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BACKGROUND AND OBJECTIVE: Though public health is an information-intense profession, there is a paucity of workforce with Public Health Informatics and Technology (PHIT) skills, which was evident during the coronavirus disease 2019 (COVID-19) pandemic. This need is addressed through the PHIT workforce program (2021-2025) by the Office of the National Coordinator for training and to increase racial and ethnic diversity in the PHIT workforce. The objective is to share details on the Training in Informatics for Underrepresented Minorities in Public Health (TRIUMPH) consortium, funded by the PHIT workforce program. METHODS: The TRIUMPH consortium is a collaboration between academic and practice partners with a commitment to training 879 students in PHIT. The Schools of Public Health and Nursing at the University of Minnesota, Jiann-Ping Hsu College of Public Health at Georgia Southern University, Morehouse School of Medicine, and Public Health Informatics Institute offer PHIT training through various programs. Academic institutions focus on student recruitment, developing courses/curriculum, and granting degrees/certificates, and the role of practice partners is to support experiential learning through internships/practicums. RESULTS: The TRIUMPH consortium is progressing toward its goals, with 692 students (79%) already trained in a PHIT modality as of December 2023. The learners comprise diverse race/ethnicity, including White (48%), Black/African American (32%), Asian (10%), White Hispanic (5%), American Indian/Alaska Native (2%), and Black Hispanic (1%). Numerous internships have been completed in settings ranging from state/local public health agencies to health care delivery systems. Diversity initiatives were supported by partnering with existing programs (e.g., the AMIA First Look program and the Nursing Knowledge Big Data Science conference). CONCLUSION: This consortium model is an excellent approach to informatics training and sharing expertise across partners. It provides scalability and broader geographic outreach while presenting opportunities to students from underrepresented backgrounds. Lessons learned have implications for overall informatics training (e.g., partnerships models, promoting racial/ethnic diversity).
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Problem-Based Learning , Public Health Informatics , Humans , Minority Groups/education , Curriculum , Public Health/educationSubject(s)
Lung , Reference Values , Respiratory Function Tests , Humans , Black or African American , WhiteABSTRACT
BACKGROUND: The current state of practices in health care remediation is not well known. The purpose of this review is to characterize, assess, and present synthesized results of current student and professional remediation practices described in the literature. METHODS: This study used an integrative review process including article extraction and review, descriptive characterization and statistics, classification of levels of evidence, assessment of risk of bias, and examination of relationships between factors and types of remediation. Articles were located in a search of PubMed (MEDLINE) and EBSCO (CINAHL Complete) last accessed in May 2022. INCLUSION CRITERIA: Full text journal articles and Briefs published between January 2001 and May 2022, English language, focus on remediation in health science education programs and professionals, identified key words in title, abstract, or article. EXCLUSION CRITERIA: Published outside the date range; focus of study or article outside health sciences; main focus not on remediation process or program (defined above), books, presentations and abstracts. RESULTS: 97 articles were included. Design rigor clustered around Level 6 (case-controlled studies, case series, case reports). All programs and activities were reported as successful. There was a statistically significant relationship (p < 0.01) between healthcare discipline and type of remediation. CONCLUSIONS: A variety of remediation methods for health care students and professionals are reported to be successful. Higher level studies are needed to help define best practices for remediation activities in health care professional knowledge and skill.
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Delivery of Health Care , Students, Health Occupations , Humans , Case-Control Studies , Learning , Health OccupationsABSTRACT
ABSTRACT: Data from electronic health records (EHRs) are becoming accessible for use in clinical improvement projects and nursing research. But the data quality may not meet clinicians' and researchers' needs. EHR data, which are primarily collected to document clinical care, invariably contain errors and omissions. This article introduces nurses to the secondary analysis of EHR data, first outlining the steps in data acquisition and then describing a theory-based process for evaluating data quality and cleaning the data. This process involves methodically examining the data using six data quality dimensions-completeness, correctness, concordance, plausibility, currency, and relevance-and helps the clinician or researcher to determine whether data for each variable are fit for use. Two case studies offer examples of problems that can arise and their solutions.
