Homo- und heteronukleare Bindungen bei schweren Elementen der 15. und 16. Gruppe

Binuclear molecules R 2 E-ER 2 or R-Y-Y-R, formed by the heavier pnicogen (E) or chalkogen atoms (Y), respectively, tend to align in homonuclear linear chains in the solid state, if steric requirements introduced by the substituents R do not prevent this association. Going from the third period elements phosphorus or sulfur to their higher homologues, the longer intermolecular distances within these chains gradually change in nature from normal van der Waals contacts to secondary bonds. For distibanes and dibismuthanes the differing bonding situations between the solid and liquid states are reflected in a bathochromic colour shift upon crystallization. Mononuclear halogenostibanes and -bismuthanes with aromatic groups are subject to intermolecular association, too, if there are enough electronegative substituents to invoke a sufficient Lewis acidity at the pnicogen atom. Non-classical pnicogen-arene interactions are found together with asymmetrie halogeno bridges for aryl-substituted stibanes. Only one of the corresponding bismuthanes has been investigated up to now; it shows symmetrie halogeno bridges, but no bismuth-arene coordination

Sensitization of catastrophic cognition in cognitive-behavioral therapy for panic disorder

<p>Abstract</p> <p>Background</p> <p>Cognitive model of panic disorder have proposed that panic attacks result from the catastrophic misinterpretation of certain bodily sensations. Cognitive-Behavioral Therapy (CBT) for panic disorder aims to change these catastrophic cognitions. CBT intervention successfully caused reduction of catastrophic cognitions and symptomatic improvement in the majority of cases. However there are some patients who fail to modify their catastrophic cognitions or rather experience an increase in them during CBT treatment. It is clinically and theoretically important to understand about cognitive sensitization of panic disorder during CBT sessions. The purpose of the present study is 1) to clarify the baseline characteristics of panic patients who would experience sensitization of their catastrophic cognitions through the CBT treatment, and 2) to examine the course of symptomatic changes for them.</p> <p>Methods</p> <p>Of ninety-five outpatients with panic disorder started the group CBT program for treatment of panic disorder, seventy-nine completer were classified as "cognitively sensitized (CS)" or "cognitive responding (CR)" or "no-responder" according to the difference of the Agoraphobic Cognitions Questionnaire score across treatment. We compared the CS and CR patients in terms of their baseline clinical characteristics. Then we assessed the symptomatic and functional changes for both groups.</p> <p>Results</p> <p>At the start of the CBT program, despite of the same degree of panic disorder severity, CS scored significantly lower on ACQ score than CR. CS also showed significantly lower score on anticipatory anxiety compared to CR. At the end of treatment CS showed significant improvement in severity of panic disorder, although the degree of improvement was smaller than that for CR. Then CS would progressively reduce their agoraphobic fear and avoidance, and would improve their functional impairment up to three month of follow-up.</p> <p>Conclusion</p> <p>Panic patients who would experience sensitization of their catastrophic cognitions through the CBT treatment could nonetheless gradually improve. They showed a relatively low level of catastrophic cognition and anticipatory anxiety before starting the CBT program. We might conclude that temporary sensitization of catastrophic cognition may be necessary before improvement especially among those with initially low catastrophic body sensation fears and that we need not be concerned too much with temporary increase in catastrophic cognition in the process of CBT for panic disorder.</p

Failure to Detect the Novel Retrovirus XMRV in Chronic Fatigue Syndrome

BACKGROUND:In October 2009 it was reported that 68 of 101 patients with chronic fatigue syndrome (CFS) in the US were infected with a novel gamma retrovirus, xenotropic murine leukaemia virus-related virus (XMRV), a virus previously linked to prostate cancer. This finding, if confirmed, would have a profound effect on the understanding and treatment of an incapacitating disease affecting millions worldwide. We have investigated CFS sufferers in the UK to determine if they are carriers of XMRV. METHODOLOGY:Patients in our CFS cohort had undergone medical screening to exclude detectable organic illness and met the CDC criteria for CFS. DNA extracted from blood samples of 186 CFS patients were screened for XMRV provirus and for the closely related murine leukaemia virus by nested PCR using specific oligonucleotide primers. To control for the integrity of the DNA, the cellular beta-globin gene was amplified. Negative controls (water) and a positive control (XMRV infectious molecular clone DNA) were included. While the beta-globin gene was amplified in all 186 samples, neither XMRV nor MLV sequences were detected. CONCLUSION:XMRV or MLV sequences were not amplified from DNA originating from CFS patients in the UK. Although we found no evidence that XMRV is associated with CFS in the UK, this may be a result of population differences between North America and Europe regarding the general prevalence of XMRV infection, and might also explain the fact that two US groups found XMRV in prostate cancer tissue, while two European studies did not

