A Complete Triad of Zero-Valent 17-Electron Monoradicals of Group 7 Elements Stabilized by m-Terphenyl Isocyanides.

The first consistent series of mononuclear 17-electron complexes of three Group 7 elements has been isolated in crystalline form and studied by X-ray diffraction and spectroscopic methods. The paramagnetic compounds have a composition of [M0 (CO)(CNp-F-ArDArF2 )4 ] (M=Mn, Tc, Re; ArDArF2 =2,6-(3,5-(CF3 )2 C6 H3 )2 C6 H2 F) and are stabilized by four sterically encumbering isocyanides, which prevent the metalloradicals from dimerization. They have a square pyramidal structure with the carbonyl ligands as apexes. The frozen-solution EPR spectra of the rhenium and technetium compounds are clearly anisotropic with large 99 Tc and 185,187 Re hyperfine interactions for one component. High-field EPR (Q band and W band) has been applied for the elucidation of the EPR parameters of the manganese(0) complex.

Intermolecular 2+2 imine-olefin photocycloadditions enabled by Cu(I)-alkene MLCT.

2 + 2 Photocycloadditions are idealized, convergent construction approaches of 4-membered heterocyclic rings, including azetidines. However, methods of direct excitation are limited by the unfavorable photophysical properties of imines and electronically unbiased alkenes. Here, we report copper-catalyzed photocycloadditions of non-conjugated imines and alkenes to produce a variety of substituted azetidines. Design principles allow this base metal-catalyzed method to achieve 2 + 2 imine-olefin photocycloaddition via selective alkene activation through a coordination-MLCT pathway supported by combined experimental and computational mechanistic studies.

Investigation of Immobilization Effects on Ni(P2N2)2 Electrocatalysts.

A new synthetic route to complexes of the type Ni(P2N2)22+ with highly functionalized phosphine substituents and the investigation of immobilization effects on these catalysts is reported. Ni(P2N2)22+ complexes have been extensively studied as homogeneous and surface-attached molecular electrocatalysts for the hydrogen evolution reaction (HER). A synthesis based on postsynthetic modification of PArBr2NPh2 was developed and is described here. Phosphonate-modified ligands and their corresponding nickel complexes were isolated and characterized. Subsequent deprotection of the phosphonic ester derivatives provided the first Ni(P2N2)22+ catalyst that can be covalently attached via pendent phosphonate groups to an electrode without involvement of the important pendent amine groups. Mesoporous TiO2 electrodes were surface modified by attachment of the new phosphonate functionalized Ni(P2N2)22+ complexes, and these provided electrocatalytic materials that proved to be competent and stable for sustained HER in aqueous solution at mild pH and low overpotential. We directly compared the new ligand to a previously reported complex that utilized the amine moiety for surface attachment. Using HER as the benchmark reaction, the P-attached catalyst showed a marginally (9-14%) higher turnover number than its N-attached counterpart.

A closed-shell monomeric rhenium(1-) anion provided by m-terphenyl isocyanide ligation.

The mixed isocyanide/carbonyl complexes cis- and trans-[Re(CO)3Br(CNArDipp2)2] (ArDipp2 = 2,6-(2,6-(i-Pr)2C6H3)2C6H3) can be synthesized from reactions of [Re(CO)5Br] and CNArDipp2 depending on the conditions applied. Reduction of the neutral Re(i) species gives the monoanionic complex [Re(CO)3(CNArDipp2)2]- or the neutral [Re(CO)3(CNArDipp2)2], which contain rhenium in the formal oxidation states "-1" and "0", respectively.

Dianionic Mononuclear Cyclo-P4 Complexes of Zero-Valent Molybdenum: Coordination of the Cyclo-P4 Dianion in the Absence of Intramolecular Charge Transfer.