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Data Accuracy , Electronic Health Records , HumansABSTRACT
OBJECTIVES: Sensory impairments are prevalent among older adults and have been associated with cognitive challenges in later life, yet mechanisms are less well understood. We examined the mediating role of social isolation in the longitudinal relationship between self-reported sensory difficulty and impaired cognitive functioning among older adults. METHODS: Data were taken from the NHATS Study, an annual survey of Medicare beneficiaries' age ≥ 65. Participants (N = 6,338) provided data at Rounds 5, 6, and 7 (2015, 2016, 2017). Structural equation models were estimated to test longitudinal direct and indirect associations. RESULTS: All sensory difficulties were negatively associated with all cognitive functioning measures cross-sectionally through social isolation. Longitudinally, vision difficulty and dual sensory difficulty were indirectly associated with cognitive functioning across time. Hearing difficulty had no longitudinal indirect associations with cognitive functioning through social isolation. DISCUSSION: Social isolation is an important pathway through which late-life vision difficulty is associated with decreased cognitive function.
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Cognitive Dysfunction , Hearing Loss , Aged , Cognition , Cognitive Dysfunction/psychology , Hearing , Hearing Loss/psychology , Humans , Longitudinal Studies , Medicare , Social Isolation , United States , Vision Disorders/psychologyABSTRACT
OBJECTIVES: Sensory disabilities, including vision disability and hearing disability, increase risk for social isolation, which is associated with multiple negative health outcomes. Existing literature suggests that the cultural value of familism may provide a buffer against social isolation. We examined the longitudinal trajectory of social isolation among Hispanic older adults with self-reported vision disability (SRVD) and self-reported hearing disability and tested a modified measure of social isolation incorporating familism. METHODS: We compared 8-year trajectories of social isolation among Hispanics (n = 445) and non-Hispanic Whites (n = 4,861) from the National Health and Aging Trends Study. We used structural equation modeling to explore the longitudinal relationships between sensory disability and social isolation while comparing 2 measures of social isolation. RESULTS: Social isolation increased longitudinally for both groups, with SRVD significantly associated with higher initial levels. Social isolation started and remained higher across time among Hispanics. Using an adjusted measure of social isolation (added familial support), neither initial levels nor trajectories of social isolation differed between Hispanic and non-Hispanic White participants. DISCUSSION: Initially, Hispanics appeared more socially isolated, reporting less social support from outside the home. Yet, we found that they were more likely to report family social connections. Traditional measures of social isolation focusing on social support outside of the home (neglecting support by family) may lack content validity among Hispanic groups. Culturally sensitive measures of social isolation will be increasingly consequential for future research and health policy to meet the needs of a diverse older population.
Subject(s)
Disabled Persons , Hispanic or Latino , Humans , Aged , Social Isolation , Social Support , Vision DisordersABSTRACT
Eyewitness evidence often plays a critical role in decisions made in the criminal justice system. To evaluate eyewitness testimony accurately, judges must be aware of factors that can contaminate this type of evidence. In 2008, a survey of judges in Norway revealed a lack of awareness of several factors that affect eyewitness testimony. In the current study, a survey was administered to Norwegian judges (N=98) to evaluate their knowledge of factors that affect eyewitness testimony. Results showed that judges' overall knowledge scores were similar to those reported in 2008, but substantial increases and decreases in knowledge were observed for specific factors. Additional analyses indicated that increased uncertainty regarding some eyewitness factors led to a decline in accuracy when compared to responses observed in 2008. The current study provides an updated assessment of judges' knowledge of eyewitness factors and highlights the need for more comprehensive training for judges regarding these factors.
