HAA by the first {Mn(iii)OH} complex with all O-donor ligands.

There is considerable interest in MnOHx moieties, particularly in the stepwise changes in those O-H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOHx}, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pinF)2- including the first example of a crystallographically characterized mononuclear {Mn(iii)OH} with all O-donors, K2[Mn(OH)(pinF)2], 3. Complex 3 is prepared via deprotonation of K[Mn(OH2)(pinF)2], 1, the pKa of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large ΔEp, assigned to the Mn(iii/ii) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O-H bond in {Mn(ii)-OH2} is estimated to be 67-70 kcal mol-1. Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K2[Mn(OAc)(pinF)2], 2, proposed to result from the oxidation of Et2O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et2O, but addition of O2 at low temperature effects the formation of a new chromophore proposed to be a Mn(iv) species. The related complexes K(18C6)[Mn(iii)(pinF)2], 4, and (Me4N)2[Mn(ii)(pinF)2], 5, have also been prepared and their properties discussed in relation to complexes 1-3.

Novel CRISPR-based sequence specific enrichment methods for target loci and single base mutations.

The programmable sequence specificity of CRISPR has found uses in gene editing and diagnostics. This manuscript describes an additional application of CRISPR through a family of novel DNA enrichment technologies. CAMP (CRISPR Associated Multiplexed PCR) and cCAMP (chimeric CRISPR Associated Multiplexed PCR) utilize the sequence specificity of the Cas9/sgRNA complex to target loci for the ligation of a universal adapter that is used for subsequent amplification. cTRACE (chimeric Targeting Rare Alleles with CRISPR-based Enrichment) also applies this method to use Cas9/sgRNA to target loci for the addition of universal adapters, however it has an additional selection for specific mutations through the use of an allele-specific primer. These three methods can produce multiplex PCR that significantly reduces the optimization required for every target. The methods are also not specific to any downstream analytical platform. We additionally will present a mutation specific enrichment technology that is non-amplification based and leaves the DNA in its native state: TRACE (Targeting Rare Alleles with CRISPR-based Enrichment). TRACE utilizes the Cas9/sgRNA complex to sterically protect the ends of targeted sequences from exonuclease activity which digests both the normal variant as well as any off-target sequences.

Are Polydrug Users More Physically and Verbally Aggressive? An Assessment of Aggression Among Mono- Versus Polydrug Users in a University Sample.

Early research has revealed that patterns of aggression and antisocial behavior are present among polydrug users. Often missing from this discourse is the examination of whether polydrug users are quantitatively different from monodrug users in their use of aggression. Theoretical perspectives are often centered on the psychopharmacological effects of substance use on behavior. Consideration of possible poly- versus monodrug use differences and their impact on aggression has not been investigated. Data from this study were derived from a sample of Midwestern university students (N = 793). The relationship between violence, aggression, and concurrent polydrug use in the last year is assessed with a series of multivariate ordinary least squares (OLS) regression models. Results demonstrate that higher incidents of physical and verbal aggression are reported among polydrug users compared to monodrug users and abstainers. When analyses were broken down by polydrug users (those who engaged in alcohol/marijuana and alcohol/NMUPD [nonmedical use of prescription drugs] stimulants), polydrug users reported higher levels of physical aggression compared to monodrug users. Similarly, monodrug users reported higher levels of physical aggression compared to nonusers. This research extends our understanding of aggression among users from two different subcategories: polydrug users in comparison to those who only engage in one form of substance use. Scholars and practitioners who work with violent offenders should consider patterns of drug use behavior when addressing substance use-related aggression.

A novel CRISPR/Cas9 associated technology for sequence-specific nucleic acid enrichment.

Massively parallel sequencing technologies have made it possible to generate large quantities of sequence data. However, as research-associated information is transferred into clinical practice, cost and throughput constraints generally require sequence-specific targeted analyses. Therefore, sample enrichment methods have been developed to meet the needs of clinical sequencing applications. However, current amplification and hybrid capture enrichment methods are limited in the contiguous length of sequences for which they are able to enrich. PCR based amplification also loses methylation data and other native DNA features. We have developed a novel technology (Negative Enrichment) where we demonstrate targeting long (>10 kb) genomic regions of interest. We use the specificity of CRISPR-Cas9 single guide RNA (Cas9/sgRNA) complexes to define 5' and 3' termini of sequence-specific loci in genomic DNA, targeting 10 to 36 kb regions. The complexes were found to provide protection from exonucleases, by protecting the targeted sequences from degradation, resulting in enriched, double-strand, non-amplified target sequences suitable for next-generation sequencing library preparation or other downstream analyses.

Square-planar Co(iii) in {O4} coordination: large ZFS and reactivity with ROS.

