Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides.

The kinetics of hydride transfer from Re(Rbpy)(CO)3H (bpy = 4,4'-R-2,2'-bipyridine; R = OMe, tBu, Me, H, Br, COOMe, CF3) to CO2 and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re(Rbpy)(CO)3H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysis indicates that hydride transfer reactions with greater thermodynamic driving force are less sensitive to changes in the electronic properties of the metal hydride, presumably because there is less buildup of charge in the increasingly early transition state. Bronsted α values were obtained for a range of hydride transfer reactions and along with DFT calculations suggest the reactions are concerted, which enables the use of Marcus theory to analyze hydride transfer reactions involving transition metal hydrides. It is notable, however, that even slight perturbations in the steric properties of the Re hydride or the hydride acceptor result in large deviations in the predicted rate of hydride transfer based on thermodynamic driving forces. This indicates that thermodynamic considerations alone cannot be used to predict the rate of hydride transfer, which has implications for catalyst design.

Exploring downstream effects of gender roles in healthcare decision-making and relationships within systems: A cross-sectional analysis of openness to treatment in pediatric headache.

OBJECTIVE: Socio-culturally defined identity factors present significant and often understudied influences on the experience, management, and treatment of chronic pain. For instance, there exist societal narratives about how males and females are expected to experience and express pain. Such gender roles may impact youth and caregiver openness to individual multidisciplinary treatments for pediatric headache. METHODS: In this cross-sectional study, participants (N = 1087 youth/caregiver dyads, Mage = 14.5 years, 71% female, 97% cisgender, 77% White) completed a series of questionnaires, including Openness to Headache Treatment (OHT), upon presenting for initial multidisciplinary evaluation of chronic headache. Pearson correlations, independent samples t-tests and hierarchical regressions were used to analyze potential gender differences in youth and caregiver openness, as well as its relationships with pain-related and psychological factors. RESULTS: Overall, female youth and their caregivers were more open to headache treatment, broadly and for individual interventions, when compared to male counterparts. Caregiver distress related to their child's headaches (i.e., fear and avoidance) was significantly correlated with openness in female youth and their caregivers, but not males. CONCLUSION: Gendered patterns in healthcare decision-making in youth and caregivers provide insight on individual, societal, and systemic gender bias.

Aligning with Patients and Families: Exploring Youth and Caregiver Openness to Pediatric Headache Interventions.

Primary headache disorders are common yet underestimated in youth, resulting in functional disability, decreased quality of life, and caregiver burden. Despite the ubiquity of options, adherence remains challenging for families. One potential factor impacting willingness to engage in recommended treatments is openness. This study explored openness to multidisciplinary headache interventions and the relationships with demographic, pain-related, and psychological variables, among youth and their caregivers. Participants (n = 1087) were youth/caregiver dyads presenting for initial headache evaluation. They completed assessments of openness to headache treatments, medical information, functional disability, and pain-related distress. Overall openness was moderately high for youth and caregivers, and highly correlated between them (r = 0.70). Relationships between youth/caregiver openness to specific interventions were moderate-high (r = 0.42-0.73). These were stronger for interventional techniques but weaker for lifestyle changes. In hierarchical regression models predicting youth and caregiver openness, we found that counterpart openness accounted for the largest portion of variance in their own openness (31-32%), beyond demographic (3%), pain-related (10%), and psychological variables (2-3%). Our findings highlight the importance of involving caregivers in pediatric headache management, given their influence on youth openness and potential involvement in adherence. Awareness of youth/caregiver openness may guide clinicians providing recommendations.

Promoting readiness and engagement in pain rehabilitation for youth and families: Developing a pediatric telehealth motivational interviewing protocol.

