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IMPORTANCE: Ventricular tachycardia (VT) is associated with high mortality in patients with cardiac sarcoidosis (CS), and medical management of CS-associated VT is limited by high failure rates. The role of catheter ablation has been investigated in small, single-center studies. OBJECTIVE: To investigate outcomes associated with VT ablation in patients with CS. DESIGN, SETTING, AND PARTICIPANTS: This cohort study from the Cardiac Sarcoidosis Consortium registry (2003-2019) included 16 tertiary referral centers in the US, Europe, and Asia. A total of 158 consecutive patients with CS and VT were included (33% female; mean [SD] age, 52 [11] years; 53% with ejection fraction [EF]

Background Sarcoidosis is a granulomatous disease usually affecting the lungs, although cardiac morbidity may be common. The risk of these outcomes and the characteristics that predict them remain largely unknown. This study investigates the epidemiology of heart failure, atrioventricular block, and ventricular tachycardia among patients with and without sarcoidosis. Methods and Results We identified California residents aged ≥21 years using the Office of Statewide Health Planning and Development ambulatory surgery, emergency, or inpatient databases from 2005 to 2015. The risk of sarcoidosis on incident heart failure, atrioventricular block, and ventricular tachycardia were each determined. Linkage to the Social Security Death Index was used to ascertain overall mortality. Among 22 527 964 California residents, 19 762 patients with sarcoidosis (0.09%) were identified. Sarcoidosis was the strongest predictor of heart failure (hazard ratio [HR], 11.2; 95% CI, 10.7–11.7), atrioventricular block (HR, 117.7; 95% CI, 103.3–134.0), and ventricular tachycardia (HR, 26.1; 95% CI, 24.2–28.1) identified among all risk factors. The presence of any cardiac involvement best predicted each outcome. Approximately 22% (95% CI, 18%–26%) of the relationship between sarcoidosis and increased mortality was explained by the presence of at least 1 of these cardiovascular outcomes. Conclusions The magnitude of risk associated with sarcoidosis as a predictor of heart failure, atrioventricular block, and ventricular tachycardia, exceeds all established risk factors. Surveillance for and anticipation of these outcomes among patients with sarcoidosis is indicated, and consideration of a sarcoidosis diagnosis may be prudent among patients with heart failure, atrioventricular block, or ventricular tachycardia.

Objective: To test the hypothesis that sarcoidosis would be associated with the risk of atrial fibrillation (AF). Background: Most studies investigating cardiac manifestations of sarcoidosis have described the risks of heart failure, conduction system disease, and ventricular arrhythmias. The relationship between AF and sarcoidosis has been scarcely investigated. Methods: We analyzed a population-based cohort study of California residents aged ≥ 21 years in the Office of Statewide Health Planning and Development ambulatory surgery, emergency, or inpatient databases from 2005-2015 investigating risk and predictors of incident AF diagnoses in those with and without sarcoidosis. Those with prevalent AF were excluded. Linkage to the social security death index was utilized to ascertain mortality. Results: Among 21,969,699 California residents, 19,225 (0.09%) patients with sarcoidosis were identified. AF developed in 2,283 (11.6%) of those with sarcoidosis. Sarcoidosis was the strongest predictor of incident AF (HR 10.5, 95% CI 9.9-11.1) identified among all risk factors, including conventional AF predictors. The presence of evidence of cardiac involvement, namely heart failure and ventricular tachycardia, best predicted incident AF among those with sarcoidosis, while traditional risk factors better predicted incident AF in those without sarcoidosis. Approximately 44% (95 CI 31%-57%) of the increased mortality associated with sarcoidosis was statistically explained by the presence of AF. Conclusions: Sarcoidosis is a more potent predictor of incident AF than other well-established risk factors, underscoring the need for surveillance for AF among this population. These data suggest that AF in the absence of an identifiable cause should arouse suspicion for the disease.

