Synthesis and X-ray crystal structure of a dinuclear platinum hydride complex of tetracyanobiimidazole

Reaction of the diacid form of tetracyanobiimidazole via oxidative addition with two equivalents of Pt(PPh3)4 produces a dinuclear complex whose structure is solved by X-ray analysis. The presence of dihydride is confirmed by observation of IR shift of a deuterium-labelled compound.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/26946/1/0000512.pd

Anisotropic Conductors Based On Tetracyanobiimidazole Complexes Of Iridium.

Mixed valence metal chain compounds based on the monoanion (Ir(CO)\sb 2Tcbiim) \sp- were investigated. (Tcbiim = 4,4\sp\prime,5,5\sp\prime-tetracyano-2,2\sp\prime-biimidazole, a dianion) These compounds were prepared by inert atmosphere electrochemical oxidation with a variety of alkyl ammonium cation based electrolytes. Synthetic details are presented for the preparation of several asymmetric alkyl ammonium cations, and the subsequent electrolyte salt preparation. Technique for electrochemical oxidation is described in detail. Single crystal X-ray Solutions are presented for three complex Ir(I) salts; {\rm NEt\sb 3 Me\lbrack Ir(CO)\sb 2 Tcbiim\rbrack}, {\rm NEt\sb 2 Me\sb 2\lbrack Ir(CO)\sb 2Tcbiim\rbrack,} and a dication salt {\rm NEt\sb 2 Me(CH\sb 2)\sb 4NEt\sb 2 Me\lbrack Ir(CO)\sb 2}Tcbiim) \sb 2. The first of these crystallizes in the space group Pnnm with a = 6.918A, b = 22.223A, c = 15.101A, and Z = 4. A final agreement of R = 4.25% for 133 parameters with 972 retained data was obtained. The second crystallized in the space group P2\sb{1}2\sb{1}2 with a = 7.074A, b = 19.698A, c = 15.336A, and Z = 4. Here, the obtained final agreement was R = 3.94% for 236 parameters with 1505 retained data. The dication structure was refined in the nonstandard space group P22\sb 1 2\sb 1 with a = 15.751A, b = 7.233A, c = 19.135A, and Z = 4. For this compound, a final agreement of R = 5.1% for 130 parameters with 789 retained data was concluded. Solid state packing for this series of compounds is discussed. Packing diagrams reveal molecular interactions responsible for earlier observations of thermochromic behavior. A series of insoluble mixed valence compounds formulated as \lbrack{\rm cat\rbrack\sb 5\lbrack Ir(CO)\sb 2}Tcbiim) \sb 6(an) where (cat) (an) denotes included supporting electrolyte were prepared. Conductivity data are presented. A similar, soluble compound, formulated as \lbrack{\rm cat\rbrack\sb 4\lbrack Ir(CO)\sb 2Tcbiim\rbrack\sb 6} was studied by ESR and UV-VIS during the course of its preparation. A reaction of (cat) \sb 4(Ir(CO)\sb 2Tcbiim) \sb 6 with an isoelectronic analog of the stacking unit, (Pt(CN)\sb 2Tcbiim) \sp{--} produced a unique one dimensional alloy in single crystal form. This compound, (NEt\sb 3Me) \sb 3(Ir(CO)\sb 2Tcbiim) \sb 2(Pt(CN)\sb 2Tcbiim) crystallized in the space group P2\sb 1 with a = 13.412A, b = 6.874A, c = 13.409A, and $\beta$ = 111.21\sp\circ. Since Z = 2, the stacking units are disorderd along the stack. Perspective plots clearly reveal a metal atom chain. Final agreement of R = 4.01% was observed for 223 parameters with 2227 retained data.Ph.D.Inorganic chemistryPure SciencesUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/128058/2/8720294.pd

Massive Open Online Courses (MOOCs) and their impact on academic library services: exploring the issues and challenges

2012 was a year of rapid change for education with the advent of MOOCs—Massive Open Online Courses—available for the world to use to learn for free. But what does this mean for the role of the librarian? How has the landscape in education changed, and what are the issues and challenges that librarians now face? This article reviews the position of libraries in the emergence of MOOCs and the role that a librarian could undertake within the research, production, and presentation of MOOCs

The Effect of Intraoperative Hypothermia on Shoulder Arthroplasty.

