Sudden cardiac death due to an obstructive large right atrial myxoma.

Sudden cardiac death is a phenomenon that affects more than 200,000 individuals annually in the United States. Among sudden cardiac deaths, only a fractionally small portion is thought to be attributable to intracardiac neoplasms. Though rarely implicated as the primary cause of death, cardiac myxomas are the most common benign neoplasms of the heart and have been known to cause death due to multifactorial embolic events, fatal arrhythmias, and frank obstructive events. In this case, a healthy, asymptomatic young male was found unresponsive in his residence. Examination of the heart at autopsy revealed dilation of the right atrium and a large, hemorrhagic, irregular, and obstructing mass arising from the right atrium, consistent with cardiac myxoma. When unusual cardiac findings are discovered at autopsy, a systematic investigation of the heart, including retaining the organ for cardiac pathology consultation, is mandatory to correctly identify the cause of death.

An Abnormal Presentation of Rocky Mountain Spotted Fever: A Case Report.

The intracellular coccobacilli Rickettsia rickettsii causes Rocky Mountain Spotted Fever, a potentially fatal illness. This bacterium is transmitted to humans through a tick vector. Patients classically present with a triad of symptoms, including fever, headache, and a rash that begins on the extremities and spreads proximally to the trunk. Diagnosis of this disease can prove difficult when patients have unusual symptoms, such as hypertensive crisis. In this case report, we present a 29-year-old male who arrived at the emergency room with altered mental status and a hypertensive crisis after his family reported one week of changes in his behavior. The patient had no evidence of ticks, tick bites, fever, or rash. Positive findings in the emergency room included a WBC of 14.9 × 109. All other physical exams, imaging, and laboratory findings were non-contributory. The patient was promptly given IV hydralazine to control his blood pressure and empiric IV ceftriaxone for potential infection, and he was admitted for observation. Over the course of three days, WBC levels decreased, and his altered mental status improved. On day 3, the patient remembered a tick crawling across his hand, and this prompted the ordering of immunoglobulin levels for tick-borne illnesses. IgM for RMSF was positive. This case presentation illustrates the need for clinicians to keep the potential diagnosis of RMSF high on the differential, even in the presence of a paucity of symptoms, as prompt treatment with doxycycline can be lifesaving. This case may also be one of the first reported in the literature of hypertension being a symptom of Rocky Mountain Spotted Fever. It is plausible, however, that this patient's hypertension was due to an acute stress response.

A Clinical Suspicion of Quetiapine-Induced Psychosis: A Case Report and Literature Review.

Quetiapine, a pharmacological agent within the class of atypical antipsychotics, is characterized by its efficacy in mood stabilization and its role in the modulation of serotonergic and dopaminergic pathways. Its therapeutic utility is broad, encompassing the management of acute psychotic episodes, schizophrenia, bipolar disorder, and treatment-resistant depressive states. Quetiapine's effectiveness extends to depressive disorders that do not exhibit classic psychotic features, with a side effect profile that is less burdensome than many alternative psychotropic medications. Its versatility in addressing a range of psychiatric conditions is useful in the psychopharmacological management of mood and thought disorders. However, like all drugs, quetiapine may have different effects relative to the individual. It is imperative to approach the administration of quetiapine carefully, ensuring any adverse effects are ameliorated for beneficial therapeutic outcomes. In this case report, we present a psychosis-naive 42-year-old male who developed psychotic symptoms after beginning a quetiapine regimen in order to manage major depressive disorder with suicidal ideation. Clinical suspicion of quetiapine-induced psychosis was a diagnosis considered due to symptom remission secondary to ziprasidone in the place of quetiapine. The determination of a suspected adverse drug reaction can utilize the Naranjo scale to demonstrate the likelihood of an adverse drug reaction. This patient scored a three on the Naranjo scale, indicating a possible adverse effect from quetiapine. Other potential etiologies of psychosis include medication-induced psychosis, major depressive disorder exacerbation, cocaine use/withdrawal, and brief psychotic disorder. Quetiapine-induced psychosis has not been described in the current literature, and therefore, this case report is solely based on clinical evaluation and is intended for educational purposes due to possible confounding factors and etiologies.