The risks of industrial pollutants are well documented,1 but few studies have examined the public health consequences of climate change–related events such as wildfires. The health benefits of physical activity and harms of sedentary behavior are well established.2,3 Although air pollution has been associated with self-reported reductions in physical activity, such ascertainment may be prone to recall bias.4,5 Accelerometer-based trackers have become increasingly used to estimate physical activity and can accurately measure step counts.6

This study investigated the association between left ventricular ejection fraction (LVEF) and the risk of ventricular arrhythmias (VA), heart transplantation, and death in cardiac sarcoidosis (CS). We identified 110 CS patients meeting 2014 Heart Rhythm Society (HRS) diagnostic criteria with baseline LVEF35% (n = 32) or ≥35% (n = 78). The primary end point was sustained VA or sudden cardiac death (SCD), and secondary end points included risk of heart transplantation, death, or a composite. Logistic regression determined risk factors for VA/SCD, and Cox proportional hazards regression analysis was performed for secondary end points. Receiver operating curve analysis determined the best discrimination point of LVEF for each end point; sensitivity analyses evaluated the effects of higher LVEF on each end point. Over a follow-up of 2.6 (range 1.0 to 5.8) years, 49 (44.5%) CS patients experienced VA/SCD, including 19 of 32 (59.4%) with LVEF35%, and 30 of 78 (38.5%) with LVEF ≥35%. After adjustment, LVEF35% was not significantly associated with an increased risk of VA/SCD compared with LVEF ≥35% (odds ratio 1.3, 95% confidence intervals 0.5 to 3.7). Although LVEF35% was associated with an increased risk of heart transplantation and death (28.1% vs 12.8%, p = 0.05), this was not significant after adjustment (hazard ratio 1.7, 95% confidence intervals 0.5 to 9.0, p = 0.53). In conclusion, patients with CS experience high rates of VA, SCD, and heart transplantation, even when LVEF is mildly impaired or normal. Patients with LVEF35% are at particularly elevated risk of VA/SCD. Our findings highlight the imperative to investigate arrhythmia risk in all patients with CS, even in the setting of an otherwise reassuring LVEF.

The prevalence of cardiac involvement in sarcoidosis is under-recognized and is associated with multiple complications, including conduction block, arrhythmias, and sudden death. The comparative roles of common therapies have been inadequately studied. The purpose of this review is to examine the literature regarding treatments utilized to manage arrhythmias associated with cardiac sarcoidosis.

Introduction The diagnosis of cardiac sarcoidosis (CS) is difficult to ascertain due to the insensitivity of endomyocardial biopsy. Current diagnostic criteria require a positive endomyocardial biopsy or extra-cardiac biopsy with clinical features suggestive of CS. Common tests for diagnosis of pulmonary sarcoidosis include bronchoalveolar lavage (BAL), lung and mediastinal lymph node (MLN) biopsies. Our objective was to determine the diagnostic utility of these tests in patients with suspected CS and without prior history of pulmonary involvement. Methods This retrospective cohort study included 37 patients without history of extra-cardiac sarcoidosis referred for suspected CS. All patients underwent chest computed tomography (CT) staged using the modified Scadding criteria, and had BAL, and/or lung or MLN biopsy. BAL cellular analyses with lymphocytes>15% and/or CD4/CD8 ratio≥ 4 were considered suggestive of sarcoidosis. The number of positive biopsies and BALs were compared between normal CT (Scadding stage 0) and abnormal CT (Scadding stage 1–4) groups. Results A definitive diagnosis of sarcoidosis was ascertained in 18/31 (58%) patients undergoing lung or lymph node biopsy, and a potential diagnosis in 18/27 (67%) patients with BAL CD4/CD8>4 or lymphocytes>15%. Of the 12 patients in the normal CT group, 4/10 (40%) had positive lung biopsies, and 9/12 (75%) patients had either positive biopsy or BAL criteria. Conclusions In suspected cardiac sarcoidosis, a diagnosis of extra-cardiac sarcoidosis was ascertained in a majority of patients irrespective of degree of lung involvement on chest CT. Our results support referral for pulmonary biopsy/bronchoalveolar lavage in suspected CS to confirm the diagnosis of sarcoidosis.