Objective: Intensive interdisciplinary pain treatment (IIPT) is a promising approach for youth with complex, disabling, refractory pain conditions. However, youth and families who initiate IIPT without sufficient acceptance of its focus on functional rehabilitation or readiness to adopt a self-management approach to their pain may face challenges in IIPT and/or experience suboptimal outcomes. Motivational interviewing (MI) techniques have been shown to enhance readiness to make a number of health behavior changes for adults and youth, but it has not been systematically examined in the context of pediatric IIPT. The authors developed an MI telehealth intervention protocol explicitly designed to prepare youth and families for admission to IIPT. Method: The protocol development process is detailed here, including influential models, expert consultation, and feedback from IIPT clinical experts. The intervention protocol was then piloted with a group of eligible families to elicit feedback and prompt further refining. Feasibility and acceptability were explored through measures of treatment engagement and satisfaction. Results: The Promoting Readiness and Engagement in Pain Rehabilitation (PREPaRe) intervention protocol contains four modules aimed to enhance youth and parent readiness to adopt a self-management approach to persistent pain, through a motivational interviewing approach. Initial responses from the test group suggested high levels of treatment engagement and treatment satisfaction with PREPaRe. Conclusions: PREPaRe appears feasible to administer and acceptable to families of youth with persistent pain seeking IIPT. Implications for implementation are discussed. Further study via randomized control trial is warranted. Trial registration: ClinicalTrials.gov identifier: NCT04093921.

Will This Treatment Help My Child?: How Parent/Caregiver Treatment Expectations Relate to Intensive Pain Rehabilitation Outcomes for Youth With Chronic Pain.

OBJECTIVE: An extensive body of research has highlighted the impact that parent/caregiver factors have on functioning and treatment outcomes among youth with chronic pain. However, parent/caregiver expectations in pain treatment have been largely understudied, despite strong evidence that treatment expectations are associated with treatment engagement and overall outcomes in nonpain populations. Accordingly, the primary aim of this investigation was to preliminarily examine the manifestation and measurement of parent/caregiver treatment expectations in an intensive interdisciplinary pediatric pain treatment (IIPT) setting. METHODS: Participants in this study (N=328) included children and adolescents who attended an IIPT program for chronic pain between August 2013 and March 2020 and their parent/caregiver(s). Outcomes examined include parent/caregiver self-report of treatment expectations for their child upon admission to the IIPT in addition to pain-related and psychosocial factors at admission and discharge. RESULTS: Findings revealed a high level of expectations (ie, belief that the treatment will be helpful) on average, with higher parent/caregiver expectations associated with poorer functioning at admission to and discharge from the IIPT program. CONCLUSION: Extremely high treatment expectations among parents of more disabled youth may be indicative of unrealistic hopes or the "need" for IIPT to help their child; tempering parental expectations with psychoeducation about IIPT goals and realistic outcomes may indirectly improve treatment outcomes for their children. Future research should examine the potentially unique and important role that treatment expectations, of both parent/caregivers and their children, may have in overall IIPT outcomes.

Development and Feasibility of the Headache-Related Light and Sound Sensitivity Inventories in Youth.

Youth with chronic headache disorders often experience sensitivities to light and sound that trigger or exacerbate their headaches and contribute to functional disability. At present, there are no known validated measures for assessing these sensitivities and their impact on functioning in youth with chronic headaches. This pilot study sought to develop and assess the feasibility of measures of headache-related light and sounds sensitivities in youth with chronic headache disorders. The initial item pools were generated via an intensive literature review, an informal quality improvement project, and a panel of experts in chronic pain. Then, youth (n = 20) presenting for clinical evaluation of headaches completed the revised items as well as assessments of the measures' feasibility and items' understandability. A subset (n = 2) completed formal cognitive interviews as well. The resulting 20-item Headache-Related Light Sensitivity Inventory (HALSI) and 18-item Headache-Related Sound Sensitivity Inventory (HASSI) for youth assess headache-related sensory sensitivities, as well as related emotional and behavioral responses. Through the iterative incorporation of feedback, these measures appear to be feasible to administer and understandable tools for assessing light and sound sensitivity in youth with chronic headache disorders. Once they are empirically validated, they have the potential to serve as important tools for understanding the patient experience, developing interventions, and assessing treatment response.