Oxidation of distorted square-planar perfluoropinacolate Co compound [CoII(pinF)2]2-, 1, to [CoIII(pinF)2]1-, 2, is reported. Rigidly square-planar 2 has an intermediate-spin, S = 1, ground state and very large zero-field splitting (ZFS) with D = 67.2 cm-1; |E| = 18.0 cm-1, (E/D = 0.27), g⊥ = 2.10, g‖ = 2.25 and χTIP = 1950 × 10-6 cm3 mol-1. This Co(iii) species, 2, reacts with ROS to oxidise two (pinF)2- ligands to form tetrahedral [CoII(Hpfa)4]2-, 3.

Race and General Strain Theory: Examining the Impact of Racial Discrimination and Fear on Adolescent Marijuana and Alcohol Use.

BACKGROUND: To extend our knowledge of general strain theory by exploring how under-researched strains such as racial discrimination, witnessing violence, physical victimization and verbal bullying affect adolescent substance use while considering differences according to racial identification. METHODS: This research utilized data from wave three of the Project on Human Development in Chicago Neighborhoods. Statistical analysis was primarily composed of path analysis using full information maximum likelihood parameter estimates. RESULTS: The findings reveal that reporting fear decreased alcohol and marijuana use among adolescents and that racial discrimination, witnessing violence, and being the victim of verbal bullying indirectly affected marijuana and alcohol use through fear. No support was found for depression as a mediating variable. Physical victimization was the only social strain that had a direct positive effect on marijuana and alcohol use but only for Hispanics and African Americans. CONCLUSIONS: The results suggest that strains may be operating differently and there may be differential levels of exposure to certain strains according to one's race.

Nonmedical use of prescription drugs in emerging adulthood: differentiating sex from gender.

Male-female variations in health-behavior continue to be of national and international significance with men generally being more likely to be engaged in behaviors that enhance risk across an array of preventable diseases and injuries as well as premature deaths. The literature has identified non-medical use of prescription drugs (NMUPD) as a developing and particularly dangerous substance use behavior among college students. The literature has reported sex differences (male; female) in NMUPD but has yet to explain how gender-orientation (e.g., masculine, feminine) might impact NMUPD. The purpose of this study is to address this gap by examining the influence of gender-orientation on NMUPD. Using survey data collected during the 2013-2014 academic year from a convenience sample of college students at a mid-sized Midwestern university, we examine the association of gender-orientation with NMUPD (N=796). To do this, we separate masculine and feminine scales from the BEM Sex Role Inventory and use logistic regression to test whether masculine or feminine gender characteristics influence the likelihood of NMUPD (lifetime measure of any use and by category). This analysis shows that self-identified characteristics associated with masculinity increase the odds of NMUPD while femininity is associated with lower odds of NMUPD. Findings from this study increase our knowledge of gender-orientation and sex interactions as factors that might influence NMUPD thus demonstrating the importance of differentiating sex from gender-orientation.

Do telephone call interruptions have an impact on radiology resident diagnostic accuracy?

RATIONALE AND OBJECTIVES: The purpose of this study was to measure the effect of distractions, in the form of telephone call interruptions, on radiology resident diagnostic accuracy. MATERIALS AND METHODS: Radiology resident discrepancy reports and reading room telephone logs at an academic tertiary care pediatric hospital were collected over a 13-month period. Phone call times and durations were recorded. Major discrepancy shifts (defined as a call shift where at least one major discrepancy was discovered the following morning by the attending radiologist between the resident preliminary and attending final reports), and dictation time stamps for each discrepant preliminary dictation were also recorded. Telephone call volume and preliminary report time stamps were compared between "discrepancy shifts" and "no discrepancy shifts." RESULTS: Each call shift spanned 14 hours, during which one radiology resident was responsible for the generation of preliminary interpretations. Review of the discrepancy log data revealed 51 major discrepancies in 41 shifts, of which 39 discrepancies had documented error details and resident preliminary report time stamps. The average number of telephone calls for the "discrepancy shifts" was slightly greater than the "no discrepancy shifts" (48.59 vs. 44.02) but was not statistically significant (P = .0575). However, there was a statistically significant increase in the average number of phone calls in the 1 hour preceding the generation of a discrepant preliminary report versus the "no discrepancy shifts" (4.23 vs. 3.24 calls, P = .027). One additional phone call during the hour preceding the generation of a discrepant preliminary report resulted in a 12% increased likelihood of a resident error (P = .017). CONCLUSIONS: Distractions in the form of telephone call interruptions may negatively impact on-call radiology resident diagnostic accuracy. Efforts should be made to limit distractions in the reading room.

National dissemination of interpersonal psychotherapy for depression in veterans: therapist and patient-level outcomes.