Orthotopic heart transplant (OHT) is increasingly used for end-stage heart failure due to cardiac sarcoidosis (CS). However, concern regarding long-term outcomes in patients with CS after OHT persists because of multiorgan involvement.Baseline demographics and invasive hemodynamics were measured in 12 patients with CS and 28 patients with nonischemic cardiomyopathy requiring OHT at the time of transplantation, 1 week after OHT, and in routine follow-up. Primary endpoints included changes in pulmonary artery pressure, right ventricular stroke work index, and pulmonary compliance. Secondary endpoints included degree of allograft rejection and death.During a mean follow-up of 73.8 months, no differences in pulmonary artery pressures, right ventricular stroke work index, or cardiac index were observed in patient with CS (n = 12) compared with those without CS (n = 28) between 1 week after OHT and the most recent follow-up. Long-term follow-up showed that pulmonary hemodynamics remained normal in the CS group. International Society for Heart and Lung Transplantation (ISHLT) 1990 grade ≥ 1a rejection occurred less frequently in the CS group (17% vs 68%, P = 0.006), and 0 of 12 patients in the CS group experienced histologic or clinical recurrence of sarcoidosis or ≥2 rejection. Patients with CS had excellent survival after OHT, with 0 deaths or significant rejection.Patients with CS have similar post-transplant hemodynamics as patients without CS, without evidence of right ventricular dysfunction or pulmonary hypertension. Neither significant rejection nor recurrence of sarcoid in the allograft was observed in this cohort of patients with CS. Survival is similar between patients with CS and those without CS. Heart transplant is a viable strategy in selected patients with CS with excellent outcomes.

The purpose of this review is to examine the rapidly expanding literature regarding the effects of prenatal tobacco and postnatal secondhand smoke (SHS) exposure on child health and development. Mechanisms of SHS exposure are reviewed, including critical periods during which exposure to tobacco products appears to be particularly harmful to the developing fetus and child. The biological, biochemical, and neurologic effects of the small fraction of identified components of SHS are described. Research describing these adverse effects of both in utero and childhood exposure is reviewed, including findings from both animal models and humans. The following adverse physical outcomes are discussed: sudden infant death syndrome, low birth weight, decreased head circumference, respiratory infections, otitis media, asthma, childhood cancer, hearing loss, dental caries, and the metabolic syndrome. In addition, the association between the following adverse cognitive and behavioral outcomes and such exposures is described: conduct disorder, attention-deficit/hyperactivity disorder, poor academic achievement, and cognitive impairment. The evidence supporting the adverse effects of SHS exposure is extensive yet rapidly expanding due to improving technology and increased awareness of this profound public health problem. The growing use of alternative tobacco products, such as hookahs (a.k.a. waterpipes), and the scant literature on possible effects from prenatal and secondhand smoke exposure from these products are also discussed. A review of the current knowledge of this important subject has implications for future research as well as public policy and clinical practice.

Background Prior studies have shown that late gadolinium enhancement (LGE) on cardiac magnetic resonance (CMR) and fluorodeoxyglucose (FDG) positron emission tomography (PET) confer incremental risk assessment in patients with cardiac sarcoidosis (CS). However, the incremental prognostic value of the combined use of LGE and FDG compared to either test alone has not been investigated, and this is the aim of the present study. Methods Retrospective observational study of 56 symptomatic patients with high clinical suspicion for CS who underwent LGE-CMR and FDG-PET and were followed for the occurrence of death and/or malignant ventricular arrhythmias (VA). Results The combination of PET and CMR yielded the following groups: 1) LGE-negative/normal-PET (n=20), 2) LGE-positive/abnormal-FDG (n=20), and 3) LGE-positive/normal FDG (n=16). After a median follow-up of 2.6years (IQR 1.2–4.1), 16 patients had events (7 deaths, 10 VA). All, but 1, events occurred in patients with LGE. LGE-positive/abnormal-FDG (7 events, HR 10.1 [95% CI 1.2–84]; P =0.03) and LGE-positive/normal-FDG (8 events, HR 13.3 [1.7–107]; P =0.015) patients had comparable risk of events compared to the reference LGE-negative/normal-PET group. In adjusted Cox-regression analysis, presence of LGE (HR 18.1 [1.8–178]; P =0.013) was the only independent predictor of events. Conclusion CS patients with LGE alone or in association with FDG were at similar risk of future events, which suggests that outcomes may be driven by the presence of LGE (myocardial fibrosis) and not FDG (inflammation).

