Cyclic voltammetry and chronoamperometry: mechanistic tools for organic electrosynthesis.

Electrochemical methods offer unique advantages for chemical synthesis, as the reaction selectivity may be controlled by tuning the applied potential or current. Similarly, measuring the current or potential during the reaction can provide valuable mechanistic insights into these reactions. The aim of this tutorial review is to explain the use of cyclic voltammetry and chronoamperometry to interrogate reaction mechanisms, optimize electrochemical reactions, or design new reactions. Fundamental principles of cyclic voltammetry and chronoamperometry experiments are presented together with the application of these techniques to probe (electro)chemical reactions. Several diagnostic criteria are noted for the use of cyclic voltammetry and chronoamperometry to analyze coupled electrochemical-chemical (EC) reactions, and a series of individual mechanistic studies are presented. Steady state voltammetric and amperometric measurements, using microelectrodes (ME) or rotating disk electrodes (RDE) provide a means to analyze concentrations of redox active species in bulk solution and offer a versatile strategy to conduct kinetic analysis or determine the species present during (electro)synthetic chemical reactions.

Differential Associations between Guilt and Shame Proneness and Religious Coping Styles in a Diverse Sample of Young Adults.

Positive religious coping is linked with better mental health outcomes following physical and sexual abuse while negative religious coping is associated with poorer outcomes. Religious coping styles may be linked with dispositional tendencies to experience guilt or shame. This study compared the associations between guilt and shame proneness and religious coping styles and tested whether abuse history moderated these relationships. We conducted a cross-sectional study with 425 college students (n = 145 with physical and/or sexual abuse history, n = 280 with no abuse history). Participants completed questionnaires assessing positive and negative religious coping style, as well as two dimensions of guilt proneness and shame proneness. Structural equation models were fitted to examine associations between guilt proneness and shame proneness, and positive and negative religious coping, respectively, accounting for abuse history as a binary moderator. Across the full sample, positive religious coping was positively associated with guilt repair (i.e., the tendency to engage in reparative behaviors following one's wrongdoing), guilt negative behavior evaluation (i.e., the tendency to feel bad about how one acted in a given scenario), and shame withdrawal (i.e., the tendency to try and avoid unpleasant situations in which one has done something wrong), and negatively associated with shame negative self-evaluation (i.e., the tendency to make internal, negative self-attributions about one's wrongdoing). Negative religious coping was positively associated with shame withdrawal and, for participants with no abuse history, shame negative self-evaluation. Results suggest that positive religious coping is more closely related to guilt proneness, and negative religious coping to shame proneness. Additional research with longitudinal designs and more defined abuse history subgroups is needed.

Diagnostic Differential Between Pedophilic-OCD and Pedophilic Disorder: An Illustration with Two Vignettes.

Despite the prevalence of atypical sexual thoughts in OCD presentations, research suggests that treatment providers often misclassify OCD with pedophilic obsessions (P-OCD) as pedophilic disorder. Such misdiagnoses can have adverse effects including inappropriate treatment, worsening of symptoms, and potential legal complications. Given these iatrogenic effects, clinicians must be competent in differentiating between these two conditions. To clarify the difficult differential between P-OCD and pedophilic disorder, the current paper provides readers with two vignettes that illustrate the differential process. These vignettes highlight important distinctions in symptom presentations and common pitfalls when assessing for P-OCD and pedophilic disorder. The first vignette describes a 32-year-old married woman who experienced pedophilic-themed intrusive thoughts, leading her to avoid children and certain interactions with her daughter. The second vignette describes a 42-year-old married man who experienced ego-dystonic attraction toward minors, particularly 8-10-year-old girls. Following these vignettes, treatment implications and forensic implications are discussed. Finally, recommendations for future clinical and empirical work are made.

Donor-Acceptor-Acceptor 1,3-Bisdiazo Compounds: An Exploration of Synthesis and Stepwise Reactivity.

Metal carbenes, derived from the decomposition of diazo compounds, are valued for their capacity to perform a variety of transformations. A unique class of acyclic, bis-diazo compounds, the donor-acceptor-acceptor 1,3-bisdiazo compounds, are described herein. These compounds are available from acyclic ß-keto esters and especially reactive at the donor-acceptor diazo unit. These bisdiazo compounds react smoothly with rhodium acetate and alcohols to give monodiazo, cyclic orthoesters, presumably through the capture of a transient oxonium ylide.

Recent applications of C-H functionalization in complex natural product synthesis.

In this review, recent examples featuring C-H functionalization in the synthesis of complex natural products are discussed. A focus is given to the way in which C-H functionalization can influence the logical process of retrosynthesis, and the review is organized by the type and method of C-H functionalization.

Set shifting and visuospatial organization deficits in body dysmorphic disorder.

Individuals with body dysmorphic disorder (BDD) over-attend to perceived defect(s) in their physical appearance, often becoming "stuck" obsessing about perceived flaws and engaging in rituals to hide flaws. These symptoms suggest that individuals with BDD may experience deficits in underlying neurocognitive functions, such as set-shifting and visuospatial organization. These deficits have been implicated as risk and maintenance factors in disorders with similarities to BDD but have been minimally investigated in BDD. The present study examined differences in neurocognitive functions among BDD participants (n = 20) compared to healthy controls (HCs; n = 20). Participants completed neuropsychological assessments measuring set-shifting (Cambridge Neuropsychological Test Automated Battery Intra-Extra Dimensional Set Shift [IED] task) and visuospatial organization and memory (Rey-Osterrieth Complex Figure Test [ROCF]). Results revealed a set-shifting deficit among BDD participants compared to HCs on the IED. On the ROCF, BDD participants exhibited deficits in visuospatial organization compared to HCs, but they did not differ in visuospatial memory compared to HCs. Results did not change when accounting for depression severity. Findings highlight neurocognitive deficits as potential endophenotype markers of clinical features (i.e., delusionality). Understanding neuropsychological deficits may clarify similarities and differences between BDD and related disorders and may guide targets for BDD treatment.

Toward a mild dehydroformylation using base-metal catalysis.

Dehydroformylation, or the reaction of aldehydes to produce alkenes, hydrogen gas, and carbon monoxide, is a powerful transformation that is underdeveloped despite the high industrial importance of the reverse reaction, hydroformylation. Interestingly, nature routinely performs a related transformation, oxidative dehydroformylation, in the biosynthesis of cholesterol and related sterols under mild conditions using base-metal catalysts. In contrast, chemists have recently developed a non-oxidative dehydroformylation method; however, it requires high temperatures and a precious-metal catalyst. Careful study of both approaches has informed our efforts to design a base-metal catalyzed, mild dehydroformylation method that incorporates benefits from each while avoiding several of their respective disadvantages. Importantly, we show that cooperative base metal catalysis presents a powerful, mechanistically unique approach to reactions which are difficult to achieve using conventional catalyst design.