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The iridium-catalyzed C-H borylation of benzamides typically leads to meta and para selectivities using state-of-the-art iridium-based N , N -chelating bipyridine ligands. However, reaching ortho selectivity patterns requires extensive trial-and-error screening via molecular design at the ligand first coordination sphere. Herein, we demonstrate that triazolylpyridines are excellent ligands for the selective iridium-catalyzed ortho C-H borylation of tertiary benzamides and, importantly, we demonstrate the almost negligible effect of the first coordination sphere in the selectivity, which is so far unprecedented in iridium C-H bond borylations. Remarkably, the activity is dramatically enhanced by exploiting a remote Zn⋯O[double bond, length as m-dash]C weak interaction between the substrate and a rationally designed molecular-recognition site in the catalyst. Kinetic studies and DFT calculations indicate that the iridium-catalyzed C-H activation step is not rate-determining, this being unique for remotely controlled C-H functionalizations. Consequently, a previously established supramolecular iridium catalyst designed for meta -borylation of pyridines is now compatible with the ortho -borylation of benzamides, a regioselectivity switch that is counter-intuitive regarding precedents in the literature. In addition, we highlight the role of the cyclohexene additive in avoiding the formation of undesired side-products as well as accelerating the HBpin release event that precedes the catalyst regeneration step, which is highly relevant for the design of powerful and selective iridium borylating catalysts., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The replacement of palladium catalysts for Wacker-type oxidation of olefins into ketones by first-row transition metals is a relevant approach for searching more sustainable protocols. Besides highly sophisticated iron catalysts, all the other first-row transition metal complexes have only led to poor activities and selectivities. Herein, we show that the cobalt-tetraphenylporphyrin complex is a competent catalyst for the aerobic oxidation of styrenes into ketones with silanes as the hydrogen sources. Remarkably, under room temperature and air atmosphere, the reactions were exceedingly fast (up to 10 minutes) with a low catalyst loading (1 mol %) while keeping an excellent chemo- and Markovnikov-selectivity (up to 99 % of ketone). Unprecedently high TOF (864 h -1 ) and TON (5,800) were reached for the oxidation of aromatic olefins under these benign conditions. Mechanistic studies suggest a reaction mechanism similar to the Mukaiyama-type hydration of olefins with a change in the last fundamental step, which controls the chemoselectivity, thanks to a unique hydrogen bonding network between the ethanol solvent and the cobalt peroxo intermediate., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Transition metal catalysis benefitting from supramolecular interactions in the secondary coordination sphere in order to pre-organize substrates around the active site and reach a specific selectivity typically occurs under long reaction times and mild reaction temperatures with the aim to maximize such subtle effects. Herein, we demonstrate that the kinetically labile Zn⋯N interaction between a pyridine substrate and a zinc-porphyrin site serving for substrate binding is a unique type of weak interaction that enables identification of supramolecular effects in transition metal catalysis after one hour at a high reaction temperature of 130 °C. Under carefully selected reaction conditions, supramolecularly-regulated palladium-catalyzed Mizoroki-Heck reactions between 3-bromopyridine and terminal olefins (acrylates or styrenes) proceeded in a more efficient manner compared to the non-supramolecular version. The supramolecular catalysis developed here also displayed interesting substrate-selectivity patterns.

In the California compliance cap-and-trade carbon market, improved forest management (IFM) projects generate carbon credits in the initial reporting period if their initial carbon stocks are greater than a baseline. This baseline is informed by a "common practice" stocking value, which represents the average carbon stocks of surveyed privately owned forests that are classified into the same general forest type by the California Air Resources Board. Recent work has called attention to the need for more ecologically informed common practice carbon stocking values for IFM projects, particularly those in areas with sharp ecological gradients. Current methods for estimating common practice produce biases in baseline carbon values that lead to a clustering of IFM projects in geographical areas and ecosystem types that in fact support much greater forest carbon stocks than reflected in the common practice. This phenomenon compromises additionality, or the increases in carbon sequestration or decreases in carbon emissions that would not have occurred in the absence of carbon crediting. This study seeks to expand upon recent work on this topic and establish unbiased common practice estimates along sharp ecological gradients using methods that do not rely upon discrete forest classification. We generated common practice values for credited IFM projects in the Southern Cascades using a principal components analysis on species composition over an extensive forest inventory to determine the ecological similarity between inventoried forests and IFM project sites. Our findings strengthen the results of recent research suggesting common practice bias and adverse selection. At several sites, even after controlling for private ownership, 100% of the initial carbon stocks could be explained by ecological variables. This result means that improved management did not preserve or increase carbon stocks above what was typical, suggesting that no carbon offsets should have been issued for these sites. This result reveals greater bias than that been found at project sites in this region by research that has used discrete forest categorization., (© 2023 Environmental Defense Fund. Ecological Applications published by Wiley Periodicals LLC on behalf of The Ecological Society of America.)

