Electrochemical Cycling of Liquid Organic Hydrogen Carriers as a Sustainable Approach for Hydrogen Storage and Transportation.

Hydrogen (H), as a high-energy-density molecule, offers a clean solution to carry energy. However, the high diffusivity and low volumetric density of H pose a challenge for long-term storage and transportation. Liquid organic hydrogen carriers (LOHCs) have been suggested as a strategic way to store and transport hydrogen in stable molecules.

Structural and kinetic characterization of DUSP5 with a Di-phosphorylated tripeptide substrate from the ERK activation loop.

Introduction: Dual specific phosphatases (DUSPs) are mitogen-activated protein kinase (MAPK) regulators, which also serve as drug targets for treating various vascular diseases. Previously, we have presented mechanistic characterizations of DUSP5 and its interaction with pERK, proposing a dual active site.

Methods: Herein, we characterize the interactions between the DUSP5 phosphatase domain and the pT-E-pY activation loop of ERK2, with specific active site assignments.

A Co(III)-peroxo-arylboronate complex formed by nucleophilic reaction of a Co(III)-peroxo species.

In this work, we report the generation and characterization of two new Co(III)-peroxo complexes 2 and 3. 2 is best described as a mononuclear Co-(O) complex that exhibits an O-isotope sensitive OO bond stretching vibration at 845(-49) cm, indicating a relatively weak peroxo moiety compared to those of other Co-(O) complexes reported previously. Complex 3 is a Co-peroxo-arylboronate species having a rare {CoOOBO} five-membered metallocycle, which is structurally characterized using X-ray crystallography.

The Role of Matrix Metalloproteinases in Thoracic Aortic Disease: Are They Indicators for the Pathogenesis of Dissections?

The pathogenesis of aortic aneurysm and dissection continues to be under discussion. Extracellular matrix (ECM) remodeling processes in the aortic wall are hypothesized to be involved in the development of the disorders. Therefore, in a histological study, we investigated the expression of metalloproteases 1 and 9 (MMP1 and MMP9) and their inhibitors (TIMP 1 and TIMP 2) in cardiac surgery patients.

Sequential composite BIMA grafting for 3v-CAD: factors that predict successful outcome of the one-inflow and two-inflow revascularization techniques.

Objective: The effect of one-inflow and two-inflow coronary surgical revascularization techniques inclosing skeletonized double mammary artery (BIMA) as T-graft on outcome is studied.

Methods: Early ad mid-term outcome of complete BIMA revascularization (C-T-BIMA) versus left-sided BIMA with right-sided aorto-coronary bypass (L-T-BIMA + R-CABG) is quantified and analyzed by multivariate logistic regression, Cox-regression, and Kaplan-Meier analysis in a series of 204 consecutive patients treated for triple-vessel coronary disease (3v-CAD).

Results: The L-T-BIMA + R-CABG technique (n = 104) enables higher number of total (4.

Reduction of volume loss after left atrial injury by balloon occlusion-an experimental study.

Background: Advanced-stage lung cancers sometimes require an extensive surgical approach. There is a risk of severe bleeding due to injury to the cardiac atria. Due to the fact that in most cases the surgical planning does not involve the expertise of a heart surgeon or the availability of a heart lung machine, only rapid effective action can avert this life-threatening complication.

Outcome of Surgery for Ischemic Mitral Regurgitation Depends on the Type and Timing of the Coronary Revascularization.

Objective: Long-term outcomes of mitral valve (MV) repair versus MV replacement for ischemic mitral regurgitation (IMR) in patients undergoing either prior (PCR) or concomitant coronary revascularization (CCR) by surgery (CABG) or intervention (PCI) are uncertain.

Methods And Results: Of 446 patients receiving MV surgery for IMR between July 2006 and December 2010, 125 patients-87 CCR (69.1%) and 38 PCR (30.

Direct Activation of the C(sp)-NH Bond of Primary Aliphatic Alkylamines by a High-Valent Co(μ-O) Diamond Core Complex.

Aliphatic alkylamines are abundant feedstock and versatile building blocks for many organic transformations. While remarkable progress has been made to construct C-N bonds on aliphatic and aromatic carbon centers, the activation and functionalization of C(sp)-NH bonds in primary alkylamines remain a challenging process. In the present work, we discovered an unprecedented method to directly activate the C(sp)-NH bond of primary alkylamines by a high-valent dinuclear Co(μ-O) diamond core complex.

