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Peritoneal dialysis (PD) is an increasingly needed, life-maintaining kidney replacement therapy; efficient solute transport is critical for patient outcome. While the role of peritoneal perfusion on solute transport in PD has been described, the role of cellular barriers is uncertain, the mesothelium has been considered irrelevant. We calculated peritoneal blood microvascular endothelial (BESA) to mesothelial surface area (MSA) ratio in human peritonea in health, chronic kidney disease, and on PD, and performed molecular transport related gene profiling and single molecule localization microscopy in two mesothelial (MC) and two endothelial cell lines (EC). Molecular-weight dependent transport was studied in-vitro, ex-vivo and in mice. Peritoneal BESA is 1-3-fold higher than MSA across age groups, and increases with PD, while the mesothelium is preserved during the first two years of PD. Tight junction, transmembrane and transcytotic transporter expression are cell-type specifically expressed. At nanoscale, tight junction anchoring protein Zonula occludens-1 is more abundant and more continuously expressed along the MC than the EC. Ionic conductance is 3-fold lower across the MC than human microvascular EC, as is the permeability for creatinine, 4- and 10-kDa, but not for 70-kDa dextran. MC removal from sheep peritoneum abolishes ionic barrier function. Short term intraperitoneal LPS exposure in mice selectively affects peritoneal mesothelial integrity and increases transperitoneal solute transport. We provide molecular correlates and consistent functional evidence for the mesothelium as a barrier for peritoneal solute transport, i.e., essential information on peritoneal transport modelling, and for interventions to improve PD efficiency and biocompatibility, and beyond., (© The Author(s) 2024. Published by Oxford University Press on behalf of American Physiological Society.)

Background: Wood Harvesting and Storage (WHS) is a form of Biomass Carbon Removal and Storage (BiCRS) that utilizes a combined natural and engineered process to harvest woody biomass and put it into long term storage, most frequently in the form of subterranean burial. This paper aims to quantify the availability of woody biomass for the purposes of WHS in the continental United States using a carbon cycle modeling approach. Using a regional version of the VEGAS terrestrial carbon cycle model at 10 km resolution, this paper calculates the annual woody net primary production in the continental United States. It then applies a series of constraints to exclude woody biomass that is unavailable for WHS. These constraints include fine woody biomass, current land use, current wood utilization, land conservation, and topographical limitations. These results were then split into state by state and regional totals., Results: In total, the model projects the continental United States could produce 1,274 MtCO 2 e (CO 2 equivalent) worth of coarse woody biomass annually in a scenario with no anthropogenic land use or constraints. In a scenario with anthropogenic land use and constraints on wood availability, the model projects that 415 MtCO 2 e of coarse woody biomass is available for WHS annually. This is enough to offset 8.5% of the United States' 2020 greenhouse gas emissions. Of this potential, 20 MtCO 2 e is from the Pacific region, 77 MtCO 2 e is from the Western Interior, 91 MtCO 2 e is from the Northeast region, and 228 MtCO 2 e is from the Southeast region., Conclusion: There is enough coarse woody biomass available in the continental United States to make WHS a viable form of carbon removal and storage in the country. There is coarse woody biomass available across the continental United States. All four primary regions analyzed have enough coarse woody biomass available to justify investment in WHS projects., (© 2024. The Author(s).)

Background:  The benefits of minimally invasive techniques in cardiac surgery remain poorly defined. We evaluated the short- and mid-term outcomes after surgical aortic valve replacement through partial upper versus complete median sternotomy (MS) in a large, German multicenter cohort., Methods:  A total of 2,929 patients underwent isolated surgical aortic valve replacement via partial upper sternotomy (PUS, n  = 1,764) or MS ( n  = 1,165) at nine participating heart centers between 2016 and 2020. After propensity-score matching, 1,990 patients were eligible for analysis. The primary end point was major adverse cardiac and cerebrovascular events (MACCE), a composite of death, myocardial infarction, and stroke at 30 days and in follow-up, up to 5 years. Secondary end points were acute kidney injury, length of hospital stay, transfusions, deep sternal wound infection, Dressler's syndrome, rehospitalization, and conversion to sternotomy., Results:  Unadjusted MACCE rates were significantly lower in the PUS group both at 30 days ( p  = 0.02) and in 5-year follow-up ( p  = 0.01). However, after propensity-score matching, differences between the groups were no more statistically significant: MACCE rates were 3.9% (PUS) versus 5.4% (MS, p  = 0.14) at 30 days, and 9.9 versus 11.3% in 5-year follow-up ( p  = 0.36). In the minimally invasive group, length of intensive care unit (ICU) stay was shorter ( p  = 0.03), Dressler's syndrome occurred less frequently ( p  = 0.006), and the rate of rehospitalization was reduced significantly ( p  < 0.001). There were 3.8% conversions to full sternotomy., Conclusion:  In a large, German multicenter cohort, MACCE rates were comparable in surgical aortic valve replacement through partial upper and complete sternotomies. Shorter ICU stay and lower rates of Dressler's syndrome and rehospitalization were in favor of the partial sternotomy group., Competing Interests: None declared., (Thieme. All rights reserved.)