A novel enantiopure π-allylruthenium(IV) precatalyst allowed the enantioselective and stereospecific allylations of indoles and gave access to indolin-3-ones, containing vicinal stereogenic centers. Facile separation of diastereoisomers exhibiting opposite circularly polarized luminescence (CPL) activities in diverse solvents, including water, demonstrated the potential of these sustainable transformations and of the newly prepared molecules., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The Wacker reaction is the oxidation of olefins to ketones and typically requires expensive and scarce palladium catalysts in the presence of an additional copper co-catalyst under harsh conditions (acidic media, high pressure of air/dioxygen, elevated temperatures). Such a transformation is relevant for industry, as shown by the synthesis of acetaldehyde from ethylene as well as for fine-chemicals, because of the versatility of a carbonyl group placed at specific positions. In this regard, many contributions have focused on controlling the chemo- and regioselectivity of the olefin oxidation by means of well-defined palladium catalysts under different sets of reaction conditions. However, the development of Wacker-type processes that avoid the use of palladium catalysts has just emerged in the last few years, thereby paving the way for the generation of more sustainable procedures, including milder reaction conditions and green chemistry technologies. In this Minireview, we discuss the development of new catalytic processes that utilize more benign catalysts and sustainable reaction conditions., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Electronic and steric properties of NHC ligands functionalized with porphyrins were investigated. When porphyrins are used as NHC-wingtips, nickel(II) in the macrocyle significantly improves the catalytic activity of the neighbouring NHC-Rh(I) complex in the conjugate addition of phenylboronic acid to cyclohexen-2-one.

Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C-H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent of the action modes of enzymes, new elementary catalytic steps (i. e. C-B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Invited for the cover of this issue are Matthieu Jouffroy from Discovery Process Research at Janssen Pharmaceutica N.V. and the group of Rafael Gramage-Doria at the University of Rennes. The image depicts an Ir-based catalytic system "fueled" by hydrogen for the direct reductive amination of ketones and secondary amines, allowing complex aliphatic tertiary amines to be prepared and, so, new chemical space to be reached. Read the full text of the article at 10.1002/chem.202201078., (© 2022 Wiley-VCH GmbH.)

Direct reductive amination (DRA) is a ubiquitous reaction in organic chemistry. This transformation between a carbonyl group and an amine is most often achieved by using a super stoichiometric amount of hazardous hydride reagents, thus being incompatible with many sensitive functional groups. DRA could also be achieved by means of chemo- or biocatalysis, thereby attracting the interest of industry as well as academic laboratories due to the virtually perfect atom economy. Although DRAs are well-established for substrate pairs such as aldehydes with either 1° or 2° amines as well as ketones with 1° amines, the current methodologies are limited in the case of ketones with 2° amines. Herein, we present a general DRA protocol that overcomes this major limitation by means of iridium catalysis. The applicability of the methodology is demonstrated by accessing an unprecedented range of biologically relevant tertiary amines starting from both aliphatic ketones and aliphatic amines. The choice of a disphosphane ligand (Josiphos A or Xantphos) is essential for the success of the transformation., (© 2022 Wiley-VCH GmbH.)

The voluntary carbon market needs to embrace changes for the land sector.