Differentiated impact of pulmonary hypertension on outcome after left ventricular assist device implantation and tricuspid valve repair.

The present study aimed to investigate the impact of pulmonary hypertension (PH) on short-term survival after LVAD implantation with or without tricuspid annuloplasty valve repair (TVr) performed to treat regurgitation and avoid RV-failure post-LVAD insertion. Data of 24 patients receiving LVAD-implantation are assessed and compared. The primary outcome is in-hospital survival.

Impact of the underlying aortic pathology on postimplantation syndrome after endovascular thoracic aortic repair.

Background: Thoracic endovascular aortic repair (TEVAR) is the treatment option of choice for almost all pathologies of the descending thoracic aorta. The aim of the present study was to determine the impact of aortic pathology on the occurrence of postimplantation syndrome (PIS) after TEVAR.

Methods: Seventy-four patients undergoing TEVAR for aortic dissection (TAD, 25), aortic aneurysm (TAA, 26), and aortic rupture or perforated ulcer (TAR/PAU, 23) were included in this retrospective study.

Unusual In-plane Aromaticity Facilitates Intramolecular Hydrogen Transfer in Long-Bonded -Isonitrosyl Methoxide.

The hydrogen-atom transfer from methoxy radical to nitric oxide, leading to the formation of formaldehyde and nitroxyl, represents a secondary reaction of photodissociation of methyl nitrite, which is used as rocket fuel. In this study, we explored the potential energy profile of the hydrogen-atom transfer using the electronic structure calculations at the DLPNO-CCSD(T)/aug-cc-pVTZ level of theory for two isomeric forms ( and ) of the pre-reaction complex. The -oriented pre-reaction complex has a weak elongated O─O bond, which gets further elongated in the hydrogen transfer transition state.

Risk factors for postoperative delirium after cardiac surgical procedures with cardioplegic arrest.

Objectives: The pathophysiology of delirium after cardiac surgery is complex. The present study aims to determine perioperative risk factors and construct a scoring system for postoperative delirium based on the type of surgery.

Methods: Three hundred patients undergoing coronary artery bypass grafting (CABG; n = 150) or valve and/or aortic surgery ± CABG (n = 150) were retrospectively evaluated.

Urinary TIMP-2 and IGFBP-7 protein levels as early predictors of acute kidney injury after cardiac surgery.

Background: Acute kidney injury (AKI) is a frequent complication associated with on-pump cardiac surgery. Early recognition may alter their prognosis. Therefore, the urinary concentrations of TIMP-2 (tissue inhibitor of metalloproteinases-2) and IGFBP7 (insulin-like growth factor-binding protein) as predictors for AKI were studied.

Efficient Protocol for Expression and Purification of DUSP5.

Dual Specificity Phosphatase 5 (DUSP5) is a human protein that targets specific kinases and dephosphorylates phosphoserine/threonine and phosphotyrosine residues. DUSP5 is found to be involved in cardiovascular diseases and many cancer pathways, including skin and breast cancer. For this reason, availability of an efficient protocol of expression and purification of DUSP proteins can play a crucial role in their studies towards better understanding of the disease process and development of better therapeutic approaches.

Video-assisted minimal access surgery for complicated mitral valve endocarditis, tricuspid valve insufficiency and progressive coronary disease after previous CABG - in the time of COVID-19: a case report.

Background: The timing for heart surgery following cerebral embolization after cardiac valve vegetation is vital to postoperative recovery being uneventful, additionally Covid-19 may negatively affect the outcome. Minimally invasive methods and upgraded surgical instruments maximize the benefits of surgery also in complex cardiac revision cases with substantial perioperative risk.

Case Presentation: A 68 y.

Regioselectivity in the Scholl Reaction: Mono and Double [7]Helicenes.

We employed the density functionaly theory (DFT)-predicted regioselectivity of the intramolecular Scholl reaction in phenanthrene and dibenzo[,]chrysene frameworks to obtain π-extended mono and double [7]helicenes, respectively. The formation of these helical structures occurs despite the buildup of a large strain energy up to 30 kcal/mol compared with their most stable isomers. The twisted and strained structures were characterized and analyzed by experimental (NMR, UV-vis, emission, electrochemistry, and single-crystal X-ray diffraction) techniques and were further supported by DFT calculations.

[Pathogenesis, diagnosis, prevention and treatment of disseminated intravascular coagulation syndrome in COVID-19 infection].