Relative to other cyclic poly-phosphorus species (that is, cyclo-Pn ), the planar cyclo-P4 group is unique in its requirement of two additional electrons to achieve aromaticity. These electrons are supplied from one or more metal centers. However, the degree of charge transfer is dependent on the nature of the metal fragment. Unique examples of dianionic mononuclear η4 -P4 complexes are presented that can be viewed as the simple coordination of the [cyclo-P4 ]2- dianion to a neutral metal fragment. Treatment of the neutral, molybdenum cyclo-P4 complexes Mo(η4 -P4 )I2 (CO)(CNArDipp2 )2 and Mo(η4 -P4 )(CO)2 (CNArDipp2 )2 with KC8 produces the dianionic, three-legged piano stool complexes, [Mo(η4 -P4 )(CO)(CNArDipp2 )2 ]2- and [Mo(η4 -P4 )(CO)2 (CNArDipp2 )]2- , respectively. Structural, spectroscopic, and computational studies reveal a similarity to the classic η6 -benzene complex (η6 -C6 H6 )Mo(CO)3 regarding the metal-center valence state and electronic population of the planar-cyclic ligand π system.

Report of the 2017-2018 Student Affairs Standing Committee.

The 2017-2018 American Association of Colleges of Pharmacy (AACP) Student Affairs Standing Committee addressed charges related to student wellness and resilience and identified ways where AACP can assist member organizations to build positive wellbeing in students. The Committee report provides nine recommendations to AACP, three suggestions for colleges and schools of pharmacy, and one proposed policy statement related to student wellness and resilience. The report focuses on themes of consequences of burnout and declining resilience, culture shift around wellness, creating community around times of grief, partnerships with member organizations to create campus cultures that promote overall wellbeing and strategies to help students to manage stress in healthy ways. Committee members challenge AACP, and other professional organizations, to include the student voice when future programs and strategies are developed. Finally, this report provides future recommendations for the Student Affairs Standing Committee.

Oxidative-Insertion Reactivity Across a Geometrically Constrained Metal→Borane Interaction.

While interest in cooperative reactivity of transition metals and Lewis acids is receiving significant attention, the scope of known reactions that directly exploit the polarized reverse-dative σ-bond of metal-borane complexes (i.e., M→BR3 ) remains limited. Described herein is that the platinum (boryl)iminomethane (BIM) complex [Pt(κ2 -N,B-Cy2 BIM)(CNArDipp2 )] can effect the oxidative insertion of a range of unsaturated organic substrates, including azides, isocyantes, and nitriles, as well as CO2 and elemental sulfur (S8 ). In addition, alkyl migration processes available to the BIM framework allow for post-insertion reaction sequences resulting in product release from the metal center.

A 10-year Study of the Academic Progress of Students Identified as Low Performers after Their First Semester of Pharmacy School.

Objective. To examine whether pharmacy students characterized as low performers at the conclusion of their first semester remained low performers throughout their academic career. Methods. Bottom quartile performance on first semester grade point average (GPA) was compared to licensing examination success, cumulative grade point average at the end of the didactic education and whether the student graduated on time, using cross tabulation analysis. Relative risk ratios and confidence intervals were calculated. Results. Students in the bottom quartile for GPA at the end of their first semester in pharmacy school were approximately six times more likely not to graduate on time, not to pass the North American Pharmacist Licensure Exam on their first attempt and to remain in the bottom quartile for GPA at the end of their didactic education. Conclusion. This study suggests that pharmacy students who score in the bottom quartile for GPA at the end of their first semester are more likely to underperform academically unless they take corrective action.

Structural Properties of the Acidification Products of Scandium Hydroxy Chloride Hydrate.

The structural properties of a series of scandium inorganic acid derivatives were determined. The reaction of Sc(0) with concentrated aqueous hydrochloric acid led to the isolation of [(H2O)5Sc(µ-OH)]24Cl·2H2O (1). Compound 1 was modified with a series of inorganic acids (i.e., HNO3, H3PO4, and H2SO4) at room temperature and found to form {[(H2O)4Sc(κ(2)-NO3)(µ-OH)]NO3}2 (2a), [(H2O)4Sc(κ(2)-NO3)2]NO3·H2O (2b) (at reflux temperatures), {6[H][Sc(µ-PO4)(PO4)]6}n (3), and [H][Sc(µ3-SO4)2]·2H2O (4a). Additional organosulfonic acid derivatives were investigated, including tosylic acid (H-OTs) to yield {[(H2O)4Sc(OTs)2]OTs}·2H2O (4b) in H2O and [(DMSO)3Sc(OTs)3] (4c) in dimethyl sulfoxide and triflic acid (H-OTf) to form [Sc(H2O)8]OTf3 (4d). Other organic acid modifications of 1 were also investigated, and the final structures were determined to be {([(H2O)2Sc(µ-OAc)2]Cl)6}n (5) from acetic acid (H-OAc) and [Sc(µ-TFA)3Sc(µ-TFA)3]n (6) from trifluoroacetic acid (H-TFA). In addition to single-crystal X-ray structures, the compounds were identified by solid-state and solution-state (45)Sc nuclear magnetic resonance spectroscopic studies.