Reversible PCET and Ambient Catalytic Oxidative Alcohol Dehydrogenation by {V=O} Perfluoropinacolate Complexes.

A new air-stable catalyst for the oxidative dehydrogenation of benzylic alcohols under ambient conditions has been developed. The synthesis and characterization of this compound and the related monomeric and dimeric V(IV)- and V(V)-pinF (pinF = perfluoropinacolate) complexes are reported herein. Monomeric V(IV) complex (Me4N)2[V(O)(pinF)2] (1) and dimeric (µ-O)2-bridged V(V) complex (Me4N)2[V2(O)2(µ-O)2(pinF)2] (3a) are prepared in water under ambient conditions. Monomeric V(V) complex (Me4N)[V(O)(pinF)2] (2) may be generated via chemical oxidation of 1 under an inert atmosphere, but dimerizes to 3a upon exposure to air. Complexes 1 and 2 display a perfectly reversible VIV/V couple at 20 mV (vs Ag/AgNO3), whereas a quasi-reversible VIV/V couple at -865 mV is found for 3a. Stoichiometric reactions of 3a with both fluorenol and TEMPOH result in the formation of (Me4N)2[V2(O)2(µ-OH)2(pinF)2] (4a), which contains two V(IV) centers that display antiferromagnetic coupling. In order to structurally characterize the dinuclear anion of 4a, {K(18C6)}+ countercations were employed, which formed stabilizing K···O interactions between the counterion and each terminal oxo moiety and H-bonding between the oxygen atoms of the crown ether and µ-OH bridges of the dimer, resulting in {K(18C6)}2[V2(O)2(µ-OH)2(pinF)2] (4b). The formal storage of H2 in 4a is reversible and proton-coupled electron transfer (PCET) from crystals of 4a regenerates 3a upon exposure to air over the course of several days. Furthermore, the reaction of 3a (2%) under ambient conditions with excess fluorenol, cinnamyl alcohol, or benzyl alcohol resulted in the selective formation of fluorenone (82% conversion), cinnamaldehyde (40%), or benzaldehyde (7%), respectively, reproducing oxidative alcohol dehydrogenation (OAD) chemistry known for VOx surfaces and demonstrating, in air, the thermodynamically challenging selective oxidation of alcohols to aldehydes/ketones.

Diazepam Premedication in Primary Augmentation Mammoplasty.

Goals/Purpose: To evaluate the effects of preoperative oral diazepam on the postoperative course of patients undergoing primary augmentation mammoplasty in an outpatient surgical center. Methods/Technique: A retrospective review was conducted of 189 patients undergoing primary breast augmentation at an outpatient surgical center from 2012 to 2015. Patients receiving same-day premedication with oral diazepam were compared with a control group without premedication. Patients with combined surgical procedures were excluded with the exception of minor, superficial procedures. Patient demographics, perioperative medication use, operative details, and postoperative numeric pain scale (0-10) scores were collected. Results/Complications: Ninety-three patients (49%) were included in the premedication group and 96 (51%) in the control group. Difference in age, body mass index, implant size, and intraoperative opioid use were not statistically significantly different between the treatment and control groups (P > .05). No difference was noted in postoperative nausea, emesis, or antiemetic use between the 2 groups. The operative time was slightly longer in the control group (64.5 minutes vs 58.5 minutes, P = .006). Immediate postoperative pain (3.6 vs 4.4) and time to discharge (101 minutes vs 110 minutes) were slightly decreased in the premedication group; however, these values did not reach statistical significance. Intraoperative narcotic use was the same between groups, but postoperative narcotic pain medication use was higher in the premedication group (9.68 mg vs 8.26 mg, P = .036). Predischarge pain scores (2.87 vs 2.29, P = .006) were also noted to be slightly higher in the premedication group. Conclusions: Preoperative diazepam administration does not significantly decrease time to discharge in primary breast augmentation mammoplasty. Furthermore, its use may result in increased postoperative narcotic use and higher pain scores at the time of discharge.

High-throughput screening for discovery of benchtop separations systems for selected rare earth elements.