The use of parsimony network analysis for the formal delineation of phylogenetic species of yeasts: Candida apicola, Candida azyma, and Candida parazyma sp. nov., cosmopolitan yeasts associated with floricolous insects.

Parsimony network analysis of rDNA sequences was used to delimit phylogenetic species of yeasts in an objective, formal manner. Many strains assigned to Candida apicola (Starmerella clade), when compared to the type, fell outside the inclusion limits proposed by Kurtzman and Robnett (1998) based on a pair-wise comparison of the large subunit rRNA gene D1/D2 domains. However, when these sequences were analyzed jointly with ITS rDNA sequences by parsimony network analysis, 28 of the 30 strains formed a cohesive set. Two strains, MUCL 45721 and CBS 4353, were excluded from the species, but there was no evident justification to subdivide the rest. A similar analysis of 81 isolates originally assigned to Candida azyma (Wickerhamiella clade) yielded dramatically different results, giving rise to six independent networks corresponding to Candida azyma sensu stricto (18 strains), Candida azymoides (2 strains), a pair of isolates from Australian hibiscus flowers, a single isolate from the same substrate, a single isolate from Malaysian bertam palm nectar, and 57 isolates that are assigned to the new species Candida parazyma (type = UWOPS 91-652.1(T) = CBS 11563(T) = NRRL Y-48669(T)). The strains retained in C. azyma sensu stricto differed from one another by up to four substitutions in their D1/D2 sequences, but their polymorphism at the level of the ITS was considerable and suggested a history of divergence resulting from dispersal. Strains of C. parazyma fell into seven variant haplotypes based on sequences of the rDNA ITS and D1/D2 regions. The most abundant haplotype occurred across the global range of the species. Others were either endemic to Belize, Costa Rica, Rarotonga, or Tennessee, suggestive of vicariance, or occurred across remote localities, offering partial support to the notion of rapid dispersal.

Clinical Outcomes of Specialized Treatment Units for Patients With Serious Mental Illness in the New York City Jail System.

OBJECTIVE: New York City's (NYC) Correctional Health Services has introduced specialized treatment units for patients with serious mental illness in the NYC jail system. With multidisciplinary mental health staffing and a coordinated approach with NYC's Department of Correction, these units expand therapeutic options for patients vulnerable to clinical instability and physical harm, including those at high risk of psychiatric medication nonadherence and those returning to jail from psychiatric hospitalization. This study evaluated the extent to which these units improve clinical outcomes for this population. METHODS: This retrospective, observational cohort study included adult males with serious mental illness with a length of jail stay of ≥14 days between January 1, 2016, and March 31, 2018. Patients on treatment units were matched with patients of similar characteristics (control group) by using propensity score matching (N=302 pairs). Rates of self-injury, injury due to violence, and psychiatric medication adherence were analyzed. RESULTS: Most patients on treatment units had diagnoses of schizophrenia spectrum and other psychotic disorders (81%), and most had a violent felony as their most severe charge (68%). Compared with patients in a control group, those on the treatment units had lower rates per 100 person-days of injury due to violence at 30 and 60 days (0.04, 95% confidence interval [CI]=0.02-0.07, and 0.03, 95% CI=0.02-0.06, respectively) and higher mean medication adherence (77% versus 55%, p<0.001). They also experienced lower rates of self-injury, although the difference was not statistically significant. CONCLUSIONS: Initial outcomes indicate substantial benefits to patients, demonstrating the value of a rehabilitative approach to psychiatric care in jail.

Avoid or engage? Outcomes of graded exposure in youth with chronic pain using a sequential replicated single-case randomized design.