Objectives: Degeneration of mitral prostheses/rings may be treated by redo surgery, and, recently, by transcatheter valve-in-valve/ring implantation. This multicenter registry presents results of transcatheter valve-in-valve and repeat surgery for prostheses/rings degeneration., Methods: Data provided by 10 German heart centers underwent propensity score-matched retrospective analysis. The primary endpoint was 30-day/midterm mortality. Perioperative outcome was assessed according to the Mitral Valve Academic Research Consortium criteria. Further, the influence of moderate or greater tricuspid regurgitation (TR) on 30-day/midterm mortality was analyzed., Results: Between 2014 and 2019, 273 patients (79 transcatheter mitral valve-in-valve [TM-ViV] and 194 redo mitral valve replacement [Re-MVR]) underwent repeat procedure for mitral prosthesis/ring degeneration. Propensity score matching distinguished 79 patient pairs. European System for Cardiac Operative Risk Evaluation (EuroSCORE) II-predicted risk was 15.7 ± 13.7% in the TM-ViV group and 15.0% ± 12.7% in the Re-MVR group (P = .5336). TM-ViV patients were older (74.73 vs 72.2 years; P = .0030) and had higher incidence of atrial fibrillation (54 vs 40 patients; P = .0233). Severe TR incidence was similar (17.95% in TM-ViV vs 14.10%; P = .1741). Sixty-eight TM-ViV patients previously underwent mitral valve replacement, whereas 41 Re-MVR patients underwent valve repair (P < .0001). Stenosis was the leading degeneration mechanism in 42 TM-ViV versus 22 Re-MVR patients (P < .0005). The 30-day/midterm mortality did not differ between groups. Moderate or greater TR was a predictor of total (odds ratio [OR], 4.36; P = .0011), 30-day (OR, 3.76; P = .0180), and midterm mortality (OR, 4.30; P = .0378), irrespective of group., Conclusions: In both groups, observed mortality was less than predicted. Redo surgery enabled treatment of concomitant conditions, such as atrial fibrillation or TR. TR was shown to be a predictor of total, 30-day, and midterm mortality in both groups., (Copyright © 2022 The American Association for Thoracic Surgery. Published by Elsevier Inc. All rights reserved.)

We present an experimental and computational study to investigate noncovalent interactions between silyl groups that are often employed as "innocent" protecting groups. We chose an extended cyclooctatetraene (COT)-based molecular balance comprising unfolded (1,4-disubstituted) and folded (1,6-disubstituted) valance bond isomers that typically display remote and close silyl group contacts, respectively. The thermodynamic equilibria were determined using nuclear magnetic resonance measurements. Additionally, we utilized Boltzmann weighted symmetry-adapted perturbation theory (SAPT) at the sSAPT0/aug-cc-pVDZ level of theory to dissect and quantify noncovalent interactions. Apart from the extremely bulky tris(trimethylsilyl)silyl "supersilyl" group, there is a preference for the folded 1,6-COT valence isomer, with London dispersion interactions being the main stabilizing factor. This makes silyl groups excellent dispersion energy donors, a finding that needs to be taken into account in synthesis planning.

We have conducted an experimental and computational study of cyclooctatetraene-1,4/1,6-dimethanol ( 1,4 and 1,6 ) as a molecular balance with the goal in mind to determine the otherwise inaccessible hydrogen bonding energy (HBE) of the cyclic water dimer, which constitutes a transition state. The 1,4/1,6 folding equilibrium is governed by an intramolecular hydrogen bond in the folded 1,6 -isomer, in which the OH groups adopt a cyclic planar geometry, akin to the structure of the cyclic water dimer transition state. We characterized hydrogen bonding in 1,6 and reference complexes utilizing SAPT2 + (3)δMP2/aug-cc-pVTZ and selected quantum theory of atoms in molecule descriptors at M06-2XD3(0)/ma-def2-TZVPP. Additionally, we computed HBEs at the DLPNO-CCSD(T)/aug-cc-pVQZ level of theory. We find that hydrogen bonding in 1,6 is very similar to the interaction in the C i symmetric cyclic water dimer TS, both in magnitude and character. We experimentally determined the Gibbs free energy of the folding process (Δ G eq ) in a variety of organic solvents via nuclear magnetic resonance spectroscopy measurements at room temperature. By combining experimentally obtained Δ G eq values with corrections derived from accurate computational methods, we provide estimates for the HBE of cyclic water dimers and the cyclic water dimer TS, as the most stable cyclic water dimer.