Extensive research shows maternal depression to be associated with poorer child outcomes, and characteristics of these mothers have been described. Recent research describes associations of paternal depressive symptoms and child behavioral and emotional outcomes, but characteristics of these fathers have not been investigated. This study describes characteristics of fathers with depressive symptoms in the USA. Utilizing data from 7,247 fathers and mothers living in households with children aged 5-17 years who participated in the Medical Expenditure Panel Survey 2004-2006, the Patient Health Questionnaire-2 was used to assess parental depressive symptoms, the Short Form-12 was used to examine paternal and maternal physical health, the Columbia Impairment Scale was used to measure child behavioral or emotional problems, and the Children with Special Health Care Needs Screener was used to identify children with special health care needs. In multivariate analyses, poverty (AOR 1.52; 95% CI 1.05-2.22), maternal depressive symptoms (AOR 5.77; 95% CI 4.18-7.95), living with a child with special health care needs (AOR 1.42, 95% CI 1.04-1.94), poor paternal physical health (AOR 3.31; 95% CI 2.50-4.38) and paternal unemployment (AOR 6.49; 95% CI 4.12-10.22) were independently associated with increased rates of paternal depressive symptoms. These are the first data that demonstrate that poverty, paternal physical health problems, having a child with special health care needs, maternal depressive symptoms, and paternal unemployment are independently associated with paternal depressive symptoms, with paternal unemployment associated with the highest rates of such problems.

BACKGROUND: The negative effects of maternal mental health problems on child health are well documented. In contrast, there is a profound paucity of information about paternal mental health's association with child health. OBJECTIVE: To investigate the association of paternal mental health problems and depressive symptoms and children's emotional or behavioral problems. METHODS: We analyzed Medical Expenditure Panel Survey data, which included a representative sample of US children (N = 21 993) aged 5 to 17 years and their mothers and fathers. The main outcome measure was child emotional or behavioral problems assessed by using the Columbia Impairment Scale. RESULTS: Paternal depressive symptoms, as assessed using the Patient Health Questionnaire–2, and mental health problems, more generally, assessed by using the Short-Form 12 Scale, were independently associated with increased rates of child emotional or behavioral problems even after controlling for numerous potential confounders including maternal depressive symptoms and other mental health problems. The adjusted odds ratio (aOR) for emotional or behavioral problems among children of fathers with depressive symptoms was 1.72 (95% confidence interval [CI]: 1.33–2.23) and the aOR associated with abnormal paternal scores on the mental component scale of the Short-Form 12 was 1.33 (95% CI: 1.10–1.62) for those within 1 SD below average and 1.48 (95% CI: 1.20–1.84) for those >1 SD below average. CONCLUSIONS: To the best of our knowledge, this is the first study to use a representative US sample to demonstrate that living with fathers with depressive symptoms and other mental health problems is independently associated with increased rates of emotional or behavioral problems of children.

(2011). Examining the Effects of Intrauterine and Postnatal Exposure to Tobacco Smoke on Childhood Cognitive and Behavioral Development. International Journal of Mental Health: Vol. 40, No. 1, pp. 39-64.

(2011). Nicotine Addiction: Mechanisms and Consequences. International Journal of Mental Health: Vol. 40, No. 1, pp. 22-38.

The diagnosis and management of cancer and cardiovascular disease during pregnancy poses a clinical challenge, with the potential for significant morbidity and mortality. A 30-year-old woman, g2p1, 10 weeks pregnant, noted progressive dyspnea and one episode of syncope. Past history was

Hemophagocytic lymphohistiocytosis (HLH) in immunocompromised hosts is a fulminant syndrome of immune activation with high rates of mortality that may be triggered by infections or immunodeficiency. Rapid diagnosis and treatment of the underlying disorder is necessary to prevent progression to multiorgan failure and death. We report a case of HLH in a patient with human immunodeficiency virus, disseminated histoplasmosis, Mycobacterium avium complex, and Escherichia coli bacteremia. We discuss management of acutely ill patients with HLH and treatment of the underlying infection versus initiation of HLH-specific chemotherapy.

