Exploring Electrophilic Hydrophosphination via Metal Phosphenium Intermediates.

Two Mo(0) phosphenium complexes containing ancillary secondary phosphine ligands have been investigated with respect to their ability to participate in electrophilic addition at unsaturated substrates and subsequent P-H hydride transfer to "quench" the resulting carbocations. These studies provide stoichiometric "proof of concept" for a proposed new metal-catalyzed electrophilic hydrophosphination mechanism. The more strongly Lewis acidic phosphenium complex, [Mo(CO)4(PR2H)(PR2)]+ (R=Ph, Tolp), cleanly hydrophosphinates 1,1-diphenylethylene, benzophenone, and ethylene, while other substrates react rapidly to give products resulting from competing electrophilic processes. A less Lewis acidic complex, [Mo(CO)3(PR2H)2(PR2)]+, generally reacts more slowly but participates in clean hydrophosphination of a wider range of unsaturated substrates, including styrene, indene, 1-hexene, and cyclohexanone, in addition to 1,1-diphenylethylene, benzophenone, and ethylene. Mechanistic studies are described, including stoichiometric control reactions and computational and kinetic analyses, which probe whether the observed P-H addition actually does occur by the proposed electrophilic mechanism, and whether hydridic P-H transfer in this system is intra- or intermolecular. Preliminary reactivity studies indicate challenges that must be addressed to exploit these promising results in catalysis.

Systemic Haemophilus parainfluenzae Infection Manifesting With Endocarditis and Membranoproliferative Glomerulonephritis.

Infective endocarditis (IE) is a potentially fatal disease that is primarily caused by Staphylococci and Streptococci. The HACEK group of bacteria (Hemophilus species, Aggregatibacter species, Cardiobacterium hominis, Eikenella corrodens, Kingella kingae) account for only 1-3% of reported IE cases. IE has long been known to cause glomerulonephritis. The most common histologic patterns seen are crescentic and diffuse proliferative glomerulonephritis. Notably, membranoproliferative glomerulonephritis (MPGN) is one of the less common patterns seen with IE. We present a rare case of MPGN associated with Haemophilus parainfluenzae endocarditis. A 56-year-old male with no significant past medical history presented to a local hospital with complaints of fever, night sweats, dyspnea, diarrhea, and dark urine for about a month. He was found to have a hemoglobin of 4g/dL, requiring multiple transfusions. He also had bilateral pleural effusions and pulmonary edema. In the following days, he had worsening renal function and was transferred to our hospital for further workup. Initial labs showed anemia, thrombocytopenia, and leukocytosis. He had creatinine elevated at 5.28 mg/dL and a low estimated glomerular filtration rate (eGFR) of 12 mL/min/1.73m2. Urinalysis showed proteinuria, urine hemoglobin, urine white blood cells (WBCs), and red blood cells (RBCs). Blood cultures revealed H. parainfluenzae. Transesophageal echocardiogram (TEE) showed large vegetations with perforation of the mitral valve leaflet. Serology showed low complement levels. Renal biopsy displayed a membranoproliferative pattern of glomerulonephritis on light microscopy. The hepatitis panel was negative, as was the autoimmune workup. The patient was diagnosed with MPGN associated with H. parainfluenzae endocarditis. His complex clinical course required mitral valve replacement and aortic valve repair. He completed the course of antibiotics, with improvement in renal and cardiac function.

A Case of Mixed Type II Cryoglobulinemic Vasculitis Associated With Marginal Zone B-cell Lymphoma.

Our patient is a male in his 40s with a past medical history of sickle cell trait, factor V Leiden mutation, marginal zone B-cell lymphoma, gastric mucosa-associated lymphoid tissue (MALT) lymphoma, and sarcoidosis who presented with the complaint of hemoptysis, dyspnea, abdominal pain, arthralgias, peripheral edema of the lower extremities with petechial rash, and oliguria. Investigations revealed acute kidney injury and bilateral transudative pleural effusion. Serology was positive for elevated rheumatoid factor, low complement components, and cryoglobulins. Renal biopsy showed membranoproliferative cryoglobulinemic glomerulonephritis with deposition of monoclonal IgM and IgG3 with kappa light chain and C3 component. The patient was diagnosed with mixed type II cryoglobulinemic vasculitis in the setting of untreated marginal B-cell lymphoma. He had a complex clinical course, requiring multiple intubations, hemodialysis, and treatment with intravenous immunoglobulin, plasmapheresis, steroids, and chemotherapy, to which he initially responded. During treatment, he developed cardiomyopathy associated with congestive heart failure and passed away due to cardiac arrest. We present a rare case of mixed type II cryoglobulinemic vasculitis secondary to untreated marginal zone B-cell lymphoma in a hepatitis C virus (HCV) negative patient, which has not been reported before.

