture (CC) as comparator, which isolated 42 pathogens in 40 (27.