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Taub v. State.

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Academies and Institutes↗

Electronic States and Spectra of BiO.

The electronic spectrum of the BiO radical has been studied by Fourier transform emission spectroscopy, laser-induced fluorescence, and excimer laser photolysis techniques. Six new electronic states, A1 (Omega = 3/2) (Te = 11 528.8 cm-1, omegae = 530.4 cm-1, omegaexe = 2.42 cm-1), G (Omega = 3/2) (Te = 20 273 cm-1, omegae = 499 cm-1, omegaexe = 2.6 cm-1), H (Omega = 1/2) (Te = 20 469.76(6) cm-1, omegae = 471.63(18) cm-1, omegaexe = 2.153(35) cm-1), I (Omega = 1/2) (Te = 21 982.50(2) cm-1, omegae = 506.50(11) cm-1, omegaexe = 3.263(34) cm-1), J (Omega = 3/2) (Te = 25 598.95(42) cm-1, omegae = 489.95(16) cm-1, omegaexe = 2.309(45) cm-1), and K (Omega = 1/2) (Te = 26 744.7(2) cm-1, omegae = 420.6(4) cm-1, omegaexe = 5.25(5) cm-1), and 14 new electronic transitions (A1 <-- X1, G --> X2, H left and right arrow X1, H --> A2(A), I left and right arrow X1, I --> A2, J left and right arrow X1, J left and right arrow X2, K left and right arrow X1, K left and right arrow X2, K --> A2, B left and right arrow X2, B --> A2, C left and right arrow X2) have been detected. Time-resolved measurements of the fluorescence decays have yielded the radiative lifetimes of the v = 0 levels of most states up to <30 500 cm-1 energy (tauX2 = 480 +/- 100 µs, tauA2 = 9.3 +/- 1.5 µs, tauH = 15 +/- 3 µs, tauI = 16 +/- 3 µs, tauJ = 4.9 +/- 0.9 µs, tauK = 2.6 +/- 0.3 µs, tauB = 0.55 +/- 0.08 µs, tauC = 0.84 +/- 0.15 µs) and rate constants for quenching of the states by some rare gas atoms and simple molecules. The new electronic states A1, G, H, I, J, and K and the previously known levels X1, X2, A2(A), B, C, and D are assigned to spin-orbit states arising from low-energy valence configurations of BiO with the help of detailed theoretical data calculated by Alekseyev et al. (J. Chem. Phys. 100, 8956-8968 (1994)). Copyright 1998 Academic Press.

Journal Article↗

Current treatment options and biology of peritoneal mesothelioma: meeting summary of the first NIH peritoneal mesothelioma conference.

Peritoneal mesothelioma is a rare cancer of the peritoneum with about 250 new cases diagnosed each year in the United States. It is the second most common site for mesothelioma development and accounts for 10-20% of all mesotheliomas diagnosed in the United States. A meeting sponsored by the NIH Office of Rare Diseases was held in Bethesda, Maryland on September 13 and 14, 2004. The objective of this meeting was to review the epidemiology, biology and current surgical and medical management of peritoneal mesothelioma. In addition, the meeting also discussed clinical and pre-clinical evaluation of novel treatments for mesothelioma as well as ongoing laboratory research to better understand this disease. This report summarizes the proceedings of the meeting as well as directions for future clinical and basic research.

Clinical Trials as Topic↗

Two-electron transfer for Tl(aq)(3+)/Tl(aq)(+) revisited. Common virtual [Tl(II)-Tl(II)](4+) intermediate for homogeneous (superexchange) and electrode (sequential) mechanisms.

Homogeneous and electrochemical two-electron transfers within the Tl(aq)(3+)/Tl(aq)(+) couple are considered on a common conceptual basis. For the 2 equiv electrochemical reduction of Tl(aq)(3+) to Tl(aq)(+), the intermediate state with a formal reduction potential, E(1) = 1.04 +/- 0.10 V vs the normal hydrogen electrode, was detected, different from the established value of 0.33 V for a Tl(3+)/Tl(2+) couple. Examination of obtained electrochemical (cyclic voltammetry (CV) and rotating disk electrode techniques, along with the CV-curve computer simulation procedure) and literature data indicate that the detected formal potential cannot be the property of electrode-adsorbed species, but rather of the covalently interacting dithallium intermediate [Tl(II)-Tl(II)](4+) located at the outer Helmholtz plane. The analysis of microscopic mechanisms, based on the recent hypothesis of H. Taube and the Marcus-Hush theory extended by Zusman and Beratan, and Koper and Schmickler, revealed that the homogeneous process most probably takes place through the superexchange inner-sphere two-electron-transfer mechanism, via an essentially virtual (undetectable) dithallium intermediate. In contrast, the electrochemical process occurs through a sequential mechanism, via the rate-determining step of Tl(aq)(2+) ion formation immediately followed by activationless formation of the metastable (CV-active) dithallium state. The second electrochemical electron-transfer step is fast, and shows up only in the peak height (but not in the shape) of the observed CV cathodic wave. The anodic wave for a microscopically reverse process of the oxidation of Tl(aq)(+) to Tl(aq)(3+) cannot be observed within the considered potential range due to the blocking of through-space electron transfer by the competitor process of ion transfer to the electrode.