The connection between housing and health is well established. Physical, chemical, and biological aspects of the child's home, such as cleanliness, moisture, pests, noise, accessibility, injury risks, and other forms of housing environmental quality, all have the potential to influence multiple aspects of the health and development of children. Basic sanitation, reduced household crowding, other improvements in housing and expanded, and improved housing regulations have led to advances in children's health. For example, lead poisoning prevention policies have profoundly reduced childhood lead exposure in the United States. This and many other successes highlight the health benefits for families, particularly children, by targeting interventions that reduce or eliminate harmful exposures in the home. Additionally, parental mental health problems, food insecurity, domestic violence, and the presence of guns in children's homes all are largely experienced by children in their homes, which are not as yet considered part of the Healthy Homes agenda. There is a large movement and now a regulatory structure being put in place for healthy housing, which is becoming closely wedded with environmental health, public health, and the practice of pediatrics. The importance of homes in children's lives, history of healthy homes, asthma, and exposures to lead, carbon monoxide, secondhand/thirdhand smoke, radon, allergy triggers is discussed, as well as how changes in ambient temperature, increased humidity, poor ventilation, water quality, infectious diseases, housing structure, guns, electronic media, family structure, and domestic violence all affect children's health.

The papillary and trabecular muscles constitute a significant percentage of left ventricular mass and volume. The influence of the papillary and trabecular muscles on left ventricular parameters has not been described with multidetector CT angiography.The aims of this study are (1) to derive reference values for left ventricular volumetric parameters both including and excluding the papillary and trabecular muscles and (2) to establish the optimal segmentation method for measuring these values.A total of 179 subjects (mean age, 55.4 ± 9 years; 102 women) without heart disease and at low risk of cardiovascular disease who underwent CT angiography were selected. Left ventricular volumes, myocardial volume, and ejection fraction were measured with epicardial and 2 endocardial trace methods, including and excluding trace for the papillary and trabecular muscles. Values of all parameters obtained by both endocardial trace methods were compared.Significant difference between both trace groups for all parameters on both sexes was found (P.001). Significant differences in precision error of remeasurement were found in the including trace (3.6%) compared with the excluding trace (4.7%; P.05) and in the epicardial trace (2.2%) compared with both endocardial traces (P.001).The left ventricular parameters measured by CT angiography were influenced significantly by the trace method by including or excluding the papillary and trabecular muscles. The dual-standard reference values of left ventricular parameters were established, and the optimal segmentation methods were definite in considering the heart size and image quality studied with retrospective and prospective CT angiography.

Numerous studies have investigated the deleterious effects of maternal depression on child outcomes. Knowledge of characteristics of these mothers is incomplete, as most studies utilize small samples or limit investigation to the postpartum period. Utilizing data from a nationally representative sample of 7,211 fathers and mothers living in households with children aged 5–17 years who participated in the Medical Expenditure Panel Survey (MEPS) 2004–2006, the Patient Health Questionnaire-2 (PHQ-2) was used to assess parental depressive symptoms, the Short Form-12 (SF-12) was used to examine paternal and maternal physical health, and the Columbia Impairment Scale was used to measure child behavioral or emotional problems. In multivariate analyses, maternal unemployment (AOR 1.76, 95 % CI 1.31–2.35); living with smokers (AOR 1.82, 95 % CI 1.12–2.94); poor maternal physical health (AOR 2.31; 95 % CI 1.81–2.94); living with children with behavioral or emotional problems (AOR 2.95, 95 % CI 2.30–3.96); and paternal depressive symptoms (AOR 5.11, 95 % CI 1.97–13.25) each were independently associated with increased rates of maternal depressive symptoms. This paper is the first we are aware of to use a nationally representative sample to investigate characteristics associated with maternal depressive symptoms and found that maternal unemployment, living with smokers, poor maternal physical health, having children with behavioral or emotional problems, and paternal depressive symptoms are each independently associated with maternal depressive symptoms. In these data, paternal depressive symptoms are associated with the greatest risk of mothers exhibiting depressive symptoms, a finding that we believe has never before been shown.

We studied 13 patients with human immunodeficiency virus (HIV) infection and a chronic pruritic folliculitis that was unresponsive to systemic treatment with bactericidal anti-staphylococcal antibiotics. The skin eruption was characterized by multiple urticarial follicular papules scattered on the trunk (100%), the head and neck (85%), and the proximal aspect of the extremities (62%). Absolute peripheral eosinophil counts were increased in six of 13 patients; a relative peripheral eosinophilia was present in 10 of 13 patients. Serum IgE levels were elevated in all seven patients tested (range, 88 to 9050 IU). Histopathologic features included a folliculitis with eosinophils. Pathogenic bacteria were not consistently found by routine bacterial skin cultures, cultures of skin biopsy specimens, or histopathologic evaluation. CD4 counts were decreased in all of the 12 patients tested (less than 300 cells per cubic millimeter) and were below 250 cells per cubic millimeter in 10 patients. A clinical response was noted to astemizole, to ultraviolet light in the B range, and to topical clobetasol propionate. These observations demonstrate that HIV-associated eosinophilic folliculitis is a unique HIV-related cutaneous disorder that is characterized by a culture-negative, chronic, pruritic folliculitis and a characteristic histopathologic picture. Of special importance, because it is associated with CD4 counts of less than 250 to 300 cells per cubic millimeter, eosinophilic folliculitis appears to be an important clinical marker of HIV infection and, particularly, of patients at increased risk of developing opportunistic infections. We suggest that the term eosinophilic pustular folliculitis (Ofuji's disease), previously used to describe this dermatosis in HIV-infected patients, should be discarded.