Synthesis, molecular and crystal structure of bis [(-2,2-dimethyl-1-trimethylsiloxypropyliden) phosphano]methane (Syntheses and properties of acylphosphanes ; 7)

Bis[bis(trimethylsilyl) phosphano]methan reagiert mit 2,2-Dimethyl-pro-pionylchlorid zum Bis[(-2,2-dimethyl-1-trimethylsiloxypropyliden)phosphano]methan. Die Verbindung (Schmp. 39°) wurde bei -95 ± 5°C röntgenstrukturanalytisch untersucht. Sie kristallisiert in der nichtzentrosymmetrischen Raumgruppe Pca21 mit a = 15,61(1);b = 12,84(1); c = 11,84(2) Å. Z = 4; R = 0,039. NMR- und IR-spektroskopische Untersuchungen zeigen, daß die Trimethylsilylgruppen an die Sauerstoffatome gebunden sind und die dritte Valenz der zweifach koordinierten Phosphoratome über Doppelbindungen zu den benachbarten Kohlenstoffatomen abgesättigt wird. Dies wird durch die Röntgenstrukturanalyse bestätigt. Die von der P C-Gruppe ausgehenden Bindungen liegen in einer Ebene; beide Ebenen des Moleküls sind um 85,1° gegeneinander verdreht. Die Anordnung der Substituenten entspricht einem Z/Z-Isomeren. In beiden Molekülhälften weichen mit Ausnahme der Winkel an den Sauerstoffatomen (141°,135°) Bindungsabstände und -winkel nur geringfügig voneinander ab.In the reaction of 2,2-dimethylpropionyl chloride with bis[bis(trimethylsilyl)-phosphano]methane bis[(-2,2-dimethyl-1-trimethylsiloxypropyliden)phosphano]methane is formed. The structure of the compound (m.p.39°C) was determined at -95 ±5°C by X-ray diffraction. It crystallizes in the non-centrosymmetric space group Pca21 with a = 15.61(1); b = 12.84(1); z = 11.84(2) Å. Z = 4; R = 0.039.N.m.r. and i.r. spectroscopic investigations show the trimethylsilyl groups to be bound to the oxygen atoms and the third valence of the twofold coordinated phosphorus atoms engaged in double bonds to the neighbouring carbon atoms. This is confirmed by the X-ray structure determination. All bonds leading to the PC group lie in a plane; both planes of the molecules are mutually inclined by 85.1°. The arrangement of substituents corresponds to a Z/Z-isomer. In both parts of the molecule bond distances and angles differ only slightly, the angles at the oxygen atoms (141°,135°) excepted

Reaction of phenylbis(trimethylsilyl)-phosphane with formaldehyde and dimethylformamide (Syntheses and properties of acylphosphanes ; 9)

Trimethylsilylphosphane reagieren mit Carbonylverbindungen unter Addition. Aus Phenylbis(trimethylsilyl)phosphan 1 und Formaldehyd 2 ist Phenyl-bis(trimethylsiloxy-methyl)phosphan 3 zugänglich. Im Gegensatz dazu beobachtet man mit Dimethylformamid 4 eine Additions-Eliminierungs-Reaktion unter Abspaltung von Hexamethyldisiloxan 6 und Bildung des N,N-Dimethylaminomethyliden-phenylphosphans 5. NMR-spektroskopische Untersuchungen zeigen eine gehinderte Rotation der Dimethylaminogruppe. Als Nebenprodukt fällt das Dimere 2,4-Bis-(N,N-dimethylamino)-l,3-diphenyl-l,3-diphosphetan 11 an.Trimethylsilylphosphanes add to carbonyl compounds. Therefore phenyl-bis(tri-methylsiloxymethyl)phosphane 3 can be prepared by reacting phenylbis(trimethylsilyl)phosphane 1 with formaldehyde 2. With dimethylformamide 4, however, an addition-elimination-reaction yields hexamethyldisiloxane 6 and N,N-dimethylaminomethyliden-phenylphosphane 5. NMR-spectroscopic studies show the rotation of the dimethylamino group to be hindered. The dimer 2,4-bis(N,N-dimethylamino)-l,3-diphenyl-l,3-diphosphetane 11 is isolated as a by-product