Rare earth (RE) elements (scandium, yttrium, and the lanthanides) are critical for their role in sustainable energy technologies. Problems with their supply chain have motivated research to improve separations methods to recycle these elements from end of life technology. Toward this goal, we report the synthesis and characterization of the ligand tris[(1-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamido)ethyl]amine, H31·TFA (TFA = trifluoroacetic acid), and complexes 1·RE (RE = La, Nd, Dy). A high-throughput experimentation (HTE) screen was developed to quantitatively determine the precipitation of 1·RE as a function of pH as well as equivalents of H31·TFA. This method rapidly determines optimal conditions for the separation of RE mixtures, while minimizing materials consumption. The HTE-predicted conditions are used to achieve the lab-scale separation of Nd/Dy (SFNd/Dy = 213 ± 34) and La/Nd (SFLa/Nd = 16.2 ± 0.2) mixtures in acidic aqueous media.

Sustainable Inorganic Chemistry: Metal Separations for Recycling.

Inorganic materials are critical components of clean energy technology. For example, rare earths are key for the function of electric car batteries and in permanent magnets used in wind turbines, and palladium helps to reduce harmful exhaust in automotive three-way catalysts. Many of the critical elements for these materials are of low abundance in the earth's crust, found in few places globally, and/or require energy- and resource-intensive purification. By comparison, many of these elements are concentrated in waste electrical and electronic equipment, which represents an attractive secondary resource. Inorganic chemists are ideally positioned to develop new chemistry and greener processes that are more efficient and use less hazardous reagents to separate high-value metals from waste electronics. The purpose of this Viewpoint is to highlight recent discoveries in fundamental inorganic chemistry that can contribute to new recycling technologies for gold, lithium, palladium, germanium, and rare earths, especially using simple approaches in solid-liquid extraction. Such fundamental studies are expected to help close metal supply chain loops and create circular economies.

The "pumpgate" incident: Stigma against lactating mothers in the U.S. workplace.

Studies conclude that breastfeeding for six months is associated with better lifelong health for the mother and the child. Mothers in the U.S. returning to work after maternity leave report difficulty with the need to take frequent breaks to pump breastmilk so many stop breastfeeding. Factors discouraging pumping breastmilk in the workplace motivated a content analysis of public comments posted in response to a legal deposition that occurred in January of 2011 in which an attorney who was a new mother was challenged about taking a break to pump breastmilk. A total of 899 public comments posted on Yahoo in 2015-2016 in response to this earlier incident were analyzed for content. Of these, only 336 mentioned breastfeeding. Overall, 148 comments showed support for breastfeeding or pumping breastmilk at work, while 182 comments showed moderate to strong disapproval (six unclassified). The majority of disapproving comments were critical of pumping breastmilk in the workplace. Implications of these findings for the duration of breastfeeding after returning to work are discussed.

Cardiac arrest risk standardization using administrative data compared to registry data.

BACKGROUND: Methods for comparing hospitals regarding cardiac arrest (CA) outcomes, vital for improving resuscitation performance, rely on data collected by cardiac arrest registries. However, most CA patients are treated at hospitals that do not participate in such registries. This study aimed to determine whether CA risk standardization modeling based on administrative data could perform as well as that based on registry data. METHODS AND RESULTS: Two risk standardization logistic regression models were developed using 2453 patients treated from 2000-2015 at three hospitals in an academic health system. Registry and administrative data were accessed for all patients. The outcome was death at hospital discharge. The registry model was considered the "gold standard" with which to compare the administrative model, using metrics including comparing areas under the curve, calibration curves, and Bland-Altman plots. The administrative risk standardization model had a c-statistic of 0.891 (95% CI: 0.876-0.905) compared to a registry c-statistic of 0.907 (95% CI: 0.895-0.919). When limited to only non-modifiable factors, the administrative model had a c-statistic of 0.818 (95% CI: 0.799-0.838) compared to a registry c-statistic of 0.810 (95% CI: 0.788-0.831). All models were well-calibrated. There was no significant difference between c-statistics of the models, providing evidence that valid risk standardization can be performed using administrative data. CONCLUSIONS: Risk standardization using administrative data performs comparably to standardization using registry data. This methodology represents a new tool that can enable opportunities to compare hospital performance in specific hospital systems or across the entire US in terms of survival after CA.