We present an experimental and computational study on the conformers of N,N'-diphenylthiourea substituted with different dispersion energy donor (DED) groups. While the unfolded anti-anti conformer is the most relevant for thiourea catalysis, intramolecular noncovalent interactions counterintuitively favor the folded syn-syn conformer, as evident from a combination of low-temperature nuclear magnetic resonance measurements and computations. In order to quantify the noncovalent interactions, we utilized local energy decomposition analysis and symmetry-adapted perturbation theory at the DLPNO-CCSD(T)/def2-TZVPP and sSAPT0/6-311G(d,p) levels of theory. Additionally, we applied a double-mutant cycle to experimentally study the effects of bulky substituents on the equilibria. We determined London dispersion as the key interaction that shifts the equilibria towards the syn-syn conformers. This preference is likely a factor why such thiourea derivatives can be poor catalysts., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Terpenes may be converted by electrochemical oxidation to various oxidized products with appealing aroma properties. In this study, ( R )-limonene was anodically oxidized in the presence of ethanol, and the resulting mixture exhibited a pleasing fruity, herbal, citrus-like, and resinous odor. The aroma-active compounds were purified by means of preparative high-performance liquid chromatography, and their structures were elucidated by means of gas chromatography (GC)-mass spectrometry and nuclear magnetic resonance spectroscopy. In addition, the odor of the isolated compounds was determined by means of GC-olfactometry. Seventeen compounds were isolated, and for only four of them, analytical data had been reported previously in the literature. Furthermore, only for two of the compounds, an odor description had been available in the literature.

Background: Wood harvesting and storage (WHS) is a hybrid Nature-Engineering combination method to combat climate change by harvesting wood sustainably and storing it semi-permanently for carbon sequestration. To date, the technology has only been purposefully tested in small-scale demonstration projects. This study aims to develop a concrete way to carry out WHS at large-scale., Results: We describe a method of constructing a wood storage facility, named Wood Vault, that can bury woody biomass on a mega-tonne scale in specially engineered enclosures to ensure anaerobic environments, thus preventing wood decay. The buried wood enters a quasi-geological reservoir that is expected to stay intact semi-permanently. Storing wood in many environments is possible, leading to seven versions of Wood Vault: (1) Burial Mound (Tumulus or Barrow), (2) Underground (Pit, Quarry, or Mine), (3) Super Vault, (4) Shelter, (5) AquaOpen or AquaVault with wood submerged under water, (6) DesertOpen or DesertVault in dry regions, (7) FreezeVault in cold regions such as Antarctica. Smaller sizes are also possible, named Baby Vault. A prototype Wood Vault Unit (WVU) occupies 1 hectare (ha, 100 m by 100 m) of surface land, 20 m tall, stores up to 100,000 m 3 of wood, sequestering 0.1 MtCO 2 . A 1 MtCO 2 y -1 sequestration rate can be achieved by collecting currently unused wood residuals (WR) on an area of 25,000 km 2 , the size of 10 typical counties in the eastern US, corresponding to an average transportation distance of less than 100 km. After 30 years of operation, such a Wood Vault facility would have sequestered 30 MtCO 2 , stored in 300 WVUs, occupying a land surface of 300 ha. The cost is estimated at $10-50/tCO 2 with a mid-point price of $30/tCO 2 . To sequester 1 GtCO 2 y -1 , wood can be sourced from currently unexploited wood residuals on an area of 9 Mkm 2 forested land (9 million square kilometers, size of the US), corresponding to a low areal harvesting intensity of 1.1 tCO 2 ha -1 y -1 . Alternatively, giga-tonne scale carbon removal can be achieved by harvesting wood at a medium harvesting intensity of 4 tCO 2 ha -1 y -1 on 3 Mkm 2 of forest (equivalent to increasing current world wood harvest rate by 25%), or harvest on 0.8 Mkm 2 forest restored from past Amazon deforestation at high harvest intensity, or many combinations of these and other possibilities. It takes 1000 facilities as discussed above to store 1 GtCO 2 y -1 , compared to more than 6000 landfills currently in operation in the US. After full closure of a Wood Vault, the land can be utilized for recreation, agriculture, solar farm, or agrivoltaics. A more distributed small operator model (Baby Vault) has somewhat different operation and economic constraints. A 10 giga-tonne sequestration rate siphons off only 5% of total terrestrial net primary production, thus possible with WHS, but extreme caution needs to be taken to ensure sustainable wood sourcing., Conclusions: Our technical and economic analysis shows that Wood Vault can be a powerful tool to sequester carbon reliably, using a variety of wood sources. Most pieces of the technology already exist, but they need to be put together efficiently in practice. Some uncertainties need to be addressed, including how durability of buried wood depends on detailed storage methods and burial environment, but the science and technology are known well enough to believe the practicality of the method. The high durability, verifiability and low-cost makes it already an attractive option in the current global carbon market. Woody biomass stored in Wood Vaults is not only a carbon sink to combat current climate crisis, but also a valuable resource for the future that can be used as biomass/bioenergy and carbon supply. The quantity of this wood utilization can be controlled carefully to maintain a desired amount of CO 2 in the atmosphere to keep the Earth's climate from diving into the next ice age, acting as a climate thermostat. The CO 2 drawdown time is on the order of 100 years while the ramp-up time is a decade. A sense of urgency is warranted because the CO 2 removal rate is limited by biosphere productivity, thus delayed action means a loss of opportunity. In conclusion, WHS provides a tool for managing our Earth system, which will likely remain forever in the Anthropocene., (© 2022. The Author(s).)

