Mechanistic Interrogation of Photochemical Nickel-Catalyzed Tetrahydrofuran Arylation Leveraging Enantioinduction Data.

This manuscript details the development of an asymmetric variant for the Ni-photoredox α-arylation of tetrahydrofuran (THF), which was originally reported in a racemic fashion by Doyle and Molander. Leveraging the enantioselectivity data that we obtained, a complex mechanistic scenario different from those originally proposed is uncovered. Specifically, an unexpected dependence of the product enantiomeric ratio was observed on both the halide identity (aryl chloride vs bromide substrates) and the Ni source.

Efficacy and safety of colistin plus beta-lactams for bone and joint infection caused by fluoroquinolone-resistant gram-negative bacilli: a prospective multicenter study.

Objectives: The prognosis of bone and joint infections (BJI) caused by Gram-negative bacilli (GNB) worsens significantly in the face of fluoroquinolone-resistance. In this setting, scarce pre-clinical and clinical reports suggest that intravenous beta-lactams plus colistin may improve outcome. Our aim was to assess the efficacy and safety of this treatment in a well-characterized prospective cohort.

Indole Nucleophile Triggers Mechanistic Divergence in Ni-Photoredox N-Arylation.

This study presents a Ni-photoredox method for indole N-arylation, broadening the range of substrates to include indoles with unprotected C3-positions and base-sensitive groups. Through detailed mechanistic inquiries, a Ni(I/III) mechanism was uncovered, distinct from those commonly proposed for Ni-catalyzed amine, thiol, and alcohol arylation, as well as from the Ni(0/II/III) cycle identified for amide arylation under almost identical conditions. The key finding is the formation of a Ni(I) intermediate bearing the indole nucleophile as a ligand prior to oxidative addition, which is rare for Ni-photoredox carbon-heteroatom coupling and has a profound impact on the reaction kinetics and scope.

Association of microbiological factors with mortality in Escherichia coli bacteraemia presenting with sepsis/septic shock: a prospective cohort study.

Objectives: This study aimed to determine the association of Escherichia coli microbiological factors with 30-day mortality in patients with bloodstream infection (BSI) presenting with a dysregulated response to infection (i.e. sepsis or septic shock).

Leveraging the Redox Promiscuity of Nickel To Catalyze C-N Coupling Reactions.

This perspective details advances made in the field of Ni-catalyzed C-N bond formation. The use of this Earth abundant metal to decorate amines, amides, lactams, and heterocycles enables direct access to a variety of biologically active and industrially relevant compounds in a sustainable manner. Herein, different strategies that leverage the propensity of Ni to facilitate both one- and two-electron processes will be surveyed.

Solar-assisted oxidation of organochlorine pesticides in groundwater using persulfate and ferrioxalate.

The oxidation of hexachlorocyclohexane isomers in the aqueous phase (Milli-Q and groundwater) was studied using persulfate activated by ferrioxalate and solar light at circumneutral pH. The experiments were conducted in a solar simulator reactor with local radiation fluxes q= 1.12·10 E cms and in compound parabolic collectors with solar light (q≈10 E cms) for 390 min.

Mechanistic Evidence of a Ni(0/II/III) Cycle for Nickel Photoredox Amide Arylation.

This work demonstrates the dominance of a Ni(0/II/III) cycle for Ni-photoredox amide arylation, which contrasts with other Ni-photoredox C-heteroatom couplings that operate via Ni(I/III) self-sustained cycles. The kinetic data gathered when using different Ni precatalysts supports an initial Ni(0)-mediated oxidative addition into the aryl bromide. Using NiCl as the precatalyst resulted in an observable induction period, which was found to arise from a photochemical activation event to generate Ni(0) and to be prolonged by unproductive comproportionation between the Ni(II) precatalyst and the in situ generated Ni(0) active species.

How Effective Was the 2014 AUA Cryptorchidism Guideline? A Multi-institutional Evaluation.

Introduction: In 2014, the AUA published guidelines regarding the evaluation of cryptorchidism. This multi-institutional study aims to determine if these guidelines reduced the age of referral and the utilization of ultrasound in boys with cryptorchidism. We hypothesize that delayed referral continues, and utilization of ultrasound remains unchanged.

Vertebral osteomyelitis after spine instrumentation surgery: risk factors and management.

Background: Vertebral osteomyelitis after spine instrumentation surgery (pVOM) is a rare complication. Most cases of infection occur early after surgery that involve skin and soft tissue and can be managed with debridement, antibiotics, and implant retention (DAIR).

Aim: To identify pVOM risk factors and evaluate management strategies.

Usefulness and limitations of convergent cross sorting and continuity scaling methods for their application in simulated and real-world time series.

Causality detection methods are valuable tools for detecting causal links in complex systems. The efficiency of continuity scaling (CS) and the convergent cross sorting (CSS) methods to detect causality was analysed. Usefulness and limitations of both methods in their application to simulated and real-world time series was explored under different scenarios.

Reduced Graphene Oxide/Waste-Derived TiO Composite Membranes: Preliminary Study of a New Material for Hybrid Wastewater Treatment.

This work reports the preliminary results of the development of composite self-assembling membranes obtained by the combination of reduced graphene oxide (rGO) with commercial Degussa P25 titanium dioxide (TiO). The purpose is to demonstrate the possibility of combining, in the same self-standing material, the capability to treat wastewater containing both inorganic and organic pollutants by exploiting the established ability of rGO to capture metal ions together with that of TiO to degrade organic substances. Moreover, this study also investigates the potential photocatalytic properties of tionite (TIO), to demonstrate the feasibility of replacing commercial TiO with such waste-derived TiO-containing material, fulfilling a circular economy approach.

spp. Infections after Instrumented Spine Surgery Have a Good Prognosis Regardless of Rifampin Use: A Cross-Sectional Study.