GDF-15 plasma levels in chronic obstructive pulmonary disease are associated with subclinical coronary artery disease.

BACKGROUND: Growth differentiation factor-15 (GDF-15), a cytokine associated with cardiovascular mortality, increases during chronic obstructive pulmonary disease (COPD) exacerbations, but any role in stable COPD is unknown. We tested associations between GDF-15 and subclinical coronary atherosclerosis, assessed by coronary artery calcium (CAC) score, in COPD subjects free of clinical cardiovascular disease (CVD). METHODS: Cross-sectional analysis of COPD participants (GOLD stages 2-4) in the COPDGene cohort without CVD at enrollment, using baseline CAC (from non-EKG-gated chest computed tomography) and plasma GDF-15 (by custom ELISA). We used multinomial logistic modeling of GDF-15 associations with CAC, adjusting for demographics, baseline risk (calculated using the HEART: Personal Heart Early Assessment Risk Tool (Budoff et al. 114:1761-1791, 2006) score), smoking history, measures of airflow obstruction, emphysema and airway disease severity. RESULTS: Among 694 participants with COPD (47% women, mean age 63.6 years) mean GDF-15 was 1,304 pg/mL, and mean CAC score was 198. Relative to the lower GDF-15 tertile, higher tertiles showed bivariate association with increasing CAC score (mid tertile odds ratio [OR] 1.80, 95% confidence interval [CI] 1.29, 2.51; higher tertile OR 2.86, CI 2.04, 4.02). This association was maintained after additionally adjusting for baseline CVD risk, for co-morbidities and descriptors of COPD severity and impact, markers of cardiac stress (N-terminal pro-B-type natriuretic peptide, troponin T) and of inflammation (Interleukin-6), and in subgroup analysis excluding men, diabetics, current smokers or those with limited ambulation. CONCLUSIONS: In ever-smokers with COPD free of clinical CVD, GDF-15 contributes independently to subclinical coronary atherosclerosis. TRIAL REGISTRATION: ClinicalTrials.gov, NCT00608764 . Registered 28 January 2008.

Evaluation of meniscal extrusion with posterior root disruption and repair using ultrasound.

BACKGROUND: Ultrasound techniques have been utilized for detection of discrete meniscus tears and extrusion. Meniscal extrusion is associated with increased contact pressure and decreased contact area contributing to the advancement of knee osteoarthritis. The purpose of this biomechanical study was to detect meniscal extrusion using a clinically available, portable ultrasound device. And further, to show that extent of injury and a weight-bearing state correlate with amount of extrusion. METHODS: A portable, hand-held ultrasound was utilized to image the lateral meniscus in association with (1) an intact posterior root attachment, (2) a 50% cut, (3) a 100% cut, and (4) repaired posterior root attachment. Images were obtained in an unloaded condition, and again under a static, physiologic (70kg) axial load for above injury levels, and again following repair. RESULTS: Significant differences in extrusion were noted between the intact and both the 50% cut (p=0.028) and 100% cut groups (p<0.001) all in the loaded position. No significant difference was found in extrusion between intact state and repaired posterior root in the axially loaded position (p=0.174). Both load (p=0.003) and injury level (p=0.005) had significant effects on the mean extrusion of the lateral meniscus. CONCLUSION: Sectioning of the lateral meniscus posterior root will produce significantly increased lateral extrusion of the meniscus under physiologic loads. Unlike MRI evaluation, weight-bearing ultrasound images allow a functional assessment of meniscus extrusion. Trans-tibial posterior root repair can restore the lateral meniscus position and integrity. CLINICAL RELEVANCE: This weight-bearing ultrasound technique can be an important assessment tool for complete evaluation of meniscus injuries.

MicroRNA-34a Negatively Regulates Efferocytosis by Tissue Macrophages in Part via SIRT1.