We present an experimental and computational study of a cyclooctatetraene (COT)-based molecular balance disubstituted with commonly used silyl groups. Such groups often serve as protecting groups and are typically considered innocent bystanders. Our motivation here is to determine the actual steric effects of such groups by employing a molecular balance. While in the unfolded 1,4-valence isomer the silyl groups are far apart ( d σ-σ ≥ 5.15 Å), the folded 1,6-isomer is affected greatly by noncovalent interactions due to close σ-σ contacts ( d σ-σ ≤ 2.58 Å). In order to investigate the thermodynamic equilibrium between the 1,6- and 1,4-valence isomers, we employed temperature-dependent nuclear magnetic resonance measurements. Additionally, we assessed the nature of attractive and repulsive interactions in 1,6-disilyl-COT derivatives via a combination of local energy decomposition analysis (LED) and symmetry-adapted perturbation theory (SAPT) at the DLPNO-CCSD(T)/def2-TZVP and sSAPT0/aug- cc -pVDZ levels of theory. We identified London dispersion interactions as the main contributor to the molecular stability of the folded states, whereas Pauli exchange repulsion and a resulting internal strain favor the unfolded diastereomer.

Surgical therapy of combined coronary artery disease (CAD) and heart failure, also referred to as end-stage CAD, has evolved throughout the years and patients are currently being offered traditional coronary artery bypass grafting (CABG), with or without surgical ventricle restoration (SVR), interventions for ischemic mitral valve regurgitation, heart transplantation or implantation of mechanical cardiovascular support systems. Among surgical methods, operative myocardial revascularization (with or without ventricle restoration) is still playing an important role, aiming at restoration of proper myocardial perfusion, especially if heart muscle viability is present. Facing the donor shortage, CABG may constitute a valuable alternative to transplantation in selected patients. In individuals considered not suitable for surgical revascularization, implantation of mechanical circulatory support (MCS) not only appears as a salvage procedure, but also allows for reevaluation of future therapy directions. This article aims at providing an overview of evolving and current surgical practices in patients with end-stage CAD., Competing Interests: Conflicts of Interest: All authors have completed the ICMJE uniform disclosure forms (available at http://dx.doi.org/10.21037/cdt-20-284). The series “Heart Failure in the Young and Old: Insights into Various Therapies” was commissioned by the editorial office without any funding or sponsorship. RH served as the unpaid Guest Editor of the series and serves as an unpaid editorial board member of Cardiovascular Diagnosis and Therapy from July 2019 to Jun 2021. The authors have no other conflicts of interest to declare., (2021 Cardiovascular Diagnosis and Therapy. All rights reserved.)