The mass spectra of several naturally occuring Sceletium alkaloids, as well as several synthetic variants, have been investigated. Techniques used include high resolution mass measurements, analysis of metastable transitions by the technique of ion defocusing and specific deuterium labeling in conjunction with low resolution mass spectrometry. Characteristic major fragmentation pathways have been determined for four basic structure types studied: the cis-3a-aryl-octahydroindole ring system, exemplified by mesembrine; its 2,3-pyrido analog, Sceletium A4; the seco series of pyridine bases, represented by tortuosamine; and the seco analog of the mesembrine-type represented by tortuosamine; and the seco analog of the mesembrine-type represented by dehydrojoubertiamine.

A new compound has been isolated from the common mushroom (Agaricus bisporus) which, on oxidation by a partially purified preparation of the enzyme "inhibitor synthetase," has been converted to a quinone present in this species. Chemical and spectral studies indicate that the structure of the quinone precursor is γ-l-glutaminyl-4-hydroxybenzene. This structure has been verified by synthesis.

Research in the "genetics" of human behavioral disorders* confronts a complex of problems from the moment of its inception. First of all, how does one go about doing this "genetic" research when one obviously has no leverage on the implicated genes per se? One cannot engage in the traditional forms of experimental breeding, so that one has no control at all over the breeding of his sample population; and that is as it should be. No matter which behavioral disorder one studies, it is apparent from the outsetand always has beenthat its distribution in families follows no Mendelian pattern. What are we talking about, then, when we talk about the "genetics" of such disorders? The truth is that much of psychiatric "genetics" has been devoted to explaining awaynot explainingthe non-Mendelian distributions found. Initially, there was a predilection for positing such factors as reduced penetrance and varying manifestation in homozygotes and heterozygotes, depending on whether one's own preference was for a "theory" of dominance or recessiveness. Such "theories? are based, in turn, on empirical statistical distributions that are fallibly determined and that vary appreciably from sample to sample and from study to study. In more recent times, the tendency has been to turn away from such theorizing and either to postulate a simple, additive, polygenic system to explain away the non-Mendelian distributions or to speculate that such disorders are genetically heterogeneous, i.e., that there are a number of different major single-genes at different loci that can lead to the same type of disorder. It is a simple matter for any investigator to choose to believe one kind of "theory" rather than another, and the fact is that the variety and abundance of "genetic theories" that have been proposed in the past fifty years constitute an eloquent testimonial to the fact that we have been offered articles of faith and fancy rather than hard substance on which to develop a genetic theory of human behavioral disorders.

The lead tetraacetate oxidation of the tertiary alcohol 1 gives rise to two products, 3a and 4a, which contain a transannular oxide bridge. These structures are determined by analytical and spectral properties and by two independent chemical interconversions. The stereochemistry can be deduced from these reactions. Two possible mechanisms for the formation of the products are presented.

Nitrosyl fluoride was added to a series of steroid 9(11)-olefins to give, in moderate yield, the corresponding 11-nitrimino-9α-fluoro derivatives. The nitrimines could be hydrolyzed to the 11-ketones, or reduced by appropriate reagents to the corresponding 11-nitramines, 11-imines, and 11-amines. These reactions constitute a convenient and direct way to introduce fluorine into the 9α position of steroids. The scope and limitations of this reaction are discussed.