Introduction and Objectives: Penile strangulation is a rare urological emergencyin our country, although not in others. Since the firstSpanish publication in 1952, 21 publications havebeen reported that have never been reviewed. The objectives of this article are to review theSpanish series and provide 2 new cases., Materials and Methods: A retrospective studyof penile ring strangulation in Spain between 1952and 2019 is carried out and 2 cases are contributed.The search for articles in Medline was done withdifferent key words in English: penile incarceration,penile strangulation, constriction penis, metallic ringsand Spanish and in Google with the Spanish ones: estrangulaciónde pene. The data of the variables studiedwere analyzed using descriptive statistics., Results: We found 21 Spanish articles on penilestrangulation by rings. These included 25 patientswith a mean age of 45.4 years (range 24-82). Ringswere metallic in 21 patients (84%), non-metallic in 3(12%) and data were unavailable in 1 (4%). The purposeof the ring was to prolong sexual activity in 36%,masturbation in 12%, due to psychiatric disease 12%,alcoholism 8%, accident and incontinence 8%, andthis data was not available in 24%. Strangulation evolutiontime ranged from 2 hours to 14 days (averageof 51 hours). The ring was cut with shears in 34.7%and with saws in 17.3%. The urologist did not need tocollaborate in 68% of cases. The cities with the mostrecorded cases were Barcelona with 5 (20%) andGranada with 4 (16%)., Conclusions: Penile strangulation is a seriousurological emergency. The metal ring section requiresprecision instruments. The collaboration oftraumatologists and firemen can be of great help. Itwould be advisable to have the Dremel Saw availablein hospitals.

Regional consistency is necessary for carbon credit integrity.

Introduction and Objectives: Multiple chemical sensitivity (MCS) is a disease due to a disproportionate systemic response to chemical agents presentin the environment. ts urinary manifestations are rare and poorly understood. We present a case with recurrent lower urinary tract symptoms (LUTS) and review these symptoms in Spanish and foreign publications., Clinical Case: A 30-year-old woman was referred for study of recurrent lower urinary tract symptoms of 17 years of evolution, triggered by food, perfumes, cleaning products, cosmetics and bleach. Repeated analytical, radiological and functional tests were normal. We suspected that she might suffer from MCS and advised a study in Preventive Medicine. The patient consulted an Environmental Medicine Center, and was diagnosed as having gradeIII-IV/IV MCS., Conclusions: This is the first case of MCS diagnosed from urinary clinical manifestations. Among the causes of LUTS we should also think of MCS.

Introduction and Objectives:  Multiple chemical sensitivity (MCS) is a multi-symptomatic systemic disease whose genitourinary symptoms are poorly known. The aim of this article is to study these symptoms in Spanish publications. MATERIALS AND METHODS: A retrospective study of descriptive type on the genitourinary symptoms of MCS is carried out in the Spanish publications between the years 2000 and 2019. The search in Medline was performed with MeSH terms "multiple chemical sensitivity Spanish" and in Google with free terms "sensibilidad química multiple España". In the publications found, only those referring to genitourinary symptoms were selected, in which year, authors, type of article (clinical case, review, casuistry), genital symptoms, urinary symptoms, specialty, hospital or centre and city were studied. The results of these variables have been analyzed with descriptive statistics., Results: We found 45 Spanish publications on MCS of which 20 (44,4%) mentioned genitourinary symptoms. The 20 articles corresponded to 7 clinical cases, 6 reviews, 2 case series, 2 updates, 1 book chapter, 1 special article and 1 consensus document. We found 12 publications on female genital symptoms (60%), 12 on urinary symptoms (60%) and 4 on male genital symptoms (20%). The specialties with the highest number of publications were Family Medicine and Psychiatry with 3 (15%) and Neumology, Toxicology and Anesthesia and Resuscitation with 2 (10%). There are publications from 13 hospitals and 7 national centers, health agencies or foundations. The publications corresponded to 10 cities, the 2 with the most publications being Madrid with 6 (30%) and Barcelona with 6 (30%). CONCLUSIONS: The genitourinary symptoms of MCS are mentioned in about half of the Spanish publications. There is a clear predominance of these symptoms in women. This "genitourinary syndrome" should be taken into account in urological and gynecological patients with MCS.

The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are found via trial-and-error screening due to the low association constants between the substrate and the catalyst in which small stereo-electronic modifications within them can lead to very different reactivities. To circumvent these limitations and to increase the level of reactivity prediction in these important reactions, we report herein a supramolecular catalyst harnessing Zn⋅⋅⋅N interactions that binds to pyridine-like substrates as tight as it can be found in some enzymes. The distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta-selective iridium-catalyzed C-H bond borylations with enzymatic Michaelis-Menten kinetics, besides unique substrate selectivity and dormant reactivity patterns., (© 2021 Wiley-VCH GmbH.)

Herein we report experimental evidence for the shortest intermolecular distance reported for two electronically-different hydrogen atoms in the solid state. The Hδ+Hδ- non-covalent interaction was studied using theoretical calculations indicating that electrostatic and dispersion forces are of paramount importance.