Reversible Silylium Transfer between P-H and Si-H Donors.

The Mo=PR2 π* orbital in a Mo phosphenium complex acts as acceptor in a new PIII -based Lewis superacid. This Lewis acid (LA) participates in electrophilic Si-H abstraction from E3 SiH to give a Mo-bound secondary phosphine ligand, Mo-PR2 H. The resulting Et3 Si+ ion remains associated with the Mo complex, stabilized by η1 -P-H donation, yet undergoes rapid exchange with an η1 -Si-H adduct of free silane in solution. The equilibrium between these two adducts presents an opportunity to assess the role of this new LA in catalytic reactions of silanes: is the LA acting as a catalyst or as an initiator? Preliminary results suggest that a cycle including the Mo-bound phosphine-silylium adduct dominates in the catalytic hydrosilylation of acetophenone, relative to a putative cycle involving the silane-silylium adduct or "free" silylium.

A thermolytic route to a polysilyne.

We report a safe and convenient method to prepare a new class of network polysilane, or polysilyne ([RSi]n). Simple thermolysis of a readily accessible linear poly(phenylsilane), [PhSiH]n, affords polysilyne [PhSi]n with concomitant evolution of monosilanes. This new polymer shows a hyperbranched structure with unique features not observed in known polysilynes prepared via hazardous Wurtz coupling routes. Despite these differences, our soluble, yellow polysilyne exhibits some important properties associated with the traditional random network structure: it absorbs up to 400 nm in the UV spectrum, yet is stable to photolysis under inert atmosphere. This efficient new synthetic route opens the door to exciting applications for these hyperbranched polymers in materials and device technologies.

Results From a Survey of American Geriatrics Society Members' Views on Physician-Assisted Suicide.

BACKGROUND: Physician-assisted suicide (PAS) is a controversial practice, currently legal in nine states and the District of Columbia. No prior study explores the views of the American Geriatrics Society (AGS) membership on PAS. DESIGN: We surveyed 1488 randomly selected AGS members via email. PARTICIPANTS: A total of 369 AGS members completed the survey (24.8% response rate). ANALYSIS: We conducted bivariate correlation analyses of beliefs related to support for PAS. We also conducted qualitative analysis of open-ended responses. RESULTS: There was no consensus regarding the acceptability of PAS, with 47% supporting and 52% opposing this practice. PAS being legal in the respondent's state, belief that respect for autonomy alone is sufficient to justify PAS, and intent to prescribe or support requests for PAS if legal in state of practice all correlated with support for PAS. There was no consensus on whether the AGS should oppose, support, or adopt a neutral stance on PAS. Most respondents believed that PAS is more complex among patients with low health literacy, low English proficiency, disability, dependency, or frailty. Most respondents supported mandatory palliative care consultation and independent assessments from two physicians. Themes identified from qualitative analysis include role of the medical profession, uncertainty of the role of professional organizations, potential unintended consequences, autonomy, and ethical and moral considerations. CONCLUSION: There was no consensus among respondents regarding the acceptability of PAS. Respondents expressed concern about vulnerable older populations and the need for safeguards when responding to requests for PAS. Ethical, legal, and policy discussions regarding PAS should consider vulnerable populations. J Am Geriatr Soc 68:23-30, 2019.

A Practical Guide for Implementing a Holistic Admissions Review.

BACKGROUND: Various minorities in terms of race, ethnicity, gender, sexual identity, and socioeconomic status experience poorer health outcomes than those in the majority. Evidence indicates that provider diversity is associated with improved access to care for minorities, increased patient satisfaction, improved outcomes, and better educational experiences for health professions students. METHOD: The holistic admissions review is a flexible, individualized way of assessing an applicant's capabilities through consideration of experiences, attributes, and metrics (EAMs) that can serve as an important tool in diversifying the nursing workforce. RESULTS: This article discusses (a) critical elements that must be addressed during the development and implementation of a holistic admissions review and (b) the creation and use of a scoring rubric based on the EAMs identified. CONCLUSION: The implementation of a rubric was found to be a helpful tool to create a more thoughtful review of noncognitive factors and greater diversity in the student body. [J Nurs Educ. 2019;58(11):669-673.].

Competitive Ligand Exchange and Dissociation in Ru Indenyl Complexes.