Infection after spinal instrumentation (IASI) by spp. is being more frequently reported. The aim of this study was to analyse the incidence, risk factors, clinical characteristics, and outcome of a spp.

Crimean-Congo Hemorrhagic Fever, Spain, 2013-2021.

Crimean-Congo hemorrhagic fever (CCHF) is a viral infectious disease for which distribution of the main vector, Hyalomma spp. ticks, is expanding. We analyzed all 10 cases of CCHF diagnosed in Spain during 2013-2021; case-patient median age was 56.

Mild Amide -Arylation Enabled by Nickel-Photoredox Catalysis.

This paper describes a mild strategy to promote amide arylations. Photoinduced oxidation of a Ni(II) aryl amido intermediate is proposed to facilitate the challenging C-N reductive elimination step at moderate temperatures. Notably, the mildly basic conditions employed facilitate access to a broad scope including protected amino acids, heterocycles, phenols, and sterically hindered substituents.

Mild Sustainable Amide Alkylation Protocol Enables a Broad Orthogonal Scope.

Herein, the development of a mild sustainable protocol to couple primary alkyl chlorides and bromides with amides is described. In contrast to current methodologies, our system does not require the use of strongly basic conditions, high temperatures, or the addition of an organometallic catalyst, thereby enabling access to a remarkably orthogonal scope. KPO is used to facilitate the formation of secondary and tertiary amides, which are ubiquitous scaffolds in bioactive molecules and natural products.

Predicting relative efficiency of amide bond formation using multivariate linear regression.

Amides are ubiquitous in biologically active natural products and commercial drugs. The most common strategy for introducing this functional group is the coupling of a carboxylic acid with an amine, which requires the use of a coupling reagent to facilitate elimination of water. However, the optimal reaction conditions often appear rather arbitrary to the specific reaction.

Establishment and Persistence of Glycopeptide-Resistant ST80 and ST117 Clones Within a Health Care Facility Located in a Low-Prevalence Geographical Region.

Vancomycin-resistant (VREfm) is one of the most important nosocomial pathogens with limited therapeutic alternatives. In this study, we followed the trends of VREfm and causing bloodstream infections (BSIs) in a Spanish hospital, from 2011 to 2020. During this period, 832 strains were isolated and 121 (14.

Methylprednisolone in adults hospitalized with COVID-19 pneumonia : An open-label randomized trial (GLUCOCOVID).

Purpose: To determine whether a 6-day course of methylprednisolone (MP) improves outcome in patients with severe SARS-CoV‑2 (Corona Virus Disease 2019 [COVID-19]).

Methods: The study was a multicentric open-label trial of COVID-19 patients who were aged ≥ 18 years, receiving oxygen without mechanical ventilation, and with evidence of systemic inflammatory response who were assigned to standard of care (SOC) or SOC plus intravenous MP (40 mg bid for 3 days followed by 20 mg bid for 3 days). The primary outcome was a composite of death, admission to the intensive care unit, or requirement for noninvasive ventilation.

Implant Removal in the Management of Prosthetic Joint Infection by : Outcome and Predictors of Failure in a Large Retrospective Multicenter Study.

Objectives: To compare the characteristics and outcomes of cases with acute prosthetic joint infection (PJI; early post-surgical or hematogenous) by managed with implant removal (IRm) or debridement and retention (DAIR). To analyze the outcomes of all cases managed with IRm (initially or after DAIR failure).

Methods: Retrospective, multicenter, cohort study of PJI by (2003-2010).

Clinical and Histological Manifestations of Chronic Coca Leaf Chewing in a Peruvian Population: A Cross-sectional Study.

Aims: This study aimed to determine the possible clinical and histological periodontal effects of long-term coca leaf chewing habit in habitants of the highland region of Peru.

Materials And Methods: A total of 100 residents, were recruited for the study. Fifty individuals were habitual coca leaf chewers and 50 were non-users.

Infections after spine instrumentation: effectiveness of short antibiotic treatment in a large multicentre cohort.

Background And Objectives: Available information about infection after spine instrumentation (IASI) and its management are scarce. We aimed to analyse DAIR (debridement, antibiotics and implant retention) prognosis and evaluate effectiveness of short antibiotic courses on early forms.

Methods: Multicentre retrospective study of patients with IASI managed surgically (January 2010-December 2016).

Artificial intelligence as an analytic approximation to evaluate associations between parental feeding behaviours and excess weight in Colombian preschoolers.

Parental practices can affect children's weight and BMI and may even be related to a high prevalence of obesity. Therefore, the aim of this study was to evaluate the relationship between parents' practices related to feeding their children and excess weight in preschoolers in Bucaramanga, Colombia, using artificial intelligence. A cross-sectional study was carried out between September and December 2017.

Biocide mechanism of highly efficient and stable antimicrobial surfaces based on zinc oxide-reduced graphene oxide photocatalytic coatings.

Highly efficient photoactive antimicrobial coatings were obtained using zinc oxide-reduced graphene oxide nanocomposites (ZnO-rGO). Their remarkable antibacterial activity and high stability demonstrated their potential use for photoactive biocide surfaces. The ZnO-rGO nanocomposites were prepared by the sol-gel technique to create photocatalytic surfaces by spin-coating.