Aim: Clinical characteristics of disseminated intravascular coagulation (DIC) in COVID-19 infection and assessment of the effectiveness of complex therapy for this syndrome at the stages of prevention and treatment of various complications.

Materials And Methods: The study of publications was carried out through search engines on the Internet using keywords. To diagnose the infection, the COVID-19 program was used on the MeDiCase platform, which is publicly available on www.

Opening the Co(μ-O) Diamond Core by Lewis Bases Leads to Enhanced C-H Bond Cleaving Reactivity.

The high-valent diiron(IV) intermediate is the key oxidant that cleaves strong C-H bonds of methane in the catalytic cycle of soluble methane monooxygenase (sMMO). sMMO- was previously reported as a bis-μ-oxo Fe(μ-O) diamond core but was recently described to have an open core with a long Fe···Fe distance. We recently reported a high-valent Co(μ-O) diamond core complex () that is highly reactive with sp C-H bonds.

Symmetry Effects in Photoinduced Electron Transfer in Chlorin-Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region.

In donor-acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and synthesized two isomeric donor-acceptor assemblies in which electronic coupling between donor and acceptor is altered by the orbital symmetry control with the reorganization energy and charge transfer exothermicity being kept unchanged. Analysis of the optical absorption and luminescence spectra, supported by the DFT and TD-DFT calculations, showed that PET in these assemblies corresponds to the Marcus inverted region (MIR) and has larger rate for isomer with weaker electronic coupling.

Structural insights into the mechanism of oxidative activation of heme-free H-NOX from Vibrio cholerae.

Bacterial heme nitric oxide/oxygen (H-NOX) domains are nitric oxide (NO) or oxygen sensors. This activity is mediated through binding of the ligand to a heme cofactor. However, H-NOX from Vibrio cholerae (Vc H-NOX) can be easily purified in a heme-free state that is capable of reversibly responding to oxidation, suggesting a heme-independent function as a redox sensor.

Protein Molecular Dynamics Simulations with Approximate QM: What Can We Learn?

Classical force fields are essential for computer simulations of proteins and are typically parameterized to reproduce secondary and tertiary structure of isolated proteins. However, while protein-protein interactions are ubiquitous in nature, they are not considered in parameterization efforts and are far less understood than isolated proteins. A better characterization of intermolecular interactions is widely recognized as a key to revolutionizing drug and therapeutic developments with high-throughput computational screening.

Crystal and mol-ecular structure of jatrophane diterpenoid (2,3,4,5,7,8,9,13,14,15)-2,3,8,9-tetra-acet-oxy-5,14-bis-(benzo-yloxy)-15-hydroxy-7-(iso-butano-yloxy)jatropha-6(17),11()-diene.

The structure of the jatrophane diterpenoid (ES2), CHO, has ortho-rhom-bic (222) symmetry. The absolute configuration in the crystal has been determined as 2,3,4,5,7,8,9,13,14,15 [the Flack parameter is -0.06 (11)].

Discovery and Characterization of Halogenated Xanthene Inhibitors of DUSP5 as Potential Photodynamic Therapeutics.

Dual specific phosphatases (DUSPs) are an important class of mitogen-activated protein kinase (MAPK) regulators, and are drug targets for treating vascular diseases. Previously we had shown that DUSP5 plays a role in embryonic vertebrate vascular patterning. Herein, we screened a library of FDA-approved drugs and related compounds, using a -nitrophenylphosphate substrate (NPP)-based assay.

Highly Reactive Co(μ-O) Diamond Core Complex That Cleaves C-H Bonds.

The selective activation of strong sp C-H bonds at mild conditions is a key step in many biological and synthetic transformations and an unsolved challenge for synthetic chemists. In nature, soluble methane monooxygenase (sMMO) is one representative example of nonheme dinuclear iron-dependent enzymes that activate strong sp C-H bonds by a high-valent diiron(IV) intermediate . To date, synthetic model complexes of sMMO- have shown limited abilities to oxidize strong C-H bonds.

Exclusively Proton Conductive Membranes Based on Reduced Graphene Oxide Polymer Composites.

Proton exchange membranes are at the heart of various technologies utilizing electrochemical storage of intermittent energy sources and powering electrical devices. Current state of the art membranes are based on perfluorosulfonic acid, introduced more than a half century ago. Low specificity to protons accompanied by permeance by other species is one of the main impediments for various promising applications in green technologies in an energy sustainable economy.