Introduction and Objectives: Juvenile gangrenous vasculitis of the scrotum was described by the Girona dermatologist Joaquín Piñol Aguadéin 1973. The objectives of this article are to review the world publications and provide a clinical case of this disease between urological and/or dermatological., Material and Methods: A review of juvenile gangrenous vasculitis of the scrotum between 1973 and 2019 is carried out and a new clinical case is contributed. The identification of articles in Medline was carried outwith MeSH terms "juvenile gangrenous vasculitis scrotum" and in Google with "juvenile gangrenous vasculitisscrotum". Ten clinical-epidemiological variables were studied in the articles: year, source, authors, number of cases, age, previous pharyngo-tonsillitis, biopsy of the lesion, treatment, days to healing, city and country. The results of the variables were analyzed with descriptive statistics. A new clinical case is described., Results: We found 26 world references, 18 of them Spanish, corresponding to 24 publications and 2 conference papers with a total of 29 patients. The meanage of the patients was 23.6 years. The treatments used were exeresis of the lesion (23%), cephalosporins and/or corticoids i.v. (15.3%), tetracyclines, ciprofloxacin or oral amoxicillin-clavulanate (15.3%), local cure and oral corticoids (11.5%) and mupirocin or topical tetracyclines (7.6%). Healing took place in an average of 21 days. The cities with the most cases reported were Barcelona with 11 (37.9%) and Pontevedra with 2 (6.8%). By country, Spain contributed 22 cases (75.8%) and Chile, Argentina, Portugal, Italy, Tunisia, Turkey and Great Britainthe remaining 7 cases (24.1%)., Conclusions: Juvenile gangrenous vasculitis of the scrotum is a benign entity with a self-limiting course. The process is preceded by pharyngo-tonsillitis in about half of the patients. The results of the study confirm the endemic nature of the disease in Mediterranean countries, including Spain.

Competing Interests: Raul DoriaEmployment: Sanatorio San Roque SRLLeadership: Sanatorio San RoqueStock and Other Ownership Interests: Sanatorio San Roque SRLNo other potential conflicts of interest were reported.

Homogeneous catalytic reactions are typically controlled by the stereoelectronic nature of the ligand(s) that bind to the metal(s). The advantages of the so-called first coordination sphere effects have been used for the efficient synthesis of fine chemicals relevant for industrial and academic laboratories since more than half a century. Such level of catalyst control has significantly upgraded in the last few decades by mastering additional interactions beyond the first coordination sphere. These so-called second coordination sphere effects are mainly inspired by the action mode of nature's catalysts, enzymes, and, in general, rely on subtle hydrogen bonding for the exquisite control of activity and selectivity. In order to span the scope of this powerful strategy to challenges that cannot be solved purely by hydrogen bonding, a variety of less common interactions have been successfully introduced in the last few years for a fine chemical synthesis. This review covers the latest and most exciting developments of this newly flourishing area with a particular focus on highlighting how these types of interactions can be rationally implemented to control the reactivity in a remote fashion, which is far away from the active site similar to what enzymes also do.

Introduction: There are currently various fixation or suspension techniques for pelvic organ prolapse (POP) surgery. Laparoscopic colposacropexy is considered the gold standard. We present the surgical steps of the laparoscopic latero-abdominal colposuspension (LACS) technique and the preliminary results obtained., Material and Methods: Patients with anterior and/or apical compartment symptomatic POP undergoing LACS are included. The Baden-Walker scale, the Overactive Bladder Questionnaire-Short Form (OAB-q SF), the Pelvic Organ Prolapse/Urinary Incontinence Sexual Questionnaire (PISQ-12) and the Patient Global Impression of Improvement (PGI-I) scale were used to assess the degree of prolapse, urinary filling and sexual symptoms and the level of satisfaction before and after surgery, respectively. Conventional laparoscopic material and a polyvinylidene fluoride (PVDF) mesh were used., Results: Eighteen patients were included with a minimum follow-up time of 6months. The mean surgical time was 70.3±23.8min. Anatomic correction of prolapse was seen in all cases. Only one recurrence was detected. High levels of patient satisfaction were achieved., Conclusion: LACS allowed the anatomical reconstruction of the pelvic floor and proved to be a minimally invasive, fast, effective, safe and reproducible technique. More series are needed to evaluate its role against laparoscopic colposacropexy., (Copyright © 2020 AEU. Publicado por Elsevier España, S.L.U. All rights reserved.)