Kinetic profiles obtained from monitoring the solution-phase substitution chemistry of [Ru(η5-indenyl)(NCPh)(PPh3)2]+ (1) by both electrospray ionization mass spectrometry and 31P{1H} NMR are essentially identical, despite an enormous difference in sample concentrations for these complementary techniques. These studies demonstrate dissociative substitution of the NCPh ligand in 1. Competition experiments using different secondary phosphine reagents provide a ranking of phosphine donor abilities at this relatively crowded half-sandwich complex: PEt2H > PPh2H ≫ PCy2H. The impact of steric congestion at Ru is evident also in reactions of 1 with tertiary phosphines; initial substitution products [Ru(η5-indenyl)(PR3)(PPh3)2]+ rapidly lose PPh3, enabling competitive re-coordination of NCPh. Further solution experiments, relevant to the use of 1 in catalytic hydrophosphination, show that PPh2H out-competes PPh2CH2CH2CO2Bu t (the product of hydrophosphination of tert-butyl acrylate by PPh2H) for coordination to Ru, even in the presence of a 10-fold excess of the tertiary phosphine. Additional information on relative phosphine binding strengths was obtained from gas-phase MS/MS experiments, including collision-induced dissociation experiments on the mixed phosphine complexes [Ru(η5-indenyl)PP'P″]+, which ultimately appear in solution during the secondary phosphine competition experiments. Unexpectedly, unsaturated complexes [Ru(η5-indenyl)(PR2H)(PPh3)]+, generated in the gas-phase, undergo preferential loss of PR2H. We propose that competing orthometallation of PPh3 is responsible for the surprising stability of the [Ru(η5-indenyl)(PPh3)]+ fragment under these conditions.

AGS Position Statement: Making Medical Treatment Decisions for Unbefriended Older Adults.

In this position statement, we define unbefriended older adults as patients who: (1) lack decisional capacity to provide informed consent to the medical treatment at hand; (2) have not executed an advance directive that addresses the medical treatment at hand and lack capacity to do so; and (3) lack family, friends or a legally authorized surrogate to assist in the medical decision-making process. Given the vulnerable nature of this population, clinicians, health care teams, ethics committees and other stakeholders working with unbefriended older adults must be diligent when formulating treatment decisions on their behalf. The process of arriving at a treatment decision for an unbefriended older adult should be conducted according to standards of procedural fairness and include capacity assessment, a search for potentially unidentified surrogate decision makers (including non-traditional surrogates) and a team-based effort to ascertain the unbefriended older adult's preferences by synthesizing all available evidence. A concerted national effort is needed to help reduce the significant state-to-state variability in legal approaches to unbefriended patients. Proactive efforts are also needed to identify older adults, including "adult orphans," at risk for becoming unbefriended and to develop alternative approaches to medical decision making for unbefriended older adults. This document updates the 1996 AGS position statement on unbefriended older adults.

Enacting a Vision for a Master's Entry Clinical Nurse Leader Program: Rethinking Nursing Education.

The need to educate nurses at the graduate level and provide them with a different skill set that broadens their view of health and nursing is clearly articulated by the American Association of Colleges of Nursing. Consequently, the role of the clinical nurse leader (CNL) was born. Responding to the need for providing a highly educated and credentialed professional at the bedside, Rush University College of Nursing made the bold move to phase out baccalaureate education and enact a prelicensure, master's entry CNL program. Although there is a clear need for this type of graduate, there is little in the literature to provide guidance to institutions that wish to develop this type of program. This paper describes the factors that came into play in making that decision, the process of curriculum development and implementation, the challenges encountered in implementing this type of program, and the outcomes that the program has evidenced since its inception.

Primary Open-Angle Glaucoma Preferred Practice Pattern(®) Guidelines.

UNLABELLED: PRIMARY OPEN-ANGLE GLAUCOMA PREFERRED PRACTICE PATTERN® GUIDELINES: Evidence-based update of the Primary Open-Angle Glaucoma Preferred Practice Pattern® (PPP) guidelines, describing the diagnosis and management of patients with primary open-angle glaucoma with an algorithm for patient management and detailed recommendations for evaluation and treatment options.

Primary Angle Closure Preferred Practice Pattern(®) Guidelines.

UNLABELLED: PRIMARY ANGLE CLOSURE PREFERRED PRACTICE PATTERN® GUIDELINES: Evidence-based update of the Primary Angle Closure Preferred Practice Pattern® (PPP) guidelines, describing the diagnosis and management of patients with primary angle closure with detailed recommendations for evaluation and treatment options.

Primary Open-Angle Glaucoma Suspect Preferred Practice Pattern(®) Guidelines.

UNLABELLED: PRIMARY OPEN-ANGLE GLAUCOMA SUSPECT PREFERRED PRACTICE PATTERN® GUIDELINES: Evidence-based update of the Primary Open-Angle Suspect Glaucoma Preferred Practice Pattern® (PPP) guidelines, describing the diagnosis and management of patients with primary open-angle glaucoma suspect with detailed recommendations for evaluation and treatment options.

Addressing the challenges of nursing student attrition.

