Insertion of reactive rhodium carbenes into boron-hydrogen bonds of stable N-heterocyclic carbene boranes.

Readily available rhodium(II) salts catalyze reactions between NHC-boranes (NHC-BH3) and diazocarbonyl compounds (N2CRCOR'). Stable α-NHC-boryl carbonyl compounds (NHC-BH2-CHRCOR') are isolated in good yields. The reaction is a reliable way to make boron-carbon bonds with good tolerance for variation in both the NHC-borane and diazocarbonyl components.

Postinterview Communication between Obstetrics and Gynecology Residency Programs and Candidates.

Introduction: Residency programs seek to match the best candidates with their positions. To avoid ethical conflicts in this process, the National Residency Matching Program (NRMP or Match) has rules regarding appropriate conduct, including guidelines on contact between candidates and programs. Our study examined communication between obstetrics and gynecology (Ob-Gyn) programs and residency candidates after interviewing and prior to ranking.

Mechanistic and preparative studies of radical chain homolytic substitution reactions of N-heterocyclic carbene boranes and disulfides.

Reactions of 1,3-dimethylimidazol-2-ylidene-borane (diMe-Imd-BH3) and related NHC-boranes with diaryl and diheteroaryl disulfides provide diverse NHC-boryl monosulfides (diMe-Imd-BH2SAr) and NHC-boryl disulfides (diMe-Imd-BH(SAr)2). Heating in the dark with 1 equiv of disulfide favors monosulfide formation, while irradiation with 2 equiv disulfide favors disulfide formation. With heteroaryl disulfides, the NHC-borane in the primary NHC-boryl sulfide product migrates from sulfur to nitrogen to give new products with a thioamide substructure.

Reductions of aldehydes and ketones with a readily available N-heterocyclic carbene borane and acetic acid.

Acetic acid promotes the reduction of aldehydes and ketones by the readily available N-heterocyclic carbene borane, 1,3-dimethylimidazol-2-ylidene borane. Aldehydes are reduced over 1-24 h at room temperature with 1 equiv of acetic acid and 0.5 equiv of the NHC-borane.

Efficient hydroxymethylation reactions of iodoarenes using CO and 1,3-dimethylimidazol-2-ylidene borane.

A hydroxymethylation reaction of a variety of iodoarenes proceeded effectively in the presence of CO, NHC-borane, diMeImd-BH3 (2) as a radical mediator, and a catalytic amount of AIBN. The reaction took place chemoselectively at the aryl-iodine bond but not at the aryl-bromine and aryl-chlorine bonds. A three-component coupling reaction comprising aryl iodides, CO, and electron-deficient alkenes also proceeded well to give unsymmetrical ketones in good yields.

Synthesis and analysis of the all-(S) side chain of phosphomycoketides: a test of NMR predictions for saturated oligoisoprenoid stereoisomers.

(4S,8S,12S,16S,20S)-Pentamethylheptacosan-1-ol has been synthesized and analyzed by resolution-enhanced NMR spectroscopy with the aid of a recent set predicted spectra of all its stereoisomers. The configuration was confirmed, but isomer purity of the sample (~70%) was lower than expected. A truncated analogue, (2S,6S,10S,14S)-2,6,10,14-tetramethylhenicosan-1-ol TBDPS ether, was prepared from a late stage synthetic intermediate.

Rotational isomers of N-methyl-N-arylacetamides and their derived enolates: implications for asymmetric Hartwig oxindole cyclizations.

The rotational preferences of N-(2-bromo-4,6-dimethylphenyl)-N-methyl 2-phenylpropanamide were studied as a model of precursors for Hartwig asymmetric oxindole cyclizations. The atropisomers of this compound were separated by flash chromatography, and then the enantiomers were resolved and the interconversions of the stereocenter and the N-Ar axis were studied. Under thermal conditions, the axis is very stable.

Eosinophil recruitment to nasal nerves after allergen challenge in allergic rhinitis.

In allergen challenged animal models, eosinophils localize to airway nerves leading to vagally-mediated hyperreactivity. We hypothesized that in allergic rhinitis eosinophils recruited to nasal nerves resulted in neural hyperreactivity. Patients with persistent allergic rhinitis (n=12), seasonal allergic rhinitis (n=7) and controls (n=10) were studied.

Risk society and the distribution of bads: theorizing class in the risk society.

Ulrich Beck states in the Risk Society (1992) that the rise of the social production of risks in the risk society signals that class ceases to be of relevance; instead the hierarchical logic of class will be supplanted by the egalitarian logic of the distribution of risks. Several trenchant critiques of Beck's claim have justified the continued relevance of class to contemporary society. While these accounts have emphasized continuity, they have not attempted to chart, as this paper will, how the growing social production of risk increases the importance of class.

Short palate, lung, and nasal epithelial clone-1 is a tightly regulated airway sensor in innate and adaptive immunity.

Short palate, lung, and nasal epithelial clone-1 (SPLUNC1) is a protein abundantly expressed by the respiratory epithelium of the proximal lower respiratory tract, a site of great environmental exposure. Previous studies showed that SPLUNC1 exerts antimicrobial effects, regulates airway surface liquid and mucociliary clearance, and suppresses allergic airway inflammation. We studied SPLUNC1 to gain insights into its role in host defense.

N-heterocyclic carbene-initiated hydrosilylation of styryl alcohols with dihydrosilanes: a mechanistic investigation.