Selective C-H bond functionalization catalyzed by metal complexes have completely revolutionized the way in which chemical synthesis is conceived nowadays. Typically, the reactivity of a transition metal catalyst is the key to control the site-, regio- and/or stereo-selectivity of a C-H bond functionalization. Of particular interests are molecules that contain multiple C-H bonds prone to undergo C-H bond activations with very similar bond dissociation energies at different positions. This is the case of benzanilides, relevant chemical motifs that are found in many useful fine chemicals, in which two C-H sites are present in chemically different aromatic fragments. In the last years, it has been found that depending on the metal catalyst and the reaction conditions, the amide motif might behave as a directing group towards the metal-catalyzed C-H bond activation in the benzamide site or in the anilide site. The impact and the consequences of such subtle control of site-selectivity are herein reviewed with important applications in carbon-carbon and carbon-heteroatom bond forming processes. The mechanisms unraveling these unique transformations are discussed in order to provide a better understanding for future developments in the field of site-selective C-H bond functionalization with transition metal catalysts., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Introduction and Objectives: Urethral-vesical and bladder foreign bodies by electric cables are the most uncommon. The objectives of this article are to present the first worldwide case of urethro-vesical foreign body by the cable of a video game and to review the 5 Spanish publications., Clinical Case: 14-year-old male attending the emergency department for urethral cable retention, urethralgia, hypogastric pain and malodorous urine incontinence. Simple abdominal radiography showed a ball of retained cable in the bladder coming out through the meatus. He was operated on by performing a cystotomy. He was discharged 24 hours later., Conclusions: Urethral and bladder foreign bodies by electric wire are a rare pathology. They can be due to different motivations. The treatment consists of the extraction of the cable, which can be carried out by endoscopic or open surgery depending on the size and morphology of the cable. It is advisable to study the mental state of these patients.

The first example of a ruthenium-catalyzed C-H bond alkylation via six-membered ruthenacycles is presented. This is disclosed for the C-H bond alkylation of biologically relevant cyclic amides with maleimide derivatives. The cyclic tertiary amide core acted as a directing group (DG) enabling formation of six-membered cycloruthenated species responsible for the control of the regio- and site selectivity of the reaction as well as the excellent functional group tolerance. Unexpectedly, cyclic amides were found to be better DGs than pyridine-containing ones or cyclic imides for this type of C-H bond functionalization.

Biologically relevant N -arylisoindolinones efficiently underwent arylation reactions under ruthenium catalysis via C-H bond functionalization. The reactions exclusively led to monoarylated products, and only ortho selectivity was observed in the aromatic ring connected to the nitrogen atom. Interestingly, no C-H bond functionalization was observed in the other benzene ring in the ortho position with respect to the carbonyl group. This ruthenium-catalyzed reaction displayed a high functional group tolerance, and it employed readily available and benchmark stable boronic acid and potassium aryltrifluoroborate derivatives as coupling partners. An appealing late-stage functionalization of indoprofen applying this methodology is showcased.

Site- and regio-selective aromatic C-H bond benzoxylations were found to take place using biologically appealing N-arylisoindolinones under ruthenium(ii) catalysis in the presence of (hetero)aromatic carboxylic acid derivatives as coupling partners. Besides the presence of two potential C(sp 2 )-H sites available for functionalization in the substrates, exclusive ortho selectivity was achieved in the phenyl ring attached to the nitrogen atom. Notably, the reactions occurred in a selective manner as only mono-functionalized products were formed and they tolerated a large number of functional chemical groups. The ability of the cyclic tertiary amide within the isoindolinone skeleton to act as a weak directing group in order to accommodate six-membered ring ruthenacycle intermediates appears to be the key to reach such high levels of selectivity. In contrast, the more sterically demanding cyclic imides were unreactive under identical reaction conditions.

We report on cyclic imides as weak directing groups for selective monohydroxylation reactions using ruthenium catalysis. Whereas acyclic amides are known to promote the hydroxylation of the C(sp 2 )-H bond enabling five-membered ring ruthenacycle intermediates, the cyclic imides studied herein enabled the hydroxylation of the C(sp 2 )-H bond via larger six-membered ruthenacycle intermediates. Furthermore, monohydroxylated products were exclusively obtained (even in the presence of overstoichiometric amounts of reagents), which was rationalized by the difficulty to accommodate coplanar intermediates once the first hydroxyl group was introduced into the substrate. The same reactivity was observed in the presence of palladium catalysts.