Evaluating the Effects of Flexible Learning about Aseptic Compounding on First-year Students in a Pharmacy Skills Laboratory.

OBJECTIVE: To evaluate how flexible learning via online video review affects the ability and confidence of first-year (P1) pharmacy students to accurately compound aseptic preparations. DESIGN: Customary instructions and assignments for aseptic compounding were provided to students, who were given unlimited access to 5 short review videos in addition to customary instruction. Student self-confidence was assessed online, and faculty members evaluated students' aseptic technique at the conclusion of the semester. ASSESSMENT: No significant difference on final assessment scores was observed between those who viewed videos and those who did not. Student self-confidence scores increased significantly from baseline, but were not significantly higher for those who viewed videos than for those who did not. CONCLUSION: First-year students performed well on final aseptic compounding assessments, and those who viewed videos had a slight advantage. Student self-confidence improved over the semester regardless of whether or not students accessed review videos.

Tasimelteon: a melatonin receptor agonist for non-24-hour sleep-wake disorder.

OBJECTIVE: To examine the efficacy of tasimelteon for the treatment of non-24-hour sleep-wake disorder using evidence from controlled clinical trials. DATA SOURCES: Citations in Google Scholar and PubMed from January 1, 2008, to May 31, 2014, were identified using tasimelteon as the search term. STUDY SELECTION AND DATA EXTRACTION: Results were limited to human trials published in English. Trials that compared tasimelteon with placebo were included. DATA SYNTHESIS: A phase II trial (n = 39) evaluated the effects of tasimelteon versus placebo on improvements in sleep efficiency and the ability to shift circadian rhythms over 3 days. Significant shifts in circadian rhythm were only observed for 100-mg tasimelteon. A phase III trial (n = 412) evaluated the effects of tasimelteon versus placebo on assessment of latency to persistent sleep and wake after sleep onset; significant advantages were observed in tasimelteon recipients. The SET (Safety and Efficacy of Tasimelteon) trial (n = 84) enrolled blind men and women with Non-24. They received placebo or tasimelteon 20 mg daily. Tasimelteon recipients had significantly (P = 0.0025) better entrainment and N24CRS scores. The RESET (Randomized Withdrawal Study of the Efficacy and Safety of Tasimelteon) trial (n = 20) enrolled entrained participants from the SET trial who received 20 mg of tasimelteon or placebo daily for 8 weeks. The primary objective was to evaluate the maintenance of effect of tasimelteon to entrain circadian rhythms. Tasimelteon was associated with significantly (P = 0.0055) greater entrainment than placebo. CONCLUSION: Tasimelteon improves sleep initiation and maintenance in patients with Non-24 who have a shift in endogenous circadian rhythms. However, the cost of this agent limits its use.

Suvorexant, a dual orexin receptor antagonist for the management of insomnia.

Suvorexant, a dual orexin receptor antagonist for the management of insomnia.

Pharmacy students' attitudes about treating patients with alcohol addiction after attending a required mutual support group.

OBJECTIVE: To implement required attendance at mutual support groups for addiction recovery as a pharmacy skills laboratory exercise, and to evaluate how attendance affected pharmacy students' attitudes about caring for patients with addiction. DESIGN: Third-year (P3) pharmacy students enrolled in a Pharmacy Skills Laboratory course were required to watch an introductory video about Alcoholics Anonymous (AA) and then attend 2 "open meetings" during the semester. Students submitted a written reflection as proof of attendance. ASSESSMENT: Pharmacy students who agreed to participate in the study completed the Short Alcohol and Alcohol Problems Perception Questionnaire (SAAPPQ) during the course orientation and again at the end of the semester. Mutual support group attendance significantly affected the students' attitudes within the domains of role adequacy, task specific self-esteem, and work satisfaction. Significant changes were not observed within the domains of motivation and role legitimacy. CONCLUSION: Mutual support group attendance exposed pharmacy students to the negative effects of alcohol abuse and increased their self-confidence to provide care to patients with alcohol addiction.