OBJECTIVE: To evaluate the effects of training in and delivery of interpersonal psychotherapy (IPT) for depression throughout the U.S. Department of Veterans Affairs health care system on therapists' competency and patients' clinical outcomes. METHOD: Participants included 124 therapists and 241 veteran patients. Therapists participated in a 3-day workshop followed by 6 months of weekly group consultation. Therapy session tapes were rated by expert IPT training consultants using a standardized competency rating form. Patient outcomes were assessed with the Beck Depression Inventory-II and the World Health Organization Quality of Life-BREF. Therapeutic alliance was assessed with the Working Alliance Inventory-Short Revised. RESULTS: Of the 124 therapists receiving IPT training, 115 (93%) completed all training requirements. Therapist competence in IPT increased from their 1st patient to their 2nd for both initial (d = 0.36) and intermediate (d = 0.24) treatment phases. Of the 241 veteran patients treated with IPT, 167 (69%) completed ≥ 12 sessions. Intent-to-treat analyses indicated large overall reductions in depression (d = 1.26) and significant improvements in quality of life (d = 0.57 to 0.86) and the therapeutic alliance (d = 0.50 to 0.83). CONCLUSIONS: National IPT training in the VA health care system was associated with significant increases in therapist competencies to deliver IPT, as well as large overall reductions in depression and improvements in quality of life among veterans, many of whom presented with high levels of depression. RESULTS support the feasibility and effectiveness of broad dissemination of IPT in routine clinical settings.

Nonmedical prescription drug use among US college students at a Midwest university: a partial test of social learning theory.

We estimate the prevalence of nonmedical prescription drug (NMPD) use and test social learning theory as an explanation for NMPD use based upon data from a large pilot study. Data were collected from 465 college students at a Midwestern university in the USA using a self-administered questionnaire. The sample was predominantly white (88%), 43% were female and the mean age was 22. Most participants (80%) were not members of social fraternities or sororities. A majority of students did not report NMPD use: 39.4% of respondents reported lifetime NMPD use, 31% reported past-year use, and 14.4% reported past-month use. Multivariate regression results partially supported social learning theory as an explanation for lifetime NMPD use. Limitations and suggestions for future research are suggested.

At the intersection of interpersonal violence, masculinity, and alcohol use: the experiences of heterosexual male perpetrators of intimate partner violence.

This article examines the relationship between violence, masculinity, and alcohol use among heterosexual, economically disadvantaged, and primarily Black men officially identified as batterers. Violence occurred against intimates and strangers. Alcohol use coupled with violence against intimates and violence against others (e.g., strangers) appeared to be used for masculinity construction. The use of alcohol before and during assaultive behavior combined with the use of violence symbolized dominance and control. This occurred in situations where markers of masculinity were largely absent (e.g., steady employment) in instances of both intimate partner violence and stranger violence.

On drinking styles and race: a consideration of the socio-structural determinants of alcohol use behavior.

Often missing from the discourse on alcohol use is that "alcohol-related problems among college students" appears to be a euphemism for "white college men" in that students who experience alcohol-related problems disproportionately tend to be white men. An important aspect of promoting social and behavioral change is to understand race-related mechanisms that structure desire for students to engage in alcohol use. This article presents findings based on undergraduate students attending a Midwest university. The current study contributes to the theoretical literature on alcohol use and race. We use logistic regression models which suggest race and attitudes pertaining to race relations matter in predicting non-binge drinking and abstinence behavior.

Synthetic, structural, and theoretical investigation of guanidinate complexes containing planar Cu(6) cores.

The addition of diethylcyanamide to a tetrahydrofuran solution of lithium dialkylamide LiN(CH(3))(2) or Li NCH(2)CH(2)CH(2) CH(2), Li(PYR), results in the corresponding lithium 1,1,3,3-tetraalkylguanidinate, Li(TAG). The subsequent metathesis reaction of Li(TAG) with CuCl generates hexanuclear copper(I) complexes with the general formula [Cu(mu-TAG)](6), where TAG = DEDMG (1) and DEPYRG (2).

Synthesis and characterization of group 11 1,1,3,3-tetraalkylguanidinate (TAG) clusters: [M2(mu-TAG){mu-N(SiMe3)2}]2 (M = Cu, Ag, and Au).

The addition of diethylcyanamide to a tetrahydrofuran solution of lithium dialkylamide {LiN(CH(3))(2) or LiN[upper bond 1 start]CH(2)CH(2)C[upper bond 1 end]H(2) CH(2), Li(PYR)} results in the corresponding lithium 1,1,3,3-tetraalkylguanidinate, Li(TAG). Two equivalents of Li(TAG) and 2 equiv of lithium bistrimethylsilylamide, LiN(SiMe(3))(2), were subsequently reacted with 4 equiv of Group 11 halide (CuCl, AgBr, and AuCl) to generate tetranuclear complexes with the general formula [M(2)(mu-TAG){mu-N(SiMe(3))(2)}](2) where M and TAG = {Cu, DEDMG, (1)}, {Ag, DEDMG, (2)}, {Au, DEDMG, (3)}, {Cu, DEPYRG, (4)}, {Ag, DEPYRG, (5)}, and {Au, DEPYRG, (6)}. Compounds 1-6 were characterized by single-crystal X-ray diffraction. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, (1)H and (13)C NMR studies.