Inspired by enzymes such as cytochrome P-450, the study of the reactivity of metalloporphyrins continues to attract major interest in the field of homogeneous catalysis. However, little is known about benefitting from the substrate-recognition properties of porphyrins containing additional, catalytically relevant active sites. Herein, such an approach is introduced by using supramolecular ligands derived from metalloporphyrins customized with rigid, palladium-coordinating nitrile groups. According to different studies (NMR and UV/Vis spectroscopy, XRD, control experiments), the supramolecular ligands are able to accommodate pyridine derivatives as substrates inside the porphyrin pocket while the reactivity occurs at the peripheral side. By simply tuning a remote metal center, different binding events result in different catalyst reactivity, and this enzyme-like feature leads to high degrees of substrate selectivity in representative palladium-catalyzed Suzuki-Miyaura reactions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Incidence and mortality from cancer is increasing in most countries in the world, with the highest burden in developing countries. City Cancer Challenge (C/Can), an initiative launched in 2017, aims to improve access to quality cancer care in metropolitan areas (1 million inhabitants or more) in low- and upper-middle income countries by transforming the way stakeholders at the city, regional, and national levels collectively design, plan, and implement local cancer solutions. The approach is built on the core principle that local leaders in cities define their own needs and craft solutions with the support of a network of global, regional, and local partners that reflect an understanding of the unique local context. C/Can aims to build a collective movement of cities that can together deliver quality, equitable, and sustainable cancer control solutions for all.

A general ruthenium(II)-catalyzed methodology enabling the (hetero)arylation of alkenylic C-H bonds utilizing a series of synthetically appealing diazines as directing groups is presented. Despite the presence of additional nitrogen lone pairs remote from the C-H bond activation site, which could eventually poison the catalyst, the reaction times are short (3 h), thus being suitable for selective double C-H bond arylation. Mixtures of E:Z isomeric products were observed in some cases, which were further hydrogenated in a tandem manner in the presence of the remaining ruthenium catalyst from the first step, representing an alternative approach to more difficult C(sp 3 )-H bond functionalization. According to mechanistic studies, the unexpected E:Z product formation seems to occur by thermal C═C bond isomerization after the reductive elimination step.

The unprecedented transformation of a wide range of synthetically appealing phthalimides into amides in a single-step operation has been achieved in high yields and short reaction times using a ruthenium catalyst. Mechanistic studies revealed a unique, homogeneous pathway involving five-membered ring opening and CO 2 release with water being the source of protons.

Objective: To determine the efficacy, safety, and tolerability of vilazodone in the treatment of posttraumatic stress disorder (PTSD) with comorbid mild-to-moderate depression., Methods: A 12-week randomized, double-blind, placebo-controlled trial was conducted in adult outpatients who met DSM-IV criteria for PTSD with comorbid depression between February 2013 and September 2015. Participants were randomly assigned to receive vilazodone 40 mg/d or placebo, and outcome measures were obtained at scheduled visits. Primary outcome measures included change in PTSD symptoms from baseline to end of study as indexed by the Clinician-Administered PTSD Scale (CAPS) and PTSD Symptom Scale-Self-Report (PSS-SR). Secondary outcome measures of anxiety, depression, and impairment were obtained, as well as biomarker assessment at baseline and end of study., Results: A total of 59 patients were randomly assigned to receive vilazodone (n = 29) or placebo (n = 30). Of those who were randomized, there were 25 completers in the vilazodone group and 22 completers in the placebo group. No significant differences were observed between the groups on any of the primary or secondary outcome measures. Vilazodone was generally well tolerated with few differences in the rate of adverse events between groups., Conclusions: Treatment with vilazodone 40 mg/d did not improve symptoms of PTSD and comorbid depression. Further investigation of the biological mechanisms underlying PTSD may lead to identification of improved therapeutic targets., Trial Registration: ClinicalTrials.gov identifier: NCT01715519., (© Copyright 2017 Physicians Postgraduate Press, Inc.)