Application of opioid analgesia concepts in a third-year pharmacy student skills laboratory on three campuses.

The objective of this study was to evaluate the effects of a skills laboratory exercise focused on principles of opioid analgesia on the knowledge, attitudes, and self-perceived skills of third-year (P3) pharmacy students on three campuses of the University of Georgia College of Pharmacy. The study evaluated the effects of a 2-hour skills laboratory exercise focused on technical aspects of opioid analgesia and included three stations: programming a pump to deliver a fentanyl drip/Richmond Agitation Sedation Scale (RAAS) scoring, using an equianalgesic dosing table, and compounding a patient-controlled analgesia syringe. A 12-item, online survey was distributed 2 weeks prior (pre-intervention) to the analgesia skills laboratory. A 2-hour laboratory was delivered on each campus and the survey was administered again (post-intervention) at the conclusion of the laboratory. One hundred and thirty-five students (93%) completed the pre- and post-intervention surveys. Significant changes (P < .05) between pre- and post-intervention scores were observed in two of five (40%) of the knowledge, all four (100%) of the self-perceived skills, and all three (100%) of the attitude items. Intercampus differences between pre- and post-intervention scores were minor. The authors concluded that skills laboratory exercises can effectively change the attitudes and self-perceived skill level of P3 pharmacy students and reinforce previously acquired knowledge.

Nepafenac: an ophthalmic nonsteroidal antiinflammatory drug for pain after cataract surgery.

OBJECTIVE: To examine the efficacy of nepafenac in the treatment of pain and inflammation in patients after cataract surgery using evidence from controlled clinical studies. DATA SOURCES: Citations in Google Scholar, PubMed, and Web of Science from January 1, 2005, to March 25, 2013, were identified using nepafenac and cataract as search terms. STUDY SELECTION AND DATA EXTRACTION: The literature search was limited to human studies published in English. Three trials that compared nepafenac with other nonsteroidal antiinflammatory drugs (NSAIDs) were included. DATA SYNTHESIS: The pharmacokinetics and pharmacodynamics of nepafenac 0.1% suspension (and its active metabolite, amfenac) were compared with bromfenac 0.09% solution and ketorolac 0.4% solution with respect to aqueous humor concentrations and ability to reduce cyclooxygenase 1 and 2 (COX-1 and COX-2) enzymes. The maximum concentration (C(max)) values of ketorolac and amfenac were statistically similar, while the C(max) of bromfenac was significantly lower than that of amfenac. Ketorolac most effectively inhibited COX-1 enzymes; COX-2 enzymes were most effectively reduced by amfenac. When nepafenac 0.1% suspension was compared with placebo and ketorolac 0.5% solution, nepafenac achieved a higher percentage cure rate than placebo at day 14 (p = 0.0241). Significant differences in cure rates between nepafenac and ketorolac were not observed. Nepafenac 0.1%, bromfenac 0.09%, and ketorolac 0.45% were compared to determine which most effectively reduced prostaglandin E2 (PGE2) following surgery. PGE2 concentrations were significantly lowest in the ketorolac group, followed by the bromfenac and nepafenac groups, respectively. Topical nepafenac 0.1% suspension was approved in 2005. A 0.3% suspension was approved in October 2012. The 0.3% product may have some advantages over its predecessor: it is dosed once rather than thrice daily, which may increase patient adherence and improve outcomes. The price and dosing frequency of the 0.3% product are comparable to those of bromfenac 0.09% solution. CONCLUSIONS: The 2 nepafenac products appear to be equally efficacious, with a slightly increased adverse event rate in patients using the 0.3% versus 0.1% formulation. Head-to-head clinical trials that compare the 0.3% product with the 0.1% product or other commercially available NSAIDs are unavailable.

Perceptions of pharmacy students, faculty members, and administrators on the use of technology in the classroom.