Apoptotic cell (AC) clearance (efferocytosis) is an evolutionarily conserved process essential for immune health, particularly to maintain self-tolerance. Despite identification of many recognition receptors and intracellular signaling components of efferocytosis, its negative regulation remains incompletely understood and has not previously been known to involve microRNAs (miRs). In this article, we show that miR-34a (gene ID 407040), well recognized as a p53-dependent tumor suppressor, mediates coordinated negative regulation of efferocytosis by resident murine and human tissue macrophages (Mø). The miR-34a expression varied greatly between Mø from different tissues, correlating inversely with their capacity for AC uptake. Transient or genetic knockdown of miR-34a increased efferocytosis, whereas miR-34a overexpression decreased efferocytosis, without altering recognition of live, necrotic, or Ig-opsonized cells. The inhibitory effect of miR-34a was mediated both by reduced expression of Axl, a receptor tyrosine kinase known to recognize AC, and of the deacetylase silent information regulator T1, which had not previously been linked to efferocytosis by tissue Mø. Exposure to AC downregulated Mø miR-34a expression, resulting in a positive feedback loop that increased subsequent capacity to engulf AC. These findings demonstrate that miR-34a both specifically regulates and is regulated by efferocytosis. Given the ability of efferocytosis to polarize ingesting Mø uniquely and to reduce their host-defense functions, dynamic negative regulation by miR-34a provides one means of fine-tuning Mø behavior toward AC in specific tissue environments with differing potentials for microbial exposure.

White matter microstructural abnormalities of the cingulum bundle in youths with 22q11.2 deletion syndrome: associations with medication, neuropsychological function, and prodromal symptoms of psychosis.

BACKGROUND: The 22q11.2 deletion syndrome (22q11.2DS) is regarded as an etiologically homogenous model for understanding neuroanatomic disruptions associated with a high risk for schizophrenia. This study utilized diffusion tensor imaging (DTI) to analyze white matter microstructure in individuals with 22q11.2DS. We focused on the cingulum bundle (CB), previously shown to be disrupted in patients with schizophrenia and associated with symptoms of psychosis. METHODS: White matter microstructure was assessed in the anterior, superior, and posterior CB using the tractography algorithm in DTIStudio. Neuropsychological function, presence of prodromal symptoms of psychosis, and medication history were assessed in all participants. RESULTS: Relative to controls, young adults with 22q11.2DS showed alterations in most DTI metrics of the CB. Alterations were associated with positive prodromal symptoms of psychosis. However, when individuals with 22q11.2DS were divided by usage of antipsychotics/mood stabilizers, the medicated and non-medicated groups differed significantly in axial diffusivity of the anterior CB and in fractional anisotropy of the superior CB. DTI metrics did not differ between the medicated group and the control group. CONCLUSIONS: Results suggest that the microstructure of the CB is altered in individuals with 22q11.2DS, and that those alterations may underlie positive prodromal symptoms of psychosis. Our findings further provide preliminary evidence that antipsychotic/mood stabilizer usage may have a reparative effect on white matter microstructure in prodromal 22q11.2DS, independent of the potential effects of psychosis. Future studies of white matter pathology in individuals with 22q11.2DS should test for potential effects of medication on white matter microstructure.

Basal gene expression by lung CD4+ T cells in chronic obstructive pulmonary disease identifies independent molecular correlates of airflow obstruction and emphysema extent.

UNLABELLED: Lung CD4+ T cells accumulate as chronic obstructive pulmonary disease (COPD) progresses, but their role in pathogenesis remains controversial. To address this controversy, we studied lung tissue from 53 subjects undergoing clinically-indicated resections, lung volume reduction, or transplant. Viable single-cell suspensions were analyzed by flow cytometry or underwent CD4+ T cell isolation, followed either by stimulation with anti-CD3 and cytokine/chemokine measurement, or by real-time PCR analysis. In lung CD4+ T cells of most COPD subjects, relative to lung CD4+ T cells in smokers with normal spirometry: (a) stimulation induced minimal IFN-γ or other inflammatory mediators, but many subjects produced more CCL2; (b) the T effector memory subset was less uniformly predominant, without correlation with decreased IFN-γ production. Analysis of unstimulated lung CD4+ T cells of all subjects identified a molecular phenotype, mainly in COPD, characterized by markedly reduced mRNA transcripts for the transcription factors controlling TH1, TH2, TH17 and FOXP3+ T regulatory subsets and their signature cytokines. This mRNA-defined CD4+ T cell phenotype did not result from global inability to elaborate mRNA; increased transcripts for inhibitory CD28 family members or markers of anergy; or reduced telomerase length. As a group, these subjects had significantly worse spirometry, but not DLCO, relative to subjects whose lung CD4+ T cells expressed a variety of transcripts. Analysis of mRNA transcripts of unstimulated lung CD4+ T cell among all subjects identified two distinct molecular correlates of classical COPD clinical phenotypes: basal IL-10 transcripts correlated independently and inversely with emphysema extent (but not spirometry); by contrast, unstimulated IFN-γ transcripts correlated independently and inversely with reduced spirometry (but not reduced DLCO or emphysema extent). Aberrant lung CD4+ T cells polarization appears to be common in advanced COPD, but also exists in some smokers with normal spirometry, and may contribute to development and progression of specific COPD phenotypes. TRIAL REGISTRATION: ClinicalTrials.gov as NCT00281229.