Journal Article↗

A new class of angiotensin-converting enzyme inhibitors.

Much current attention focuses on the renin-angiotensin system in relation to mechanisms controlling blood pressure and renal function. Recent demonstrations (ref. 1, ref. 2 and refs therein) that angiotensin-converting enzyme inhibitors show promising clinical antihypertensive properties have been of particular interest. We now report on the design of a novel series of substituted N-carboxymethyl-dipeptides which are active in inhibiting angiotensin-converting enzyme at nanomolar levels. We suggest that these compounds are transition-state inhibitors and that extensions of this design to other metalloendopeptidases merit further study.

Angiotensin-Converting Enzyme Inhibitors↗

The prognostic value of ECG-gated SPECT imaging in patients undergoing stress Tc-99m sestamibi myocardial perfusion imaging.

BACKGROUND: The ability of stress radionuclide myocardial perfusion imaging to predict adverse cardiac events is well accepted. As left ventricular systolic function has also been shown to be an important prognostic indicator, the objective of this study was to determine whether electrocardiography (ECG)-gated single photon emission computed tomography (SPECT) functional data add additional power. METHODS AND RESULTS: In this study 3207 patients who underwent stress myocardial perfusion imaging with ECG gating, without early (</=60 days) revascularization, were studied. Subsequent nonfatal myocardial infarction and cardiac death were related to perfusion and ECG-gated SPECT ventricular function parameters. Cox proportional hazards regression analysis was used to evaluate the independent predictive value of these parameters, as well as their added utility over clinical and ECG parameters. Patients with abnormal perfusion images had an annual event rate of 5.1% compared with 1.6% for patients with normal images (P <.001). An abnormal gated SPECT wall motion score was associated with an annual event rate of 6.1% compared with 1.6% for a normal score (P <.001), and an abnormal left ventricular ejection fraction was associated with an event rate of 7.4% compared with 1.8% for normal patients (P <.001). Abnormal ECG-gated SPECT results worsened outcome in both patients with normal perfusion images and those with abnormal perfusion images. Cardiac death was predicted by the number of territories with a perfusion defect and an abnormal ejection fraction, whereas myocardial infarction was predicted by the number of territories with a perfusion defect but not by ejection fraction. CONCLUSIONS: Ventricular function data from ECG-gated SPECT add important prognostic value to data obtained from perfusion imaging alone in predicting adverse cardiac events.

Adult↗

Tmtacn, tacn, and triammine complexes of (eta 6-arene)OsII: syntheses, characterizations, and photosubstitution reactions (tmtacn = 1,4,7-trimethyl-1,4,7-triazacyclononane; tacn = 1,4,7-triazacyclononane).

A series of (eta 6-arene)OsII complexes containing the saturated nitrogen donor ligands tmtacn, tacn, and NH3 are prepared and characterized. The electrochemical properties and photochemical reactions of these complexes are studied, and the solid-state structures for [(eta 6-p-cymene)Os(tacn)](PF6)2 (1) and [(eta 6-p-cymene)Os(tmtacn)](PF6)2 (2) are determined. Single-crystal X-ray data: 1, orthorhombic, space group Pbca-D2h15 (No. 61), with a = 14.716(3) A, b = 17.844(3) A, c = 18.350(4) A, V = 4819(2) A3, and Z = 8; 2, monoclinic, space group C2-C2(3) (No. 5), with a = 17.322(4) A, b = 10.481(3) A, c = 15.049(4) A, beta = 98.72 degrees, V = 2701(1) A3, and Z = 4.

Electrochemistry↗

The depressant effect of halothane and sodium thiopental on the spontaneous and evoked activity of dorsal horn cells: lamina specificity, time course and dose dependence.