Pain-related fear is typically associated with avoidance behavior and pain-related disability in youth with chronic pain. Youth with elevated pain-related fear have attenuated treatment responses; thus, targeted treatment is highly warranted. Evidence supporting graded in vivo exposure treatment (GET) for adults with chronic pain is considerable, but just emerging for youth. The current investigation represents the first sequential replicated and randomized single-case experimental phase design with multiple measures evaluating GET for youth with chronic pain, entitled GET Living. A cohort of 27 youth (81% female) with mixed chronic pain completed GET Living. For each participant, a no-treatment randomized baseline period was compared with GET Living and 3- and 6-month follow-ups. Daily changes in primary outcomes fear and avoidance and secondary outcomes pain catastrophizing, pain intensity, and pain acceptance were assessed using electronic diaries and subjected to descriptive and model-based inference analyses. Based on individual effect size calculations, a third of participants significantly improved by the end of treatment on fear, avoidance, and pain acceptance. By follow-up, over 80% of participants had improved across all primary and secondary outcomes. Model-based inference analysis results to examine the series of replicated cases were generally consistent. Improvements during GET Living was superior to the no-treatment randomized baseline period for avoidance, pain acceptance, and pain intensity, whereas fear and pain catastrophizing did not improve. All 5 outcomes emerged as significantly improved at 3- and 6-month follow-ups. The results of this replicated single-case experimental phase design support the effectiveness of graded exposure for youth with chronic pain and elevated pain-related fear avoidance.

Delocalization tunable by ligand substitution in [L2Al] n- complexes highlights a mechanism for strong electronic coupling.

Ligand-based mixed valent (MV) complexes of Al(iii) incorporating electron donating (ED) and electron withdrawing (EW) substituents on bis(imino)pyridine ligands (I2P) have been prepared. The MV states containing EW groups are both assigned as Class II/III, and those with ED functional groups are Class III and Class II/III in the (I2P-)(I2P2-)Al and [(I2P2-)(I2P3-)Al]2- charge states, respectively. No abrupt changes in delocalization are observed with ED and EW groups and from this we infer that ligand and metal valence p-orbitals are well-matched in energy and the absence of LMCT and MLCT bands supports the delocalized electronic structures. The MV ligand charge states (I2P-)(I2P2-)Al and [(I2P2-)(I2P3-)Al]2- show intervalence charge transfer (IVCT) transitions in the regions 6850-7740 and 7410-9780 cm-1, respectively. Alkali metal cations in solution had no effect on the IVCT bands of [(I2P2-)(I2P3-)Al]2- complexes containing -PhNMe2 or -PhF5 substituents. Minor localization of charge in [(I2P2-)(I2P3-)Al]2- was observed when -PhOMe substituents are included.

Perceptions of Pain Treatment in Pediatric Patients With Functional Gastrointestinal Disorders.

OBJECTIVES: Individual understanding of and expectations for chronic pain treatment can influence treatment adherence and thus success, but little is known about these critical factors in parents and children presenting with pain-predominant functional gastrointestinal disorders. The aim of this study was to identify parent and patient understanding of pain-predominant functional gastrointestinal disorders, expectations for treatment, and interventions utilized before presenting to a multidisciplinary clinic. MATERIALS AND METHODS: This was a prospective study of patients evaluated in a Multidisciplinary Functional Abdominal Pain Program. Before the clinic visit, parents and patients completed questionnaires regarding their understanding of chronic pain, perceptions of abdominal pain contributors, expectations regarding treatment, and identification of previous interventions utilized. RESULTS: Participants were knowledgeable regarding the biology of chronic pain. Perceptions of contributors to abdominal pain included a sensitive stomach, general stress, and nerves/worry. Most had attempted to treat their pain with medication, exercise or physical therapy, or a psychological treatment. Participants reported that receiving a definite diagnosis would be the most helpful intervention, followed by psychological treatment. DISCUSSION: Participants were knowledgeable regarding chronic pain, but still indicated that receiving a definite diagnosis would be the most helpful intervention. Most had tried multiple interventions and did not believe that further medication, testing, or surgery would solve their pain. Instead, parents presenting at this Functional Abdominal Pain Program appeared most hopeful about the benefits of multidisciplinary treatment approaches including psychological interventions, a focus on activity and functioning, and complementary and alternative medicine interventions.

Parent Attributions of Ambiguous Symptoms in Their Children: A Preliminary Measure Validation in Parents of Children with Chronic Pain.