Platinum-based antineoplastic agents play a major role in the treatment of numerous types of cancer. A new bulky, lipophilic, and chiral ligand based on 1,2-diaminodiamantane in both of its enantiomeric forms was employed for the preparation of new platinum(ii) complexes with chloride and oxalate ligands. The dichloride complexes have a higher solubility and were evaluated as anti-proliferation agents for human ovarian cancer cell lines A2780 and cisplatin-resistant A2780cis. Its R,R-enantiomer showed increased efficacy compared to cisplatin for both cancer cell lines. A chromatographic approach was used to estimate the solvent partition coefficient of the dichloride complex. The binding of diamondoid-based platinum complexes to nucleotides was tested for both enantiomers with guanosine monophosphate (GMP) and deoxyguanosine monophosphate (dGMP) and occurs at a similar or faster rate for both isomers compared to cisplatin despite greatly increased steric demand. These findings highlight the potential in 1,2-diaminodiamantane as a viable pharmacophore.

We describe a Brønsted acid-catalysed cascade reaction consisting of a Wagner-Meerwein rearrangement and a subsequent intra- or intermolecular Friedel-Crafts reaction leading to adamantane-based heterocycles. In contrast to the reported W.-M. rearrangements, in this case an iminium moiety serves as the acceptor of a migrating nucleophilic alkyl group in a [1,2]-alkyl shift.

Introduction: The recommended minimum activated clotting time (ACT) level for cardiopulmonary bypass (CPB) of 480 seconds originated from investigations with bubble oxygenators and uncoated extracorporeal circulation (ECC) systems. Modern minimal invasive ECC (MiECC) systems are completely closed circuits containing a membrane oxygenator and a tip-to-tip surface coating. We hypothesized that surface coating and the "closed-loop" design allow the MiECC to safely run with lower ACT levels and that an ACT level of 300 seconds can be safely applied without thromboembolic complications. The aim of this study was to investigate the potential risks during application of reduced heparin levels in patients undergoing coronary surgery., Methods: In this study, 68 patients undergoing coronary artery bypass grafting with MiECC were randomized to either the study group with an ACT target of 300 seconds or the control group with an ACT of 450 seconds. All other factors of MiECC remained unchanged., Results: The study group received significantly less heparin and protamine (heparin [international units] median [min-max], Red&#95;AC: 32,800 [23,000-51,500] vs. Full&#95;AC: 50,000 [35,000-65,000] p  < 0.001; protamine [international units], Red&#95;AC: 18,000 [10,000-35,000] vs. Full&#95;AC: 30,000 [20,000-45,000] p  < 0.001). The ACT in the study group was significantly lower at the start of MiECC (mean ± standard deviation: study group 400 ± 112 vs. control group 633 ± 177; p  < 0.0001). Before termination of CPB the ACT levels were: study group 344 ± 60 versus control group 506 ± 80. In both groups, the values of the endogenous thrombin potential (ETP) decreased simultaneously. None of the study participants experienced thromboembolic complications., Conclusion: Since no evidence of increased thrombin formation (ETP) was found from a laboratory standpoint, we concluded that the use of MiECC with a reduced anticoagulation strategy seems possible. This alternative anticoagulation strategy leads to significant reduction in dosages of both heparin and protamine. We can confidently move forward with investigating this anticoagulation concept. However, to establish clinical safety of ACT below 300 seconds, we need larger clinical studies., Competing Interests: Disclosure The authors report no conflicts of interest in this work., (Georg Thieme Verlag KG Stuttgart · New York.)

Background: Acrylic nails harbor more bacteria than natural nails, and wear is not recommended for health care workers (HCWs). Little is known about the new and popular gel nail products. This study sought to evaluate the bacterial burden of gel nails, standard nail polish, and natural nails on the hands of HCWs., Methods: The study was conducted at 3 health centers. Nails on the dominant hand of 88 HCWs were painted with gel polish and standard polish. Cultures were obtained on days 1, 7, and 14 of wear and before and after hand hygiene with alcohol hand gel., Results: A total of 741 cultures were obtained. Bacterial burden increased over time for all nail types (P ≤ .0001). Reductions in the bacterial burden of natural nails and standard polish, but not gel polish, (P = .001, P = .0028, and P = .98, respectively) were seen after hand hygiene. All 3 nail types become more contaminated with bacteria over time. Standard polish and natural nails may be more amenable to hand hygiene than gel polish., Conclusions: This study did not show an increased number of microorganisms on nails with gel polish; however, gel nails may be more difficult to clean using alcohol hand gel., (Copyright © 2018 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Elsevier Inc. All rights reserved.)

Phenol moieties are key structural motifs in many areas of chemical research from polymers to pharmaceuticals. Herein, we report on the design and use of a structurally demanding cyclic peroxide (spiro[bicyclo[2.2.1]heptane-2,4'-[1,2]dioxolane]-3',5'-dione, P4) for the direct hydroxylation of aromatic substrates. The new peroxide benefits from high thermal stability and can be synthesized from readily available starting materials. The aromatic C-H oxidation using P4 exhibits generally good yields (up to 96%) and appreciable regioselectivities.