The effects of halothane and sodium thiopental on dorsal horn cell unit activity were studied in the lumbar spinal cord of decerebrate, low thoracic spinal cats. Both halothane (0.5, 1 and 1.5%) and sodium thiopental (2.5, 5 and 10 mg/kg) depressed, in a dose-dependent manner, the spontaneous firing frequency of cells in Rexed laminae I, V and VI and the evoked firing frequency of cells in laminae I and V. They, however, had no effect on cells in lamina IV. The maximum depression of cell activity occurred 5 to 8 minutes after inhalation of halothane and 2 to 3 minutes after the intravenous administration of sodium thiopental. The recovery of cell activity occurred within 15 to 30 minutes after discontinuation of halothane and within 10 to 30 minutes after intravenous administration of sodium thiopental. The depressive effect of halothane and sodium thiopental, both primarily hypnotic anesthetics, on lamina VI cells is in contrast to our previous finding that morphine sulfate, nitrous oxide and ketamine hydrochloride, primarily analgesic agents, had no significant effect on this lamina.

Animals↗

Sleep pattern variations as a function of age in affective disorders.

Polygraphic features of nocturnal sleep were evaluated in young adult psychiatric patients during acute unipolar depressive episodes. Averaged values and variability of polygraphic indexes were examined in 12 depressed patients under the age of 26 individually matched with a normal control group. Sleep was polygraphically recorded in the Laboratory for three consecutive nights from 12-8.00 a.m. Although average total time asleep was approximately equivalent (greater than 7.3 hr) between groups, depressives accumulated significantly: (i) less stage 4, (ii) more stage 1, (iii) vascillations among sleep stages, but (iv) most especially increased transitions into stage 1 and (v) intermittent wakefulness. The recorded sleep perturbations in young depressives were extremely variable across nights and among individuals. This was especially conspicuous across nights as reflected by significantly larger variability (SD) for: (i) transitions into stage 1, (ii) intermittent wakefulness and (iii) epsilon accumulations of stage 2. Variability (the SD) between individuals was also more substantial for: (i) total time asleep, (ii) stage 1, (iii) intermittent wakefulness, (iv) epsilon stage shifts and (v) intrusions into stage 1. The polygraphic recordings of young depressives contained anomalies reported for clinical pathologic states accompanied by physiological disregulation such as hypersomnia, narcolepsy and schizoaffective disorders. Polygraphic indexes reflecting the capacity (i) to remain asleep (means +/- SDs) and (ii) accumulate continuous sleep (SDs) indicated an imbalance of the 24-hr rest (sleep)--activity (waking) cycle was present in this constituency concomitant with affective distress. A comparison with selected cross-sectional polygraphic studies revealed that sleep cycle aberrations in young adult depressives were less intense than those which become exacerbated as a function of advanced age. By contrast to prepubertal children or postadolescent young adults who are depressed, elderly accumulate: (i) lower total sleep times, (ii) less proportions of stages 3-4 and (iii) remain awake longer. It is concluded that sleep-polygraphic anomalies in postadolescent depression are an attenuated form of the REM-NREM cycle perturabation endemic to affective disease occurring with advanced age or senescence.

Adolescent↗

Cooperative ligation, back-bonding, and possible pyridine-pyridine interactions in tetrapyridine-vanadium(II): a visible and X-ray spectroscopic study.