With the passage of the Affordable Care Act and as the number of aging and diverse individuals in society increases, access to health care will expand and the need for more competent and diverse nursing graduates will increase. An adequate number of nurse graduates is imperative to meet societal demands; however, this is complicated by high nursing student attrition rates. This article examines the need for more nurses (including those from diverse backgrounds), current attrition rates among schools of nursing, at-risk student characteristics, and previous attempts to increase student success. Applying the evidence to practice, findings from a multipronged approach to increase student success within an associate degree nursing program located within a historically Black college and university in the midwestern United States are discussed. The program's successes and opportunities for improvement are examined, as well as the recommendations for other nursing programs facing issues with student attrition.

The diversity pyramid: an organizational model to structure diversity recruitment and retention in nursing programs.

The literature on increasing the diversity of individuals who enter and practice the nursing profession comes with sound argument, yet we have seen only modest gains in diversification over the past 10 years. This article addresses how to develop a sustainable program to increase the recruitment and retention of underrepresented students. The diversity pyramid is suggested as a conceptual planning model for increasing diversity that is matched to an institution and its resources. The foundation of the pyramid is an organizational commitment to attracting and retaining diverse students. The middle level addresses financial support for underrepresented students. From the top of the pyramid, one chooses appropriate media and relational tactics necessary to attract the underrepresented students a program seeks. All three elements of the pyramid-organizational commitment to diversity, significant financial support, and a targeted use of resources-play important and sequential roles in building a sustainable diversity initiative.

The [2+2] cycloaddition of alkynes at a Ru-P pi-bond.

The Ru[double bond, length as m-dash]P double bond in the 5-coordinate terminal phosphido complex [Ru(eta(5)-indenyl)(PR(2))(PPh(3))] undergoes regioselective [2+2] cycloaddition with simple and activated alkynes to give metallaphosphacyclobutene complexes. These unusual examples of alkyne insertion into a metal-heteroatom bond represent potentially important intermediates in stereoselective routes to new phosphine reagents and ligands.

Silane-controlled diastereoselectivity in the tris(pentafluorophenyl)borane-catalyzed reduction of alpha-diketones to silyl-protected 1,2-Diols.

B(C(6)F(5))(3)-catalyzed bis(hydrosilylation) of alpha-diketones can give high diastereomeric excess of either meso/anti (small silanes and disilane reagents) or dl/syn (bulky silanes) silyl-protected 1,2-diols. This easily tuned diastereoselectivity is rationalized based on the classic Felkin-Anh model applied to a mechanism relying on Si-H abstraction by the electrophilic borane reagent.

Toward selective functionalisation of oligosilanes: borane-catalysed dehydrogenative coupling of silanes with thiols.

Among established methods for transforming Si-H bonds, carbonyl hydrosilylation and heterodehydrogenative coupling with alcohols catalysed by B(C6F5)3 are shown to provide exceptionally clean routes to the derivatisation of tetra-substituted disilanes such as [Ph2SiH]2, giving no products resulting from Si-Si bond cleavage. Even higher activity is observed for the borane-catalysed dehydrogenative coupling of silanes with alkyl- and arylthiols, the first examples of such Si-S bond formation in the absence of a transition metal catalyst. Clean, quantitative syntheses of a range of thiosilanes are reported, and the lability of the Si-S linkage toward subsequent alcoholysis is investigated. The crystal structure of 2,3-disila-2,2,3,3-tetramethyl-1,4-benzodioxane is presented.

Effect of biofeedback on psychological burden and symptoms in older women with urge urinary incontinence.

OBJECTIVES: To determine the effect of biofeedback (BFB) therapy on psychological burden of urge urinary incontinence (UI) and whether prior depression or current depressive symptoms affect older women's response to BFB. DESIGN: Secondary analysis of an ongoing trial. SETTING: Academic medical center. PARTICIPANTS: Forty-two community-dwelling women aged 60 and older with urge UI. INTERVENTION: BFB and behavioral training in urge suppression provided over 8 weeks. MEASUREMENTS: UI frequency on 3-day bladder diary, psychological burden assessed using Urge Impact Scale (URIS-24) total and subscale scores, history of depression, and depressive symptoms on the Mental Component Subscale (MCS) of the Medical Outcomes Study 36-item Short Form Survey (SF-36). Age and chronic conditions were included as covariates. RESULTS: BFB improved UI (by 45%, P=.001) and psychological burden (P=.001 for total URIS-24 score and for all three of its subscales; P=.01 for SF36-MCS). However, although the magnitude of UI improvement was equivalent for those with and without a history of depression, improvement in psychological outcomes was twice as great in those with a history of depression, especially on the perception of control subscale, and improvement was not related to baseline depressive symptoms. CONCLUSION: In older women with urge UI, BFB significantly improves psychological burden, especially in those with a history of depression, in whom psychological burden is linked to change in perception of control. Psychological factors are relevant outcome measures for UI, and these data suggest that focusing on UI frequency alone may have underestimated BFB's efficacy and additional therapeutic benefits.