The novel heme prosthetic group of Escherichia coli NADPH-sulfite reductase (EC 1.8.1.2) has been identified as an iron tetrahydroporphyrin of the isobacteriochlorin type (adjacent pyrrole rings reduced) with eight carboxylic acid side chains. The number of carboxyl groups was established by the following experiments. Esterification with 14CH3OH resulted in incorporation of 7.4 moles of 14C per mole of heme. The fragmentation pattern of the demetallized heme (porphin) methyl ester and a comparison of the heaviest mass peaks of the porphin ethyl and methyl esters was consistent with the presence of eight carboxylate ester side chains. The porphin methyl ester migrated similarly to uroporphyrin I octamethyl ester in two thin layer chromatographic systems. The reduction state of the porphin nucleus was determined as follows. The infrared spectrum of the porphin ethyl ester showed a band at 1603 cm-1, characteristic of reduced porphins. The absorption spectra of the porphin ester (λmax (ratios) = 378 (3.3), 510 (0.37), 545 (0.67), 588 (1.00), 638 (0.15) nm) in neutral or basic media and its tin, copper, and zinc derivatives were similar to those of synthetic isobacteriochlorins and their corresponding metal derivatives. The porphin in neutral solvents exhibited an intense orange fluorescence (λmax = 597 and 640 nm for emission) indicating the presence of a cyclically conjugated porphin macrocycle. The tin porphin ester was not photoreduced under conditions which led to conversion of tin uroporphyrin octamethyl ester to the tetrahydro derivative. Precise molecular masses of several derivatives of the sulfite reductase porphin yielded a unique empirical formula for each derivative; these formulas, when restricted to a porphin with eight carboxylate side chains, require the porphin nucleus to be at the tetrahydro or more reduced level. No formulas compatible with octacarboxylate porphyrins or chlorins could be obtained. The empirical formula for the sulfite reductase heme is FeC42H44N4O16 (z ligands not included). It is suggested that the compound is an iron-containing methylated urotetrahydroporphyrin.

Fur die Bildung neuartiger Oxydationsprodukte, die bei der Reaktion eines B-Norsteroidalkohols mit Blei-tetraacetat entstehen, werden zwei Mechanismen vorgeschlagen: Die bekannte Spaltungs-Additions-Reaktion eines Alkoxy Radikals und die bisher unbekannte Umlagerung eines Alkyl-tertiaralkoxy Radikals.

Rearrangement of the molecular ions of tetracyclone, tetraphenylquinone, tetraphenylthiophene dioxide and pentaphenylcyclopentadienol prior to decomposition, rather than formation of a symmetrical [C4Ar4]+˙ ion, is considered as an alternative method for the production of [C2Ar2]+˙. The p-fluoro substituent is used to elicit information about the positional origins of the [C2Ar2]+˙ fragments. Operation of a double focusing mass spectrometer in the defocused mode reveals that the integrity of the molecular ion in different systems is affected to varying degrees, ranging from total lack of rearrangement to virtually complete scrambling.

The ruthenium porphyrin carbonyl (I) reacts with perfluorokerosene and perfluorotributylamine to give ions of the type [M – CO + CnF2n], n = 1 to 4.

A method for the identification of delta9-tetrahydrocannabinol by gas chromatography mass spectrometry has been developed, and this method has been compared with other techniques, such as detection via thin-layer chromatography using tritium labeled delta9-tetrahydrocannibinol and a dual gas chromatographic method. The gas chromatographic mass spectrometric method was found to be equal or superior to other techniques and has the added advantage of being highly specific for the compound analyzed. An alternate approach using chemical ionization is also described; however, this procedure does not show significant advantages over the electron impact method. These methods show a practical lower detection limit of 500 pg ml-1 of plasma in clinical practice.

Gas chromatography using a short packed column (45 cm, 0.2 cm i.d., 2% OV-101 on Gas-Chrom Q) with mass spectrometric detection in the selected ion monitoring mode has been found satisfactory for the analysis of lower as well as higher polybrominated biphenyls. Acceptable sensitivity (< 1 ng) may be achieved for this method by focusing selectively at either the low (m/z 20-600) or the high m/z 600-1000) range of the quadrupole filter (low range for mono- through hexabromobiphenyl, high range for hexa- through decabromobiphenyl). A tuning technique has been developed for low range and high range polybrominated biphenyls using the ion abundances of perfluorotributylamine as a standard. Standard ions for the quantitation of mono- through decabromo-biphenyls were selected and validated. The technique was applied to the analysis of a variety of environmental samples.