We have developed a synthesis of 1,2-substituted adamantane carboxylic acids and further bridged cycloalkanes (cage compounds) by palladium acetate-catalyzed C-H bond oxidation. Acetoxylation of cycloalkane framework was performed using picolylamide as a directing group. Modification of the substrate, ligand design and variation of reaction conditions enabled us to study the mechanism of acetoxylation of aliphatic compounds. Post-functionalization reactions and cleavage of the directing group were developed. For the first time the synthesis and characterization of a β-C 3 -tri-substituted adamantane derivatives was achieved., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objective: The postoperative systemic inflammatory response after cardiopulmonary bypass (CPB) is still an undesirable side-effect after cardiac surgery. It is most likely caused by blood contact with foreign surfaces and by the surgical trauma itself. However, the recirculation of activated shed mediastinal blood is another main cause of blood cell activation and cytokine release. Minimal invasive extracorporeal circulation (MiECC) comprises a completely closed circuit, coated surfaces and the separation of suction blood. We hypothesized that MiECC, with separated cell saved blood, would induce less of a systemic inflammatory response than MiECC with no cell-saver. The aim of this study was, therefore, to investigate the impact of cell washing shed blood from the operating field versus direct return to the ECC on the biomarkers for systemic inflammation., Material and Methods: In the study, patients with MiECC and cell-saver were compared with the control group, patients with MiECC and direct re-transfusion of the drawn blood shed from the surgical field., Results: High amounts of TNF-α (+ 120% compared to serum blood) were found in the shed blood itself, but a significant reduction was demonstrated with the use of a cell-saver (TNF-α ng/l post-ECC 10 min: 9.5±3.5 vs. 19.7±14.5, p<0.0001). The values for procalcitonin were not significantly increased in the control group (6h: 1.07±3.4 vs. 2.15±9.55, p=0.19) and lower for C-reactive protein (CRP) (24h: 147.1±64.0 vs.134.4±52.4 p=0.28)., Conclusion: The use of a cell-saver and the processing of shed blood as an integral part of MiECC significantly reduces the systemic cytokine load. We, therefore, recommend the integration of cell-saving devices in MiECC to reduce the perioperative inflammatory response.

This letter presents the side-chain iodination of electron-deficient benzylic hydrocarbons at rt using N-hydroxyphthalimide (NHPI) as radical initiator and 1,3-diiodo-5,5-dimethylhydantoin and 3-iodo-1,5,5-trimethylhydantoin (3-ITMH) as iodine source. Addition of a carboxylic acid increased the reactivity due to complex formation with and activation of 3-ITMH by proton transfer and halogen bond formation. No S E Ar reactions were observed under the employed reaction conditions. Our method enables convenient product isolation and gives 50-72% yields of isolated products.

A newly developed enzyme immunoassay (EIA) for the detection of the tremorgenic indole-diterpene alkaloid paxilline (PAX) and closely related analogs was used to analyze ergot sclerotia collected from rye and barley fields. The mean EIA standard curve detection limit was 0.47 ± 0.14 ng/mL; relative cross-reactivity of toxin standard solutions was found for 11-hydroxy-paspaline (terpendole E, 1.1%) but not for lolitrem B or ergot alkaloids. Sclerotia from all fields were positive in the PAX-EIA at concentration levels of 620 ± 200 and 160 ± 37 μg/kg in ergot of rye and 130 ± 47 μg/kg in ergot of barley. Confirmatory analyses of sclerotia by liquid chromatography-tandem mass spectrometric detection identified PAX and its analog 13-desoxypaxilline. To the best of our knowledge, this is the first report on the natural occurrence of tremorgenic indole-diterpene alkaloid mycotoxins in ergot sclerotia from rye and barley. Along with details on the analytical methodology developed in this study, particularly PAX-antibody production, the relevance and implications of these findings for food and feed safety are discussed. Presence or absence of elevated levels of tremorgenic mycotoxins, along with the ergot alkaloids, would help in explaining the difference between the two distinct manifestations of historic ergotism, the convulsive and the gangrenous form. Further method development for paxilline and other tremorgenic mycotoxins in cereals used for food and feed is a prerequisite for a comprehensive risk assessment, which seems to be necessary in light of the findings reported here. Paxilline in ergot of rye.