How parents attribute cause to their child’s physical symptoms is likely important in understanding how the parent responds to the child, as well as the child’s health outcomes, especially within the context of chronic illness. Here, we adapt the Symptom Interpretation Questionnaire for parent report (SIQ-PR) and provide preliminary validation in a sample of parents of children with chronic pain (N = 311). Confirmatory factor analysis revealed that the SIQ-PR structure is consistent with the original measure, with three distinct attribution types: psychological (emotional/affective), somatic (illness/disease), and environmental (situational/transient) causes. All three subscales demonstrated satisfactory to good internal consistency, and temporal stability. Parents typically endorsed more than one attribution for each symptom, indicating that parents of children with chronic pain have a multidimensional interpretation of physical symptoms in their children. Further, parent psychological and somatic attributions, but not environmental attributions, were significantly associated with (i) parent protective responses towards their child, and (ii) the child’s self-reported somatic and psychological symptoms, indicating convergent and divergent validity. The SIQ-PR may be a useful measure for future studies investigating intergenerational and interpersonal models of pediatric chronic pain, and more broadly, to examine parent attributions of children’s ambiguous symptoms within the context of childhood chronic illness.

Feeling the Pressure to Be Perfect: Effect on Pain-Related Distress and Dysfunction in Youth With Chronic Pain.

Despite clinical observation of perfectionistic tendencies among youth with chronic pain and their parents as well as established relationships between perfectionism and functional somatic symptoms in adults and youth, no research in the pediatric pain literature has examined perfectionism. This study explored the role of various types of youth and parent perfectionism on youth and parent pain-related distress and behavior and youth pain-related dysfunction. At admission, 239 parent-child pairs from outpatient and day-treatment rehabilitation settings completed several questionnaires assessing perfectionism, pain-related distress, and pain-related dysfunction. Bivariate correlations indicated that socially prescribed perfectionism in youth and parents was linked to youth pain duration, parent and youth pain-related distress and behavior, and youth somatization. Indirect relations showed that youth socially prescribed perfectionism was the only form of perfectionism directly associated with youth somatization whereas all forms of youth perfectionism were indirectly associated with somatization and functional disability through increases in youth pain-related fear and catastrophizing. Additionally, socially prescribed perfectionism was the only type of parent perfectionism linked to youth pain-related dysfunction (somatization, functional disability) through its association with youth pain-related fear. Findings support clinical observations that parent and youth perfectionism is a psychosocial factor that should be targeted in pediatric chronic pain treatment. PERSPECTIVE: Perfectionism in youth with chronic pain and their parents was indirectly linked to youth pain-related dysfunction through its effect on youth pain-related catastrophizing and fear. Findings support clinical observations that parent and youth perfectionism is a psychosocial factor that should be targeted in pediatric chronic pain treatment.

Back to Living: Long-term Functional Status of Pediatric Patients Who Completed Intensive Interdisciplinary Pain Treatment.

OBJECTIVES: To provide a descriptive account of long-term functioning (≥5 y posttreatment) among youth who completed intensive interdisciplinary pain treatment (IIPT) for pediatric chronic pain conditions. MATERIALS AND METHODS: A total of 95 patients (mean age at follow-up=20.0 y) treated at least 5 years previously at a single IIPT program completed questionnaires assessing pain, functional disability, health care utilization, academic/career achievement, and quality of life. Data analyses focused on pain, functioning, and progress toward developmental goals at long-term follow-up. RESULTS: The majority of respondents report significant reduction in pain compared with preadmission (P<0.001). Five years posttreatment, average functional disability scores were in the minimal range, with statistically significant decrease in functional disability from time of admission (P<0.001). Nearly 80% of respondents characterized themselves as having no functional difficulties at follow-up. Clinically significant improvement was established for both pain and function. Respondents generally reported developmentally appropriate status, with 89% graduating high school on schedule. DISCUSSION: Results show long-term positive functioning among individuals who underwent intensive rehabilitation treatment for chronic pain as children or adolescents. Despite experiencing one or more pain flares at some point after treatment, most former IIPT patients report minimal to no ongoing functional disability, complete or partial resolution of pain symptoms, and developmentally appropriate progress toward goals (eg, school completion, independent living).