Effect of finger tracking combined with electrical stimulation on brain reorganization and hand function in subjects with stroke.

Synergism of rehabilitative interventions could maximize recovery following stroke. We examined whether the combination of peripherally initiated electrical stimulation of finger extensors and centrally operating finger tracking training could accentuate brain reorganization and its relationship to recovery, beyond the effects of either treatment alone. Twenty subjects with stroke were randomly assigned to an electrical stimulation (ES), tracking training (TR) or combination (CM) group. Each group was trained for ten 1-h sessions over 2-3 weeks. Pretest and posttest measurements consisted of the Box and Block and Jebsen Taylor tests of manual dexterity and a finger tracking test that was performed during functional magnetic resonance imaging (fMRI). fMRI variables included laterality index and BOLD signal intensity of primary motor (M1), primary sensory (S1), sensorimotor (SMC) and premotor (PMC) cortices as well as, supplementary motor area (SMA). ES and CM groups improved on dexterity, whereas the TR group did not. Improvement in the CM group was not greater than the other two groups. Subjects who had an intact M1 showed greater functional improvement than those who had direct involvement of M1. fMRI analysis did not yield significant changes from pretest to posttest. In the CM group only, functional improvement was positively correlated with laterality index change in M1, S1, SMC and PMC, indicating greater ipsilesional control and was negatively correlated with BOLD Signal Intensity change in ipsilesional S1 and SMA, indicating neurophysiological trimming of irrelevant neurons. The correlational results suggest that the combined intervention may be more influential on brain reorganization than either treatment alone but a larger sample size, longer duration of training, or a restricted inclusion of stroke location and volume may be needed to demonstrate a difference in efficacy for producing behavioral changes.

What is the problem? The challenge of providing effective teachers for all children.

Richard Murnane and Jennifer Steele argue that if the United States is to equip its young people with the skills essential in the new economy, high-quality teachers are more important than ever. In recent years, the demand for effective teachers has increased as enrollments have risen, class sizes have fallen, and a large share of the teacher workforce has begun to retire. Women and minorities have more career options than ever before, making it increasingly difficult to attract and retain the many effective teachers who are needed. Moreover, schools are limited in their ability to identify and reward the most effective teachers. Perhaps the most urgent problem facing American education, say Murnane and Steele, is the unequal distribution of high-quality teachers. Poor children and children of color are disproportionately assigned to teachers with the least preparation and the weakest academic backgrounds. Teacher turnover is high in schools that serve large shares of poor or nonwhite students because the work is difficult, and the teachers who undertake it are often the least equipped to succeed. Murnane and Steele point out that in response to these challenges, policymakers have proposed a variety of policy instruments to increase the supply of effective teachers and distribute those teachers more equitably across schools. Such proposals include across-the-board pay increases, more flexible pay structures such as pay-for-performance, and reduced restrictions on who is allowed to teach. Several of these proposals are already being implemented, but their effectiveness remains largely unknown. To measure how well these policies attract effective teachers to the profession and to the schools that need them most, rigorous evaluations are essential. Murnane and Steele also note that policymakers may benefit from looking beyond U.S. borders to understand how teacher labor markets work in other countries. Although policies rooted in one nation's culture cannot be easily and quickly transplanted into another, it is important to understand what challenges other countries face, what policies they are using, and how well those policies are working to enhance teacher quality and improve student achievement.

Primary motor area activation during precision-demanding versus simple finger movement.

The authors used functional magnetic resonance imaging to explore whether the primary motor area (M1) serves a processing role in a finger-movement tracking task, emphasizing attention to accuracy, beyond its execution role of simple movements, with no attention to accuracy. Twenty healthy subjects performed alternating conditions: Rest, involving no finger movement; Track, involving careful control of a cursor along a target pathway with finger extension/flexion movements; and Move, involving finger extension/flexion movements without careful control. The authors compared volume of activated voxels in the M1, blood-oxygen-level-dependent (BOLD) signal intensity of activated voxels in the M1, and BOLD signal intensity of all voxels in the M1 between the Track and Move conditions. The results showed greater volume and signal intensity in both the contralateral and ipsilateral M1 during Track than during Move. Overall, the results suggest that the M1 is engaged not only in the execution of movements but also in spatial and temporal processing to produce accurately controlled movements. These findings invite further work exploring whether precision-demanding movements, such as tracking, form a more potent stimulus for promoting helpful brain reorganization in the M1 during the recovery from stroke than simple repetitive movements.