OBJECTIVES: To gather and evaluate the perceptions of students, faculty members, and administrators regarding the frequency and appropriateness of classroom technology use. METHODS: Third-year pharmacy students and faculty members at 6 colleges and schools of pharmacy were surveyed to assess their perceptions about the type, frequency, and appropriateness of using technology in the classroom. Upper-level administrators and information technology professionals were also interviewed to ascertain overall technology goals and identify criteria used to adopt new classroom technologies. RESULTS: Four hundred sixty-six students, 124 faculty members, and 12 administrators participated in the survey. The most frequently used and valued types of classroom technology were course management systems, audience response systems, and lecture capture. Faculty members and students agreed that faculty members appropriately used course management systems and audience response systems. Compared with their counterparts, tech-savvy, and male students reported significantly greater preference for increased use of classroom technology. Eighty-six percent of faculty members reported having changed their teaching methodologies to meet student needs, and 91% of the students agreed that the use of technology met their needs. CONCLUSIONS: Pharmacy colleges and schools use a variety of technologies in their teaching methods, which have evolved to meet the needs of the current generation of students. Students are satisfied with the appropriateness of technology, but many exhibit preferences for even greater use of technology in the classroom.

Tafluprost: the first preservative-free prostaglandin to treat open-angle glaucoma and ocular hypertension.

OBJECTIVE: To review the pharmacology, pharmacokinetics, clinical trial data, efficacy data, and adverse effect incidence of tafluprost. DATA SOURCES: A literature search was completed using PubMed, Web of Science, and Google Scholar. Tafluprost was the primary search term. Articles published between January 2008 and April 2012 were included in this review. Additional limits placed on the searches were "human" and "English." Citations in which tafluprost appeared in the title were 36, 29, and more than 300 in PubMed, Web of Science, and Google Scholar, respectively. STUDY SELECTION AND DATA EXTRACTION: Three clinical trials were included in this review. One trial enrolled more than 500 subjects in a randomized fashion. Another also enrolled more than 500 subjects, although the study design was not randomized. The third trial evaluated the effects of tafluprost on subjects who had recently discontinued use of latanoprost, another prostaglandin that is approved to treat glaucoma and ocular hypertension. The duration of all 3 trials was 12 weeks. DATA SYNTHESIS: Tafluprost 0.0015% is the first topical prostaglandin approved by the Food and Drug Administration for treatment of open-angle glaucoma and ocular hypertension that does not contain the widely used preservative, benzalkonium chloride (BAK). Although some controversy surrounds the long-term safety of exposure to BAK, clinical trial data are inconclusive. Tafluprost, like other prostaglandin analogues, exerts its effects on prostaglandin F receptors to reduce intraocular pressure (IOP). Results from 1 trial demonstrated significant reductions in IOP when monotherapy was switched to tafluprost monotherapy. Reductions in IOP with tafluprost use were compared with those seen with use of timolol and latanoprost in 2 trials, and noninferiority was observed. Significant reductions in tear osmolarity were noted in subjects who changed from latanoprost, another prostaglandin analogue, to tafluprost therapy. Conjunctival hyperemia is the most common adverse effect seen in patients receiving drugs from this class. Many have also reported stinging, ocular pruritus, increased darkening or growth of eyelashes, and darkening of eyelids, as well as irreversible brown pigmentation of the iris. CONCLUSIONS: Clinical trial data suggest that tafluprost is as efficacious as other agents used in the management of ocular hypertension and glaucoma. Its use may be especially advantageous in people with allergies, sensitivities to preservatives, or dry or sensitive eyes.

Inaccuracy in Legionella tests of building water systems due to sample holding time.

Most Legionella culture tests are performed on building water samples that have been shipped to analytical laboratories for analysis. Significant (≥ 1 log10 unit) changes in results were observed in 52% of held samples (6 h or longer, ambient temperature) drawn from building water systems in a 42-sample initial survey. It was not practical to use the spread plate protocol for on-site "t = 0" cultures in a larger, more diverse survey of thousands of building water systems. Two thousand four hundred twenty-one (2421) building water samples were split for on-site analysis using a field culture protocol and then also cultured after overnight shipment to the lab for analysis with the standardized spread plate method. Legionella test results from building water system samples are usually interpreted as ≥ a numerical detection or action limit. Therefore, binary statistical analyses were calculated by setting t = 0 culture results to "true". Overall in this survey, 10.4% of water samples sent to the laboratory for analysis returned either false-positive or false-negative results. The overall positive predictive value of results was poor (36%). Most (83%) false-positive results were returned from utility water systems. Most (74%) false-negative results were returned from potable water systems. These inaccuracies have serious implications in regard to interpretation and use of Legionella test results. The overall negative predictive value of results was excellent (99%) and also it was good (92%) for results from a polymerase chain reaction (PCR) assay that can be therefore used as a negative screening method.