The dilithio compound (E)-1-lithio-2-(o-lithiophenyl)-1-trimethylsilylethene (5) was synthesized from 2-trimethylsilylbenzo-[b]tellurophene (6) with lithium-6 and a detailed analysis of its 1 H, 6 Li, 13 C, and 29 Si NMR spectra showed 5 to form a dimer 5 2 in tetrahydrofuran and diethylether, while addition of tetramethylethylenediamine stabilizes a monomer 5 1 . A monomer-dimer equilibrium exists with K at 230 K = 1.25 and ΔG230o = -0.43 kJ mol -1 . Homonuclear 6 Li, 6 Li coupling of 0.25 ± 0.07 Hz in the dimer was detected by a 1D- 6 Li, 6 Li INADEQUATE experiment, and scalar 6 Li, 13 C coupling constants were obtained from 13 C satellites in the 6 Li spectrum, from 13 C multiplet simulation and 6 Li, 13 C-HMQC spectra. In addition, structures and coupling constants of 5 1 and 5 2 were calculated by density functional theory (DFT) methods. It was found that the magnitude of the 6 Li, 13 C spin-spin interactions shows an inverse correlation with the C-Li bond lengths. The intra-aggregate exchange in the dimer, caused by 180° rotation of one monomer unit within the solvent cage, was studied by 6 Li DNMR and line shape analysis and yielded ΔG298≠ = 60 ± 3 kJ mol -1 ; ΔH ≠  = 84 ± 3 kJ mol -1 ; ΔS ≠  = 80 ± 3 J mol -1  K -1 for this process. Copyright © 2015 John Wiley & Sons, Ltd., (Copyright © 2015 John Wiley & Sons, Ltd.)

Atypical chronic myeloid leukemia is a rare entity that presents diagnostic and therapeutic challenges. Traditionally utilized therapeutic agents such as hydroxyurea or interferon result in a median survival of approximately two years, thus warranting identification of better options. We report a 49-year-old Caucasian female, who presented with extreme leukocytosis (white blood cells of 148,300/µL) with left shift, severe anemia, and thrombocytopenia. Following a diagnosis of atypical chronic myeloid leukemia, she was started on intravenous decitabine. She subsequently developed paraneoplastic vasculitis of large arteries, which responded to high-dose glucocorticoid. Decitabine therapy resulted in an excellent hematologic response, transfusion independence, and successful transition to an allogeneic peripheral stem cell transplantation. However, the patient subsequently succumbed to the complications of acute graft-versus-host-disease. This case illustrates an association between atypical chronic myeloid leukemia and steroid-responsive paraneoplastic vasculitis and highlights the single-agent disease activity of decitabine in atypical chronic myeloid leukemia, which may be utilized as a bridging therapy to allogeneic stem cell transplantation., (© The Author(s) 2015.)

Twenty-nine basidiomycetes were screened in surface and liquid cultures for their capability to biotransform the chloroacetamide herbicide Dimethenamid-P (DMTA-P). The basidiomycete Irpex consors converted 70% of the herbicide (0.5 g L -1 DMTA-P) in liquid cultures within 6 days, applying a minimal medium under non-ligninolytic conditions. Nine transformation products of DMTA-P were identified by liquid chromatography-mass spectrometry analysis of the culture supernatants. The four main metabolites were isolated and subjected to GC-MS analysis and NMR spectroscopy. The analyses revealed that the thiophene ring was oxidized at three different positions. Metabolite M1 was identified as the S-oxide, which was isolable and relatively stable at room temperature. In metabolite M2, one methyl substituent of the thiophene ring was hydroxylated. The two metabolites M3A and M3B were diastereomers, but fully separated by HPLC. Here, oxidation of the aromatic CH carbon resulted in prototropic rearrangement to an αβ-unsaturated thiolactone. None of the three major metabolites of DMTA-P has been described before., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Direct unequal C-H bond difunctionalization of phosphorylated diamantane was achieved in high yield from the corresponding phosphonates. Reduction of the functionalized phosphonates provides access to novel primary and secondary alkyl/aryl diamantane phosphines. The prepared primary diamantyl phosphines are quite air stable compared to their adamantyl and especially alkyl or aryl analogues. This finding is corroborated by comparing the singly occupied molecular orbital energy levels of the corresponding phosphine radical cations obtained by density functional theory computations.