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BACKGROUND: Diminished social support lias shown to lead to worse cardiovascular outcomes and since cardiovascular disease (CVD) is the leading cause of death in the United States (U.S.), it is critical to non-invasively study its precursor- vascular disease (VD). Assessing the impact social support lias on vascular outcomes can unveil potential CVD susceptibilities in at-risk populations. African American women exhibit the greatest burden of CVD morbidity and mortality; therefore, the purpose of tins study is to examine the association between living arrangement/social support and impaired vascular function in asymptomatic African American women. METHODS: Vascular function was assessed by a non-invasive screening tool, HDI/PulseWave CR-2000, during screenings at community outreach events on participants clinically free of CVD. Vascular disease was defined as abnormal/impaired vascular function. Living arrangement, a binary variable (living with someone/living alone), was determined by survey responses (N=67) and represented social support. Multivariable analyses were used to estimate adjusted odds ratios (AORs) and 95% confidence intervals (95% CIs) to determine the association between living arrangement and vascular disease after controlling for confounders. Analyses were conducted using SAS 9.2. RESULTS: Of those who lived alone, 82% had vascular disease (p=0.03). After adjusting for family CVD, and other CVD risk factors, those who lived with a spouse/partner or relative were 78% (p=0.04) less likely to develop vascular disease (AOR=0.22; 95% 0=0.05, 0.98). CONCLUSIONS: Our study provides preliminary evidence to suggest that among African American women, clinically free of CVD, living arrangement is associated with vascular disease. While living alone may place individuals at an increased risk of CVD because of the association, living with a spouse/partner or relative may act as a protective factor against vascular disease and reduce the risk of CVD. Public health practitioners may use individuals' living arrangement as preventive measure for CVD risk.
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BACKGROUND: Hospital-acquired pressure injuries are a serious problem among critical care patients. Some can be prevented by using measures such as specialty beds, which are not feasible for every patient because of costs. However, decisions about which patient would benefit most from a specialty bed are difficult because results of existing tools to determine risk for pressure injury indicate that most critical care patients are at high risk. OBJECTIVE: To develop a model for predicting development of pressure injuries among surgical critical care patients. METHODS: Data from electronic health records were divided into training (67%) and testing (33%) data sets, and a model was developed by using a random forest algorithm via the R package "randomforest." RESULTS: Among a sample of 6376 patients, hospital-acquired pressure injuries of stage 1 or greater (outcome variable 1) developed in 516 patients (8.1%) and injuries of stage 2 or greater (outcome variable 2) developed in 257 (4.0%). Random forest models were developed to predict stage 1 and greater and stage 2 and greater injuries by using the testing set to evaluate classifier performance. The area under the receiver operating characteristic curve for both models was 0.79. CONCLUSION: This machine-learning approach differs from other available models because it does not require clinicians to input information into a tool (eg, the Braden Scale). Rather, it uses information readily available in electronic health records. Next steps include testing in an independent sample and then calibration to optimize specificity.
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Beds/classification , Critical Care/methods , Machine Learning , Pressure Ulcer/epidemiology , Pressure Ulcer/prevention & control , Adult , Aged , Electronic Health Records/statistics & numerical data , Female , Humans , Iatrogenic Disease , Male , Middle Aged , Predictive Value of Tests , ROC Curve , Risk Assessment , Risk Factors , Severity of Illness IndexABSTRACT
OBJECTIVE: According to the American Cancer Society, 25% of cancer survivors in the United States develop depression. The objective of this study is to assess factors associated with self-reported history of depression diagnosis among cancer survivors aged ≥18 years in the United States. METHODS: Data were analyzed from the 2014 Behavioral Risk Factor Surveillance System (N = 6079). The Behavioral Risk Factor Surveillance System collects data about US residents regarding their health-related risk behaviors and events, chronic health conditions, and use of preventive services. Respondents were considered to have a history of depression diagnosis if they answered yes to the question "Has a doctor or other health care provider EVER told you that you have a depressive disorder, including depression, major depression, dysthymia, or minor depression?" Bivariate and multivariable logistic regression analyses were conducted to assess factors associated with depression in cancer survivors. Analyses were conducted using SAS 9.4. RESULTS: After adjusting for demographic and socioeconomic factors, females (AOR: 1.70; 95% CI, 1.50-1.97); those with an annual household income of $24 999 or less (AOR: 2.48; 95% CI, 1.95-3.16); $25 000 to $49 999 (AOR: 1.62; 95% CI, 1.31-2.02), and $50 000 to $74 999 (AOR: 1.35; 95% CI, 1.10-1.71); those who were not married (AOR = 1.37; 95% CI, 1.17-1.60); and those who perceived their health as poor (AOR = 2.33; 95% CI, 2.01-2.70), were significantly more likely to report a diagnosis of depression. CONCLUSIONS: The results indicate that gender, income, marital status, and perceived health status were associated with self-reported depression among cancer survivors aged ≥18 years in the United States.