Non-covalent interactions between halopyridine substrates and catalytically inert building blocks, namely zinc(II)-porphyrins and zinc(II)-salphens, influence the catalytic outcome of Suzuki-Miyaura and Mizoroki-Heck palladium-catalysed cross-coupling reactions. The weak Zn⋅⋅⋅N interactions between halopyridine substrates and zinc(II)-containing porphyrins and salphens, respectively, were studied by a combination of 1 H NMR spectroscopy, UV/Vis studies, Job-Plot analysis and, in some cases, X-ray diffraction studies. Additionally, the former studies revealed unique supramolecular polymeric and dimeric rearrangements in the solid state featuring weak Br⋅⋅⋅N (halogen bonding), C-H⋅⋅⋅π, Br⋅⋅⋅π and π⋅⋅⋅π interactions. The reactivity of halopyridine substrates in homogeneous palladium-catalysed cross-coupling reactions was found to correlate with the binding strength between the zinc(II)-containing scaffolds and the corresponding halopyridine. Such observation is explained by the unfavourable formation of inactive over-coordinated halopyridine⋅⋅⋅palladium species. The presented approach is particularly appealing for those cases in which substrates and/or products deactivate (or partially poison) a transition-metal catalyst., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

China's South to North Water Diversion (SNWD) project connects portions of the Yangtze River in the south to the Yellow River system in the north, overcoming biogeographic barriers to water movement. The diversion will supply potable water to over 110 million people and provide multiple other socioeconomic benefits. However, an inadvertent negative impact of this connection includes creation of conduits for species invasions. Alligator weed (Alternanthera philoxeroides), water hyacinth (Eichhornia crassipes), and water lettuce (Pistia stratiotes) are the only aquatic plant species on China's shortlists for special control. These species are mainly invasive in the Yangtze River basin. If these species are able to invade the SNWD and further spread via the SNWD, they have the potential to alter water supply, including water quantity and quality, as well as local ecology and agriculture, threatening the goals of the diversion. Understanding the full potential for these species to invade northern China is critical to early management decisions to avoid costly negative impacts. We used Maxent modeling to evaluate the probability that each of these species might become invasive in the receiving water regions. The models predict that all three species will be able to expand their ranges northward, with alligator weed and water hyacinth having the greatest potential for range expansion. These results suggest the need for prevention, monitoring, and management strategies for these species to reduce the risk and costs of impacts.

Background: General paresis (GP) is a late form of parenchymal neurosyphilis causing dementia and neuropsychiatric disorders. The diagnosis is often difficult since the clinical signs are protean. So far, neuroimaging has played a minor role as radiological findings are not specific., Methods: We studied three immunocompetent patients, admitted to hospital for cognitive impairment. The diagnosis of neurosyphilis was formulated on the basis of serological texts and cerebrospinal fluid analysis. The patients underwent a 3 T MR examination including susceptibility-weighted imaging (SWI) sequence before and after the initiation of penicillin therapy., Results: In all patients, SWI revealed cortical hypointensity, mostly distributed in frontal and temporal lobes. In drug-naive patients, the hypointensity extended over the whole cortical thickness, from the cortical/subcortical junction to the pial surface. After starting the penicillin therapy, the cortical hypointensity partially reversed, involving only the deep cortical layers., Conclusions: The MRI pattern at SWI observed in patients with GP was not reported in other infectious or inflammatory disease of the central nervous system, thus we suggest it could be a peculiar radiological finding of the disease. On the basis of previous pathological data, we hypothesise that cortical SWI hypointensity could be expression of iron deposits within activated microglia., (Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.)

The Sea Level Affecting Marshes Model (SLAMM) was applied at six major estuaries along Florida's Gulf Coast (Pensacola Bay, St. Andrews/Choctawhatchee Bays, Apalachicola Bay, Southern Big Bend, Tampa Bay and Charlotte Harbor) to provide quantitative and spatial information on how coastal ecosystems may change with sea level rise (SLR) and to identify how this information can be used to inform adaption planning. High resolution LiDAR-derived elevation data was utilized under three SLR scenarios: 0.7 m, 1 m and 2 m through the year 2100 and uncertainty analyses were conducted on selected input parameters at three sites. Results indicate that the extent, spatial orientation and relative composition of coastal ecosystems at the study areas may substantially change with SLR. Under the 1 m SLR scenario, total predicted impacts for all study areas indicate that coastal forest (-69,308 ha; -18%), undeveloped dry land (-28,444 ha; -2%) and tidal flat (-25,556 ha; -47%) will likely face the greatest loss in cover by the year 2100. The largest potential gains in cover were predicted for saltmarsh (+32,922 ha; +88%), transitional saltmarsh (+23,645 ha; na) and mangrove forest (+12,583 ha; +40%). The Charlotte Harbor and Tampa Bay study areas were predicted to experience the greatest net loss in coastal wetlands The uncertainty analyses revealed low to moderate changes in results when some numerical SLAMM input parameters were varied highlighting the value of collecting long-term sedimentation, accretion and erosion data to improve SLAMM precision. The changes predicted by SLAMM will affect exposure of adjacent human communities to coastal hazards and ecosystem functions potentially resulting in impacts to property values, infrastructure investment and insurance rates. The results and process presented here can be used as a guide for communities vulnerable to SLR to identify and prioritize adaptation strategies that slow and/or accommodate the changes underway.