The binding of pyridine by V(II) in aqueous solution shows evidence for the late onset of cooperativity. The K(1) governing formation of [V(py)](2+) (lambda(max) = 404 nm, epsilon(max) = 1.43 +/- 0.3 M(-1) cm(-1)) was determined spectrophotometrically to be 11.0 +/- 0.3 M(-)(1), while K(1) for isonicotinamide was found to be 5.0 +/- 0.1 M(-1). These values are in the low range for 3d M(2+) ions and indicate that V(II).py back-bonding is not significant in the formation of the 1:1 complex. Titration of 10.5 mM V(II) with pyridine in aqueous solution showed an absorption plateau at about 1 M added pyridine, indicating a reaction terminus. Vanadium K-edge EXAFS analysis of 63 mM V(II) in 2 M pyridine solution revealed six first-shell N/O ligands at 2.14 A and 4 +/- 1 pyridine ligands per V(II). UV/vis absorption spectroscopy indicated that the same terminal V(II) species was present in both experiments. Model calculations showed that in the absence of back-bonding only 2.0 +/- 0.2 and 2.4 +/- 0.2 pyridine ligands would be present, respectively. Cooperativity in multistage binding of pyridine by [V(aq)](2+) is thus indicated. XAS K-edge spectroscopy of crystalline [V(O(3)SCF(3))(2)(py)(4)] and of V(II) in 2 M pyridine solution each exhibited the analogous 1s --> (5)E(g) and 1s --> (5)T(2g) transitions, at 5465.5 and 5467.5 eV, and 5465.2 and 5467.4 eV, respectively, consistent with the EXAFS analysis. In contrast, [V(py)(6)](PF(6))(2) and [V(H(2)O)(6)]SO(4) show four 1s --> 3d XAS transitions suggestive of a Jahn-Teller distorted excited state. Comparison of the M(II)[bond]N(py) bond lengths in V(II) and Fe(II) tetrapyridines shows that the V(II)[bond]N(py) distances are about 0.06 A shorter than predicted from ionic radii. For [VX(2)(R-py)(4)] (X = Cl(-), CF(3)SO(3)(-); R = 4-Et, H, 3-EtOOC), the E(1/2) values of the V(II)/V(III) couples correlate linearly with the Hammett sigma values of the R group. These findings indicate that pi back-bonding is important in [V(py)(4)](2+) even though absent in [V(py)](2+). The paramagnetism of [V(O(3)SCF(3))(2)(py)(4)] in CHCl(3), 3.8 +/- 0.2 mu(B), revealed that the onset of back-bonding is not accompanied by a spin change. Analysis of the geometries of V(II) and Fe(II) tetrapyridines indicates that the ubiquitous propeller motif accompanying tetrapyridine ligation may be due to eight dipole interactions arising from the juxtaposed C-H edges and pi clouds of adjoining ligands, worth about -6 kJ each. However, this is not the source of the cooperativity in the binding of multiple pyridines by V(II) because the same interactions are present in the Fe(II)-tetrapyridines, which do not show cooperative ligand binding. Cooperativity in the binding of pyridine by V(II) is then assigned by default to V(II)-pyridine back-bonding, which emerges only after the first pyridine is bound.

Crystallography, X-Ray↗

The effects of photic driving on mood states.

The EEG photic driving response is a sensitive neurophysiological measure. It has been used to assess drug effects, forms of epilepsy, neurological status of Alzheimer's patients, and physiological arousal. Photic driving also impacts the psychological status of a person by producing increased visual imagery and decreased physiological and subjective arousal. In this study, ten volunteers underwent nocturnal polysomnography followed by six daytime testing sessions. The six sessions consisted of the alpha attenuation test, two visual analog scales for mood, the Stanford Sleepiness Scale, photic stimulation, and the multiple sleep latency test. These tests were administered 2 hours upon awakening and every 2 hours thereafter. The mean mood across the six daytime testing sessions was computed for all mood variables pre- and post-photic stimulation. Significant differences were found for the subjective moods "sleepy," "alert," and "effort." However, no significant differences were found for pre- and post-photic driving for "angry," "irritable," "hungry," "tense," "overall," "happy," "sexual," and "sad." Additionally, all participants reported increased visual imagery during photic driving, as measured by their responses to an imagery questionnaire.

Adult↗

Disability and quality of life impact of mental disorders in Europe: results from the European Study of the Epidemiology of Mental Disorders (ESEMeD) project.

OBJECTIVE: This manuscript examines the impact of mental health state and specific mental and physical disorders on work role disability and quality of life in six European countries. METHOD: The ESEMeD study was conducted in: Belgium, France, Germany, Italy, the Netherlands and Spain. Individuals aged 18 years and over who were not institutionalized were eligible for an in-home computer-assisted interview. Common mental disorders, work loss days (WLD) in the past month and quality of life (QoL) were assessed, using the WMH-2000 version of the CIDI, the WHODAS-II, and the mental and physical component scores (MCS, PCS) of the 12-item short form, respectively. The presence of five chronic physical disorders: arthritis, heart disease, lung disease, diabetes and neurological disease was also assessed. Multivariate regression techniques were used to identify the independent association of mental and physical disorders while controlling for gender, age and country. RESULTS: In each country, WLD and loss of QoL increased with the number of disorders. Most mental disorders had approximately 1.0 SD-unit lower mean MCS and lost three to four times more work days, compared with people without any 12-month mental disorder. The 10 disorders with the highest independent impact on WLD were: neurological disease, panic disorder, PTSD, major depressive episode, dysthymia, specific phobia, social phobia, arthritis, agoraphobia and heart disease. The impact of mental vs. physical disorders on QoL was specific, with mental disorders impacting more on MCS and physical disorders more on PCS. Compared to physical disorders, mental disorders had generally stronger 'cross-domain' effects. CONCLUSION: The results suggest that mental disorders are important determinants of work role disability and quality of life, often outnumbering the impact of common chronic physical disorders.

Adult↗