Subject(s)
Cancer Survivors/psychology , Depression/psychology , Health Behavior , Health Status , Adult , Aged , Behavioral Risk Factor Surveillance System , Cancer Survivors/statistics & numerical data , Chronic Disease/psychology , Depression/epidemiology , Female , Humans , Income , Male , Marital Status , Middle Aged , Self Report , United States , Young AdultABSTRACT
In 2016, an estimated 4120 women will die as a result of cervical cancer. The objective of this study was to examine the factors associated with cervical cancer screening among women 18 years of age and older in the United States (U.S.). Using the 2012 Behavioral Risk Factor Surveillance System survey, women over the age of 18 in the U.S. were examined to assess factors associated with cervical cancer screening. Analyses were conducted using SAS 9.2. Of the 272,692 study participants, 258,496 (95 %) had obtained cervical cancer screening. After adjusting for demographic and socioeconomic factors, being non-Hispanic White, Hispanic or Latino, Asian, Native Hawaiian or Other Pacific Islander, in the age group 18-44 years and 75 years and above, having less than a high school education and an annual household income of less than a $25,000, having never married, and residing in the West region of the U.S. reduced the likelihood of participation in cervical cancer screening. Also, after adjusting for demographic and socioeconomic factors, being between the ages of 45-74 years of age, having more than a high school education, having a higher income, and residing in the South region of the U.S. increased the likelihood of participation in cervical cancer screening. The results of this study suggest that socio-demographic factors and region of residence are predictors of cervical cancer screening. These findings highlight the need to identify potential prevention strategies to promote cervical cancer screening among at-risk populations and groups.
Subject(s)
Early Detection of Cancer/statistics & numerical data , Uterine Cervical Neoplasms/prevention & control , Adolescent , Adult , Age Factors , Aged , Behavioral Risk Factor Surveillance System , Early Detection of Cancer/psychology , Female , Humans , Middle Aged , Papanicolaou Test/statistics & numerical data , Racial Groups/statistics & numerical data , Self Report , Socioeconomic Factors , United States , Young AdultABSTRACT
One mole equivalent of gaseous SO2 is absorbed by purple TDAE[O2SSO2](s), producing red, essentially spectroscopically pure TDAE[O2SS(O)2SO2](s); under prolonged evacuation, the product loses SO2(g), regenerating TDAE[O2SSO2](s). Similarly, [NR4]2[O2SS(O)2SO2](s) (R = Et, Me) can be prepared, albeit at lower purity, from the corresponding tetraalkylammonium dithionites (prepared by a modification of the known [NEt4]2[O2SSO2](s) preparation). While the [NEt4](+) salt is stable at rt; the [NMe4](+) salt has only limited stability at -78 °C. Vibrational spectra assignments for the anion in these salts were distinctly different from those for the anion in salts containing the long-known [O3SSSO3](2-) dianion, the most thermodynamically stable form of [S3O6](2-) (we prepared TDAE[O3SSSO3]·H2O(s) and obtained its structure by X-ray diffraction and vibrational analyses). The best fit between the calculated ((B3PW91/6-311+G(3df) and PBE0/6-311G(d)) and experimental vibrational spectra were obtained with the dianion having the [O2SS(O)2SO2](2-) structure. Vibrational analyses of the three [O2SS(O)2SO2](2-) salts prepared in this work showed that the corresponding [O3SSO2](2-) salts were present as a ubiquitous decomposition product. The formation of these new [O2SS(O)2SO2](2-) dianion salts was predicted to be favorable for [NMe4](+) and larger cations using a combination of theoretical calculations (B3PW91/6-311+G(3df)) and volume based thermodynamics (VBT). Similar methods accounted for the greater stabilities of the TDAE(2+) and [NEt4](+) salts of [O2SS(O)2SO2](2-) compared to [NMe4]2[O2SS(O)2SO2](s) toward irreversible decomposition to the corresponding [O3SSO2](2-) salts. These salts represent the first known examples of a new class of poly(sulfur dioxide) dianion, [SO2]n(2-) in which n > 2.