Investigation of the mechanism of the NHC-initiated hydrosilylation of styryl alcohols in the presence of a dihydrosilane suggests a general base catalysis mechanism and not the activation of the dihydrosilane by the NHC.

The impact of shame on the therapeutic alliance and intimate relationships.

Objectives: This study examined the role of shame coping styles and state shame in predicting the therapeutic alliance and intimate relationship functioning in individuals with mental health problems.

Method: A sample of 50 treatment-receiving adults aged 21 to 67 years with a mix of common mental health difficulties was recruited from a clinical psychology service. Participants were given questionnaire measures of shame states, shame coping styles, intimate relationship functioning, and the therapeutic alliance.

Oxygen switch in visible-light photoredox catalysis: radical additions and cyclizations and unexpected C-C-bond cleavage reactions.

Visible light photoredox catalyzed inter- and intramolecular C-H functionalization reactions of tertiary amines have been developed. Oxygen was found to act as chemical switch to trigger two different reaction pathways and to obtain two different types of products from the same starting material. In the absence of oxygen, the intermolecular addition of N,N-dimethyl-anilines to electron-deficient alkenes provided γ-amino nitriles in good to high yields.

Bare-minimum fluorous mixture synthesis of a stereoisomer library of 4,8,12-trimethylnonadecanols and predictions of NMR spectra of saturated oligoisoprenoid stereoisomers.

All four diastereomers of a typical saturated oligoisoprenoid, 4,8,12-trimethylnonadecanol, are made by an iterative three-step cycle with the aid of traceless thionocarbonate fluorous tags to encode configurations. The tags have a minimum number of total fluorine atoms, starting at zero and increasing in increments of one. With suitable acquisition and data processing, each diastereomer exhibits characteristic chemical shifts of methyl resonances in its (1)H and (13)C NMR spectra.

A Novel Glass Polyalkenoate Cement for Fixation and Stabilisation of the Ribcage, Post Sternotomy Surgery: An ex-Vivo Study.

This study investigates the use of gallium (Ga) based glass polyalkenoate cements (GPCs) as a possible alternative adhesive in sternal fixation, post sternotomy surgery. The glass series consists of a Control (CaO-ZnO-SiO2), and LGa-1 and LGa-2 which contain Ga at the expense of zinc (Zn) in 0.08 mol% increments.

Using the cancer registry to meet the Commission on Cancer clinical trials accrual standard.

Clinical trials are an important tool for innovation in cancer treatments. Therefore, accrual into trials has been highlighted for Commission on Cancer (CoC)-accredited hospital programs. The current Standard 5.

The trauma still goes on...: the multigenerational legacy of Northern Ireland's conflict.

Numerous studies have been conducted internationally on the subject of multigenerational trauma; however, little is currently known about its existence in the context of the Northern Ireland conflict. The present study explored the outcomes of and mechanisms through which the trauma of one generation impacts on subsequent generations in this context. Using an Interpretative Phenomenological Approach (IPA), this study examined the subjective experiences, beliefs and perceptions of four mothers from Northern Ireland, all of whom had endured trauma during their childhoods.

Quality of life analysis in patients with KRAS wild-type metastatic colorectal cancer treated first-line with cetuximab plus irinotecan, fluorouracil and leucovorin.

Background: In the CRYSTAL study adding cetuximab to first-line FOLFIRI significantly improved outcome in patients with KRAS wild-type metastatic colorectal cancer. Quality of life (QoL) was assessed, and associations with tumour response and survival were investigated.

Patients And Methods: The European Organization for Research and Treatment of Cancer QoL questionnaire-core 30 was used, focusing on global health status (GHS)/QoL and social functioning scales.

Decompressive hemicraniectomy following malignant middle cerebral artery infarctions: a mixed methods exploration of carer experience and level of burden.

Purpose: This study explores the experiences and sense of burden of family carers of survivors of malignant middle cerebral artery infarctions who had undergone decompressive hemicraniectomy. To date, there have been no studies examining carer outcomes among this unique population. This study, taken alongside an already published study of survivor outcomes, provides a more holistic picture with regard to sequelae within the sample.

Tetrahydrofuran ring opening and related reactions with an N-heterocyclic carbene-boryl trifluoromethanesulfonate.

Reaction of the triflate group in dipp-Imd-BH(2)OTf with nucleophiles generally occurs by direct substitution to give products dipp-Imd-BH(2)Nu. In contrast, reaction of this boryl triflate with aryloxides (ArO(-)) in THF resulted in insertion of THF with ring opening in between the NHC-boryl electrophile and the aryloxide to give products dipp-Imd-BH(2)O(CH(2))(4)OAr. The incorporation of THF was observed with other nucleophiles such as ethylthiolate and trimethylsilanolate whose conjugate acids have pK(a) values similar to that of phenol.

An unusual cause of a pain in the neck: pseudoaneurysm from tuberculous lymphadenitis.

A pseudoaneurysm is a haematoma which is surrounded by connective tissue and communicates with the lumen of a ruptured blood vessel. It has no true defined capsule. We describe a case of tuberculous pseudoaneurysm.

Silica gel promotes reductions of aldehydes and ketones by N-heterocyclic carbene boranes.

N-Heterocyclic carbene boranes (NHC-boranes) such as 1,3-dimethylimidazol-2-ylidine trihydridoborane (diMe-Imd-BH(3)) serve as practical hydride donors for the reduction of aldehydes and ketones in the presence of silica gel. Primary and secondary alcohols are formed in good yields under ambient conditions. Aldehydes are selectively reduced in the presence of ketones.