The fusion of the sp(3) -hybridized parent diamondoid adamantane with the sp(2) -hybridized pyrene results in a hybrid structure with a very large dipole moment which arises from bending the pyrene moiety. Presented herein is the synthesis, study of the electronic and optical properties, as well as the dynamic behavior of this new hydrocarbon., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Minimal invasive extracorporeal circulation (MiECC) systems have initiated important efforts within science and technology to further improve the biocompatibility of cardiopulmonary bypass components to minimize the adverse effects and improve end-organ protection. The Minimal invasive Extra-Corporeal Technologies international Society was founded to create an international forum for the exchange of ideas on clinical application and research of minimal invasive extracorporeal circulation technology. The present work is a consensus document developed to standardize the terminology and the definition of minimal invasive extracorporeal circulation technology as well as to provide recommendations for the clinical practice. The goal of this manuscript is to promote the use of MiECC systems into clinical practice as a multidisciplinary strategy involving cardiac surgeons, anaesthesiologists and perfusionists., (© The Author 2016. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.)

The storage of energy in a safe and environmentally benign way is one of the main challenges of today's society. Ammonia-borane (AB=NH3 BH3 ) has been proposed as a possible candidate for the chemical storage of hydrogen. However, the efficient release of hydrogen is still an active field of research. Herein, we present a metal-free bis(borane) Lewis acid catalyst that promotes the evolution of up to 2.5 equivalents of H2 per AB molecule. The catalyst can be reused multiple times without loss of activity. The moderate temperature of 60 °C allows for controlling the supply of H2 on demand simply by heating and cooling. Mechanistic studies give preliminary insights into the kinetics and mechanism of the catalytic reaction., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fluoroquinolones are considered as critically important antibiotics. However, they are used in appreciable quantities in veterinary medicine. Liquid manure and feces can contain substantial amounts of unmetabolized antibiotics and, thus, antibiotics can enter the environment if manure is used for soil fertilization. In this study, the microbial biotransformation of the synthetic veterinary fluoroquinolone danofloxacin by the ascomycete Xylaria longipes was investigated. Fungal submerged cultures led to a regioselective and almost quantitative formation of a single metabolite within 3 days. The metabolite was unequivocally identified as danofloxacin N-oxide by high-resolution mass spectrometry and one- and two-dimensional nuclear magnetic resonance spectroscopic techniques. An oxidation of the terminal nitrogen of the substituted piperazine moiety of the substance led to a remarkable reduction of 80% of the initial antibacterial activity. Thus, fungal enzymes involved in the biotransformation process might possess the potential to reduce the entrance of antibiotics via biotransformation of these compounds.

Objectives: At the moment, the main application of minimally invasive extracorporeal circulation (MiECC) is reserved for elective cardiac operations such as coronary artery bypass grafting (CABG) and/or aortic valve replacement. The purpose of this study was to compare the outcome of emergency CABG operations using either MiECC or conventional extracorporeal circulation (CECC) in patients requiring emergency CABG with regard to the perioperative course and the occurrence of major adverse cardiac and cerebral events (MACCE)., Methods: We analysed the emergency CABG operations performed by a single surgeon, between January 2007 and July 2013, in order to exclude the differences in surgical technique. During this period, 187 emergency CABG patients (113 MiECC vs 74 CECC) were investigated retrospectively with respect to the following parameters: in-hospital mortality, MACCE, postoperative hospital stay and perioperative transfusion rate., Results: The mean logistic European System for Cardiac Operative Risk Evaluation was higher in the CECC group (MiECC 12.1 ± 16 vs CECC 15.0 ± 20.8, P = 0.15) and the number of bypass grafts per patient was similar in both groups (MiECC 2.94 vs CECC 2.93). There was no significant difference in the postoperative hospital stay or in major postoperative complications. The in-hospital mortality was higher in the CECC group 6.8% versus MiECC 4.4% (P = 0.48). The perioperative transfusion rate was lower with MiECC compared with CECC (MiECC 2.6 ± 3.2 vs CECC 3.8 ± 4.2, P = 0.025 units of blood per patient)., Conclusions: In our opinion, the use of MiECC in urgent CABG procedures is safe, feasible and shows no disadvantages compared with the use of CECC. Emergency operations using the MiECC system showed a significantly lower blood transfusion rate and better results concerning the unadjusted in-hospital mortality., (© The Author 2015. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.)

A new transition-metal-free mode for the catalytic reduction of carbon dioxide via bidentate interaction has been developed. In the presence of Li2[1,2-C6H4(BH3)2], CO2 can be selectively transformed to either methane or methanol, depending on the reducing agent. The bidentate nature of binding is supported by X-ray analysis of an intermediate analogue, which experiences special stabilization due to aromatic character in the bidentate interaction. Kinetic studies revealed a first-order reaction rate. The transformation can be conducted without any solvent.