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Fukutin-related protein-muscular dystrophy is characterized by defects in glycosylation of α-dystroglycan with variable clinical phenotypes, most commonly as limb-girdle muscular dystrophy 2I. There is no effective therapy available. Glucocorticoid steroids have become the standard treatment for Duchenne and other muscular dystrophies with serious adverse effects, including excessive weight gain, immune suppression, and bone loss. Bisphosphonates have been used to treat Duchenne muscular dystrophy for prevention of osteoporosis. Herein, we evaluated prednisolone and alendronate for their therapeutic potential in the FKRPP448L-mutant mouse representing moderate limb-girdle muscular dystrophy 2I. Mice were treated with prednisolone, alendronate, and both in combination for up to 6 months. Prednisolone improved muscle pathology with significant reduction in muscle degeneration, but had no effect on serum creatine kinase levels and muscle strength. Alendronate treatment did not ameliorate muscle degeneration, but demonstrated a limited enhancement on muscle function test. Combined treatment of prednisolone and alendronate provided best improvement in muscle pathology with normalized fiber size distribution and significantly reduced serum creatine kinase levels, but had limited effect on muscle force generation. The use of alendronate significantly mitigated the bone loss. Prednisolone alone and in combination with alendronate enhance functionally glycosylated α-dystroglycan. These results, for the first time, demonstrate the efficacy and feasibility of this alliance treatment of the two drugs for fukutin-related protein-muscular dystrophy.
Subject(s)
Adrenal Cortex Hormones/pharmacology , Alendronate/pharmacology , Bone Density Conservation Agents/pharmacology , Muscle, Skeletal/drug effects , Muscular Dystrophy, Animal/pathology , Prednisone/pharmacology , Animals , Blotting, Western , Bone Density/drug effects , Dystroglycans/metabolism , Glycosylation/drug effects , Mice , Mice, Mutant Strains , Muscle, Skeletal/metabolism , Muscle, Skeletal/pathology , Muscular Dystrophies, Limb-Girdle/metabolism , Muscular Dystrophies, Limb-Girdle/pathology , Muscular Dystrophy, Animal/metabolism , PhenotypeABSTRACT
BACKGROUND: The Centers for Disease Control and Prevention (CDC) estimates that 14 percent of persons infected with HIV in the United States (US) are unaware of their infection and many of the estimated 50,000 new HIV infections each year are transmitted by people who do not know that they are HIV-positive. HIV testing is an important component of HIV prevention. This study examined predictors of self-reported HIV testing among persons 18 years and over in the US. METHODS: Data from the 2012 BRFSS were utilized. We used univariate analysis to calculate relative frequencies for gender, race or ethnicity, age, education, income, marital status, region of residence, and having engaged in HIV/AIDS risky behaviors to characterize the overall sample. We conducted bivariate analysis for an initial assessment of factors independently associated with HIV testing. Multivariable logistic regression models were used to obtain the Adjusted Odds Ratios (AORs) and 95% Confidence Intervals (95% CIs) for factors associated with getting tested for HIV. Analyses were conducted using SAS version 9.2. RESULTS: Of the 439,327 respondents, 30% had been tested for HIV. Of those who had been tested for HIV, 59% were female; 41% were two or more races and 47% were between 18-44 years of age. The majority (39%) of the respondents were college graduates. Over one-third (31%) of the participants who had been tested had annual household incomes which were less than $25,000. Half (50%) were married and 24% of the respondents were from the Western region of the US. Five percent of the respondents reported that they had engaged in HIV/AIDS risky behaviors. Factors associated with lower odds of getting tested included being Asian (AOR=0.56; 95% CI=0.41, 0.78); Native Hawaiian or Other Pacific Islander (AOR=0.42; 95% CI=0.18, 0.90); and having an income between $25,000 to $49,000 (AOR=0.82; 95% CI=0.78-0.87); $50,000 to $74,999 (AOR=0.86; 95% CI=0.79-0.93); or $75,000 or more (AOR=0.87; 95% CI=0.81-0.94). Also, respondents from the Midwest (AOR=0.78; 95% CI=0.73, 0.83) and the West (AOR=0.88; 95% CI=0.83, 0.93) were less likely to get tested for HIV. Our adjusted analyses also showed that being non-Hispanic Black or African American, Hispanic or Latino, identifying as having two or more races, and being American Indian or Alaska Native increased the likelihood of getting tested for HIV. Having engaged in HIV/AIDS risky behaviors had significantly higher odds of being tested for HIV (AOR=2.45; 95% CI=2.19, 2.74). CONCLUSION: Our findings suggest that the HIV/AIDS prevention education and training programs in the US