Disseminated histoplasmosis is an invasive fungal infection documented in patients with impaired cellular immunity coming from endemic areas (America, Asia, Africa). We report two cases of disseminated histoplasmosis in AIDS patients paradigmatic of the multifaceted nature of the disease, which may be an expression either of an advanced state of immunosuppression or the immune reconstitution inflammatory syndrome (IRIS).

Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules.

Transition metal catalysis plays an important role in both industry and in academia where selectivity, activity and stability are crucial parameters to control. Next to changing the structure of the ligand, introducing a confined space as a second coordination sphere around a metal catalyst has recently been shown to be a viable method to induce new selectivity and activity in transition metal catalysis. In this review we focus on supramolecular strategies to encapsulate transition metal complexes with the aim of controlling the selectivity via the second coordination sphere. As we will discuss, catalyst confinement can result in selective processes that are impossible or difficult to achieve by traditional methods. We will describe the template-ligand approach as well as the host-guest approach to arrive at such supramolecular systems and discuss how the performance of the catalyst is enhanced by confining it in a molecular container.

Homogeneous transition-metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mM or μM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M, inside well-defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mM levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular CO and CC bond-forming cyclization reactions., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki-Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon-carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki-Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2.

Two confining phosphane ligands derived from either α- or β-cyclodextrin produce singly P(III) -ligated metal complexes with unusual coordination spheres. High-pressure NMR studies have revealed that rhodium hydride complexes of the same type are also formed under hydroformylation conditions. This unique feature strongly favors the formation of the branched aldehyde at the expense of the linear one with high enantioselectivity in the rhodium-catalyzed hydroformylation of styrene., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objectives: The aim of this study was to investigate the diagnostic performance of (99m)Tc-hexamethypropylene amine oxime labeled autologous white blood cell ((99m)Tc-HMPAO-WBC) scintigraphy in patients with suspected infections associated with cardiovascular implantable electronic devices (CIEDs)., Background: Early, definite recognition of CIED-related infections combined with accurate localization and quantification of disease burden is a prerequisite for optimal treatment strategies., Methods: All 63 consecutive patients underwent clinical examination, blood chemistry, microbiology, and echography of the cardiac region/venous pathway of the device. Final diagnosis of infection was established in 32 of 63 patients and in 23 of 32 by microbiology., Results: Sensitivity of (99m)Tc-HMPAO-WBC single-photon emission computed tomography/computed tomography (SPECT/CT) was 94% for both detection and localization of CIED-associated infection. SPECT/CT imaging had a definite added diagnostic value over both planar and stand-alone SPECT. Pocket infection was often associated with lead(s) involvement; the intracardiac portion of the lead(s) more frequently exhibited (99m)Tc-HMPAO-WBC accumulation and presented the highest rate of complications, infectious endocarditis, and septic embolism. Two false negative cases and no false positive results were observed. None of the patients with negative (99m)Tc-HMPAO-WBC scintigraphy developed CIED-related infection during follow-up of 12 months. Echography of the cardiac region/venous pathway of the device had 90% specificity, but low sensitivity (81% when intracardiac lead[s] infection only was considered). The Duke criteria had 31% sensitivity for the definite category (100% specificity) and 81% for the definite and possible categories (77% specificity)., Conclusions: (99m)Tc-HMPAO-WBC scintigraphy enabled the confirmation of the presence of CIED-associated infection, definition of the extent of device involvement, and detection of associated complications. Moreover, (99m)Tc-HMPAO-WBC scintigraphy reliably excluded device-associated infection during a febrile episode and sepsis, with 95% negative predictive value., (Copyright © 2013 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.)