Preventive Effects of Eccentric Training on Acute Hamstring Muscle Injury in Professional Baseball.

BACKGROUND: Hamstring injuries are the second most common injury causing missed days in professional baseball field players. Recent studies have shown the preventive benefit of eccentric conditioning on the hamstring muscle group in injury prevention. Specifically, Nordic-type exercises have been shown to decrease the incidence of acute hamstring injuries in professional athletes. PURPOSE: This was a prospective study performed in coordination with a single Major League Baseball (MLB) organization (major and minor league teams) that targeted the effects of Nordic exercises on the incidence of acute hamstring injuries in the professional-level baseball player. STUDY DESIGN: Prospective cohort study; Level of evidence, 2. METHODS: The daily workouts of 283 professional baseball players throughout all levels of a single MLB organization were prospectively recorded. The intervention group participated in the Nordic exercise program and was compared with a randomly selected control group of professional athletes within the organization not participating in the exercise program. The incidence of hamstring injuries in both groups was compared, and the total number of days missed due to injury was compared with the 2 previous seasons. RESULTS: There were 10 hamstring injuries that occurred during the 2012 season among the 283 professional athletes that required removal from play. There were no injuries that occurred in the intervention group (n = 65, 0.00%; P = .0381). The number needed to treat (NNT) to prevent 1 hamstring injury was 11.3. The average repetitions per week of the injured group were assessed at multiple time points (2, 4, 6, and total weeks) prior to injury. There were significantly fewer repetitions per week performed in the injured group at all time points compared with overall average repetitions per week in the noninjured group (P = .0459, .0127, .0164, and .0299, respectively). After beginning the Nordic exercise program, there were 136 total days missed due to a hamstring injury during the 2012 season. This number was less than the 2011 season (273 days missed) and the 2010 season (309 days missed). CONCLUSION: Study results indicate the initiation of Nordic hamstring exercises may decrease the incidence of acute hamstring injuries and potentially decrease the total number of days missed due to injury in professional baseball players. CLINICAL RELEVANCE: The financial and competitive interest in professional baseball players is of large importance to the player, team, and fans. Prevention of injuries is as important to all parties involved as the treatment and rehabilitation following an injury. This prospective study shows the initiation of a simple, free exercise can reduce the incidence of hamstring injury in the professional-level baseball player.

Structural and electronic properties of old and new A2[M(pin(F))2] complexes.