that have focused on traditionally classified high-risk populations have been effective. Findings from this study uncover an interesting paradox, which suggests that populations with higher incomes have been overlooked in efforts to combat HIV/AIDS. Our results suggest that these populations are at greatest risk of not knowing their HIV status and are therefore most likely to unknowingly contribute to the number of new HIV infections. Future research on multiple interacting factors that affect HIV testing behaviors should be considered top priorities. This is of upmost importance because knowing one's HIV status allows those who are infected to seek and receive treatment and prevention services, which are designed to improve health and reduce the likelihood of further transmission.
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OBJECTIVE: It is estimated that 41 million American adults 18 and older experience poor physical or mental health which limits their ability to engage in their daily activities. The objective of this study was to assess the prevalence of and factors associated with ≥14activity limitation days (ALD) due to poor physical or mental health as self-reported by persons aged 18 years and over in the United States (U.S). METHODS: Using the 2012 Behavioral Risk Factors Surveillance System (BRFSS), persons over the age of 18 in the U.S. were examined to assess the prevalence of and factors associated with ≥ 14ALD due to poor physical or mental health. The BRFSS is administered on a continuous basis by telephone using random-digit dial sampling methods. A clustering sample design was used to account for differences in the probability of selection and non-response in order to accurately derive US and state-based population estimates. The design consists of a probability sample of all households with telephones in the state. Analyses were conducted using SAS 9.2. RESULTS: Of the 104,257 participants included in the analyses, 40% reported having ≥14 ALD due to poor physical or mental health. After adjusting for demographic and socioeconomic factors, males (AOR1.17, 95% CI: 1.14-1.21), those with high school or less education (AOR: 1.42, 95% CI: 1.37-1.21), those who were separated (AOR: 1.23; 95% CI=1.14-1.32), divorced (AOR: 1.10; 95% CI=1.06-1.15), those from the Southern Black Belt States (AOR1.14, 95% CI: 1.10-1.20), and those from the remainder of the Southern region of the U.S. (AOR1.14, 95% CI: 1.08-1.21) were significantly more likely to report ≥14ALD due to poor physical or mental health. CONCLUSION: The prevalence of ≥14ALD due to poor physical or mental health among the study population was associated with sociodemographic and region of residence factors. These findings highlight the need for prevention strategies specifically for populations who might be more at risk for ALD due to social determinants of health.
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TGFß superfamily proteins, acting via SMAD (Sma- and Mad-related protein)2/3 pathways, regulate placental function; however, the role of SMAD1/5/8 pathway in the placenta is unknown. This study investigated the functional role of bone morphogenetic protein (BMP)4 signaling through SMAD1/5 in terminal differentiation of primary chorionic gonadotropin (CG)-secreting trophoblast. Primary equine trophoblast cells or placental tissues were isolated from day 27-34 equine conceptuses. Detected by microarray, RT-PCR, and quantitative RT-PCR, equine chorionic girdle trophoblast showed increased gene expression of receptors that bind BMP4. BMP4 mRNA expression was 20- to 60-fold higher in placental tissues adjacent to the chorionic girdle compared with chorionic girdle itself, suggesting BMP4 acts primarily in a paracrine manner on the chorionic girdle. Stimulation of chorionic girdle-trophoblast cells with BMP4 resulted in a dose-dependent and developmental stage-dependent increase in total number and proportion of terminally differentiated binucleate cells. Furthermore, BMP4 treatment induced non-CG-secreting day 31 chorionic girdle trophoblast cells to secrete CG, confirming a specific functional response to BMP4 stimulation. Inhibition of SMAD2/3 signaling combined with BMP4 treatment further enhanced differentiation of trophoblast cells. Phospho-SMAD1/5, but not phospho-SMAD2, expression as determined by Western blotting was tightly regulated during chorionic girdle trophoblast differentiation in vivo, with peak expression of phospho-SMAD1/5 in vivo noted at day 31 corresponding to maximal differentiation response of trophoblast in vitro. Collectively, these experiments demonstrate the involvement of BMP4-dependent pathways in the regulation of equine trophoblast differentiation in vivo and primary trophoblast differentiation in vitro via activation of SMAD1/5 pathway, a previously unreported mechanism of TGFß signaling in the mammalian placenta.