Linkages between child abuse and attention-deficit/hyperactivity disorder in girls: behavioral and social correlates.

OBJECTIVE: The objectives of this study were to examine whether girls with attention-deficit/hyperactivity disorder (ADHD) are at increased risk of having histories of abuse and to assess whether the presence of an abuse history may constitute a distinct subgroup of youth with ADHD. METHOD: We examined rates and correlates of child abuse in an ethnically and socioeconomically diverse sample of girls with attention-deficit/hyperactivity disorder (ADHD; n=140) and a matched comparison sample of girls without ADHD (n=88), all aged 6-12 years. A thorough chart review reliably established documented rates of physical and sexual abuse in both samples. RESULTS: There were significantly higher rates of abuse for girls with ADHD (14.3%) than for the comparison sample (4.5%), with most of the abuse found in girls with the Combined as opposed to the Inattentive type. Higher rates of externalizing behaviors (including objective observations in a research summer camp) and peer rejection (indexed through peer sociometric nominations) characterized the subgroup of girls with ADHD with abuse histories compared to the subgroup without such histories, with moderate to large effect sizes. Subgroup differences regarding internalizing problems and cognitive deficits did not emerge. Findings regarding peer rejection were explained, in part, by higher rates of observed aggressive behavior in the abused subgroup. CONCLUSIONS: The findings raise important questions about the possible etiologic and/or exacerbating role of abusive trauma in a subgroup of children with ADHD.

Living Life With My Child's Pain: The Parent Pain Acceptance Questionnaire (PPAQ).

OBJECTIVE: Parents' emotional, cognitive, and behavioral responses are highly influential on children's pain and functional outcomes. One important response to pediatric pain is acceptance: the degree to which an individual participates in routine daily activities in the presence of pain and is willing to let pain be a part of their life without efforts to control or avoid it. However, no tool currently exists to assess parents' own acceptance of their child's pain. The aim of this study was to validate the Parent Pain Acceptance Questionnaire (PPAQ). MATERIALS AND METHODS: The PPAQ was administered to 310 parents of youth with chronic pain in an outpatient pediatric headache program and a day hospital pain rehabilitation program. An exploratory factor analysis revealed 2 factors for the PPAQ: an 11-item Activity Engagement scale and a 4-item Acceptance of Pain-related Thoughts and Feelings scale. RESULTS: The PPAQ total score and subscales demonstrated strong internal consistency. Greater parent pain acceptance was positively associated with child pain acceptance, and was negatively correlated with parent protective behaviors, parent minimizing behaviors, parent and child pain catastrophizing, and child fear of pain. Parent protective behaviors and child pain acceptance both served as mediators of the relationship between parent pain acceptance and child functional disability. CONCLUSIONS: The PPAQ is a valid measure of parent pain acceptance and may provide valuable insights into parent responses to child pain and the ways in which parent acceptance influences child outcomes. Clinical implications and suggestions for future research are discussed.

Parent cognitive-behavioral intervention for the treatment of childhood anxiety disorders: a pilot study.

Strong evidence supports cognitive-behavioral therapy (CBT) for the treatment of childhood anxiety. Many studies suggest that parents play an etiological role in the development and maintenance of child anxiety. This pilot study examined the efficacy of a cognitive-behavioral intervention delivered to the parents of 31 anxious children (ages 7-13). Parents were randomly assigned to an individual parent-only CBT intervention (PCBT, n = 18) or wait-list control (WL, n = 13). PCBT demonstrated significant reductions in children's number of anxiety disorder diagnoses, parent-rated interference and clinician-rated severity of anxiety, and maternal protective behaviors at post-treatment, which were maintained at 3-months. WL did not demonstrate significant changes. There were no significant differences between conditions in child self-reported or parent-report of child anxiety symptoms. Findings were replicated in a combined sample of treated participants, as well as in an intent-to-treat sample. Parent-only CBT may be an effective treatment modality for child anxiety, though future research is warranted.