Seven new homoleptic complexes of the form A2[M(pin(F))2] have been synthesized with the dodecafluoropinacolate (pin(F))(2-) ligand, namely (Me4N)2[Fe(pin(F))2], 1; (Me4N)2[Co(pin(F))2], 2; ((n)Bu4N)2[Co(pin(F))2], 3; {K(DME)2}2[Ni(pin(F))2], 4; (Me4N)2[Ni(pin(F))2], 5; {K(DME)2}2[Cu(pin(F))2], 7; and (Me4N)2[Cu(pin(F))2], 8. In addition, the previously reported complexes K2[Cu(pin(F))2], 6, and K2[Zn(pin(F))2], 9, are characterized in much greater detail in this work. These nine compounds have been characterized by UV-vis spectroscopy, cyclic voltammetry, elemental analysis, and for paramagnetic compounds, Evans method magnetic susceptibility. Single-crystal X-ray crystallographic data were obtained for all complexes except 5. The crystallographic data show a square-planar geometry about the metal center in all Fe (1), Ni (4), and Cu (6, 7, 8) complexes independent of countercation. The Co species exhibit square-planar (3) or distorted square-planar geometries (2), and the Zn species (9) is tetrahedral. No evidence for solvent binding to any Cu or Zn complex was observed. Solvent binding in Ni can be tuned by the countercation, whereas in Co only strongly donating Lewis solvents bind independent of the countercation. Indirect evidence (diffuse reflectance spectra and conductivity data) suggest that 5 is not a square-planar compound, unlike 4 or the literature K2[Ni(pin(F))2]. Cyclic voltammetry studies reveal reversible redox couples for Ni(III)/Ni(II) in 5 and for Cu(III)/Cu(II) in 8 but quasi-reversible couples for the Fe(III)/Fe(II) couple in 1 and the Co(III)/Co(II) couple in 2. Perfluorination of the pinacolate ligand results in an increase in the central C-C bond length due to steric clashes between CF3 groups, relative to perhydropinacolate complexes. Both types of pinacolate complexes exhibit O-C-C-O torsion angles around 40°. Together, these data demonstrate that perfluorination of the pinacolate ligand makes possible highly unusual and coordinatively unsaturated high-spin metal centers with ready thermodynamic access to rare oxidation states such as Ni(III) and Cu(III).

Nitrogen and sulfur requirements for Clostridium thermocellum and Caldicellulosiruptor bescii on cellulosic substrates in minimal nutrient media.

Growth media for cellulolytic Clostridium thermocellum ATCC 27405 and Caldicellulosiruptor bescii bacteria usually contain excess nutrients that would increase costs for consolidated bioprocessing for biofuel production and create a waste stream with nitrogen, sulfur and phosphate. C. thermocellum was grown on crystalline cellulose with varying concentrations of nitrogen and sulfur compounds, and growth rate and ethanol production response curves were determined. Both bacteria assimilated sulfate in the presence of ascorbate reductant, increasing the ratio of oxidized to reduced fermentation products. From these results, a low ionic strength, defined minimal nutrient medium with decreased nitrogen, sulfur, phosphate and vitamin supplements was developed for the fermentation of cellobiose, cellulose and acid-pretreated Populus. Carbon and electron balance calculations indicate the unidentified residual fermentation products must include highly reduced molecules. Both bacterial populations were maintained in co-cultures with substrates containing cellulose and xylan in defined medium with sulfate and basal vitamin supplements.

Cortical gyrification in velo-cardio-facial (22q11.2 deletion) syndrome: a longitudinal study.

INTRODUCTION: Velo-cardio-facial syndrome (VCFS) has been identified as an important risk factor for psychoses, with up to 32% of individuals with VCFS developing a psychotic illness. Individuals with VCFS thus form a unique group to identify and explore early symptoms and biological correlates of psychosis. In this study, we examined if cortical gyrification pattern, i.e. gyrification index (GI) can be a potential neurobiological marker for psychosis. METHOD: GIs of 91 individuals with VCFS were compared with 29 siblings and 54 controls. Further, 58 participants with VCFS, 21 siblings and 18 normal controls were followed up after 3 years and longitudinal changes in GI were compared. Additionally, we also correlated longitudinal changes in GI in individuals with VCFS with prodromal symptoms of psychosis on the Scale of Prodromal Symptoms (SOPS). RESULT: Individuals with VCFS had significantly lower GIs as compared to their siblings and normal controls. Longitudinal examination of GI did not reveal any significant group-time interactions between the three groups. Further, longitudinal change in GI scores in the VCFS group was negatively correlated with positive prodromal symptoms, with the left occipital region reaching statistical significance. CONCLUSION: The study confirms previous reports that individuals with VCFS have reduced cortical folding as compared to normal controls. However over a period of three years, there is no difference in the rate of change of GI among both individuals with VCFS and normal controls. Finally, our results suggest that neuroanatomical alterations in areas underlying visual processing may be an early marker for psychosis.