Subject(s)
Bone Morphogenetic Protein 4/metabolism , Cell Differentiation , Chorionic Gonadotropin/metabolism , Smad Proteins, Receptor-Regulated/metabolism , Trophoblasts/cytology , Animals , Female , Horses , Pregnancy , Primary Cell Culture , Signal Transduction/physiology , Smad1 Protein/physiology , Smad5 Protein/physiology , Smad8 Protein/physiology , Transforming Growth Factor beta/metabolism , Trophoblasts/metabolismABSTRACT
Gaseous SO2 reacts with tetrakis(dimethylamino)ethylene (TDAE) in acetonitrile in a 2:1 stoichiometric ratio to give analytically pure insoluble purple (TDAE)(O2SSO2) (1) in about 80% yield. Crystals of (TDAE)(O2SSSSO2) (2) were obtained from orange solution over the purple solid. The Raman spectrum of [TDAE](2+) was established using (TDAE)(A) salts [A = 2Br(-), 2Br(-)·2H2O (X-ray), 2[Br3](-) (X-ray)]. Vibrational spectroscopy showed that [O2SSO2](2-) in 1 has C2h geometry. The X-ray structure of 2 showed that it contained [O2SSSSO2](2-), the first example of a new class of sulfur oxyanions, the polythionites. The geometry of [O2SSSSO2](2-) consists of S2 with an S-S bond length of 2.003(1) Å connected to two terminal SO2 moieties by much longer S-S bonds of 2.337(1) Å. Calculations (B3PW91/6-311+G(3df)) show that the structural units in [O2SSSSO2](2-) are joined by the interaction of electrons in two mutually perpendicular π* SOMOs of the triplet-state diradical S2 with unpaired electrons in the π*-antibonding orbitals of the two terminal [SO2](â¢-) and polarized to delocalize the negative charge equally onto the three fragments. Thermodynamic estimates show 2 to be stable with respect to loss of sulfur and formation of 1, in contrast to [O2SSSSO2](2-) salts of small cations that are unstable toward the related dissociation. Reaction of TDAE with an excess of liquid SO2 led to (TDAE)(O3SOSO3)·SO2 (preliminary X-ray, Raman), (TDAE)(O3SSSSO3)·2SO2 (preliminary X-ray, Raman), and (TDAE)(O3SSO2) (Raman).
ABSTRACT
One mole equivalent of SO2 reversibly reacts with [N(CH3)4]2SO4(s) to give [N(CH3)4]2S2O6(s) (1) containing the [O3SOSO2](2-), shown by Raman and IR to be an isomer of the [O3SSO3](2-) dianion. The experimental and calculated (B3PW91/6-311+G(3df)) vibrational spectra are in excellent agreement, and the IR spectrum is similar to that of the isoelectronic O3ClOClO2. Crystals of [N(CH3)4]2(O2SO)2SO2·SO2 (2) were isolated from solutions of [N(CH3)4]2SO4 in liquid SO2. The X-ray structure showed that 2 contained the [(O2SO)2SO2](2-) dianion. The characterized N(CH3)4(+) salts 1 and 2 are the first two members of the (SO4)(SO2)x(2-) class of sulfur oxydianions analogous to the well-known small cation salts of the SO4(SO3)x(2-) polysulfates.