Limited evidence is available regarding the correlation between intraoperative hypothermia and perioperative complications in shoulder arthroplasty. The purpose of this study was to determine the incidence of intraoperative hypothermia in patients treated with shoulder arthroplasty and its effect on perioperative complications. A retrospective chart review was performed on 657 consecutive patients who underwent shoulder arthroplasty at a single institution between August 2013 and June 2016. Demographic data, surgery-specific data, postoperative complications, length of stay, and 30-day read-mission were recorded. Patients were classified as hypothermic if their mean intraoperative temperature was less than 36°C. Statistical analyses with univariate and multivariate logistic regression were performed to evaluate the association of intraoperative hypothermia with perioperative complications. The incidence of intraoperative hypothermia in shoulder arthroplasty was 52.7%. Increasing age (P=.002), lower body mass index (P=.006), interscalene anesthetic (P=.004), and lower white blood cell count (P\u3c.001) demonstrated increased association with hypothermia. Longer operating room times and increased estimated blood loss were not found to be associated with intraoperative hypothermia. Hypothermia demonstrated no significant association with surgical site infections nor any other perioperative complications. Patients undergoing shoulder arthroplasty showed a high incidence of intraoperative hypothermia. Lower body mass index, increasing age, interscalene anesthetic, and lower white blood cell count were associated with an increased incidence of hypothermia. Contrary to previous studies, intraoperative hypothermia was not found to contribute to perioperative complications in shoulder arthroplasty. [Orthopedics. 2018; 41(4):e523-e528.]

The Effect of Subscapularis-Specific Rehabilitation Following Total Shoulder Arthroplasty: A Prospective, Double-Blinded, Randomized Controlled Trial

BACKGROUND: Patients undergoing a total shoulder arthroplasty (TSA) through a deltopectoral approach will require repair of the subscapularis tendon. There are no universal postoperative guidelines for rehabilitation of the subscapularis specifically. We hypothesize that the addition of a subscapularis-specific regimen will result in improved subscapularis strength and function. METHODS: Adult patients undergoing anatomic TSA for the treatment of primary glenohumeral osteoarthritis were included. Patients were randomized into either the traditional rehabilitation (TR) control group or the subscapularis rehabilitation (SR) group, which consisted of the traditional therapy along with early and additional subscapularis exercises. Baseline demographics, patient reported outcome measures(PROMs), range of motion (ROM), provocative tests, and subscapularis strength using a handheld dynamometer were measured preoperatively at the initial clinic visit (ICV) as well as 3-months, 6-months, and one-year postoperatively. The primary outcome of interest was a comparison of subscapularis strength between cohorts relative to preoperative baseline, while secondary outcomes were functional, ROM and PROMs. RESULTS: Sixty-six patients were included in final analysis (32 TR vs 34 SR). There were no statistically significant differences between cohorts at the ICV with regards to demographics, baseline subscapularis strength, functional testing, or PROMs. All postoperative time points demonstrated similar subscapularis strength testing between TR and SR groups (p\u3e0.05). Additionally, peak and average subscapularis strength testing at 3, 6, and 12 months postoperatively were similar to baseline ICV testing in both groups. Both groups demonstrated improvements across several provocative tests, ROM and PROM outcome metrics at every postoperative timepoint as compared to baseline ICV values (p\u3c0.05). CONCLUSIONS: Patients undergoing anatomic total shoulder arthroplasty return to baseline internal rotation strength by 3-months postoperatively and demonstrate significant improvements in function, range of motion, and several patient reported outcome measures. The addition of early and focused subscapularis strengthening exercises does not appear to significantly impact any outcomes when compared to traditional rehabilitation programs