Ambient pressure x-ray photoelectron spectroscopy setup for synchrotron-based in situ and operando atomic layer deposition research.

An ambient pressure cell is described for conducting synchrotron-based x-ray photoelectron spectroscopy (XPS) measurements during atomic layer deposition (ALD) processes. The instrument is capable of true in situ and operando experiments in which it is possible to directly obtain elemental and chemical information from the sample surface using XPS as the deposition process is ongoing. The setup is based on the ambient pressure XPS technique, in which sample environments with high pressure (several mbar) can be created without compromising the ultrahigh vacuum requirements needed for the operation of the spectrometer and the synchrotron beamline. The setup is intended for chemical characterization of the surface intermediates during the initial stages of the deposition processes. The SPECIES beamline and the ALD cell provide a unique experimental platform for obtaining new information on the surface chemistry during ALD half-cycles at high temporal resolution. Such information is valuable for understanding the ALD reaction mechanisms and crucial in further developing and improving ALD processes. We demonstrate the capabilities of the setup by studying the deposition of TiO2 on a SiO2 surface by using titanium(IV) tetraisopropoxide and water as precursors. Multiple core levels and the valence band of the substrate surface were followed during the film deposition using ambient pressure XPS.

Role of ultrafast dissociation in the fragmentation of chlorinated methanes.

Photon-induced fragmentation of a full set of chlorinated methanes (CH3Cl, CH2Cl2, CHCl3, CCl4) has been investigated both experimentally and computationally. Using synchrotron radiation and electron-ion coincidence measurements, the dissociation processes were studied after chlorine 2p electron excitation. Experimental evidence for CH3Cl and CH2Cl2 contains unique features suggesting that fast dissociation processes take place. By contrast, CHCl3 and CCl4 molecules do not contain the same features, hinting that they experience alternative mechanisms for dissociation and charge migration. Computational work indicates differing rates of charge movement after the core-excitation, which can be used to explain the differences observed experimentally.

Fragmentation of mercury compounds under ultraviolet light irradiation.

Ultraviolet light induced photofragmentation of mercury compounds is studied experimentally with electron energy resolved photoelectron-photoion coincidence techniques and theoretically with computational quantum chemical methods. A high resolution photoelectron spectrum using synchrotron radiation is presented. Fragmentation of the molecule is studied subsequent to ionization to the atomic-mercury-like d orbitals. State dependent fragmentation behaviour is presented and specific reactions for dissociation pathways are given. The fragmentation is found to differ distinctly in similar orbitals of different mercury compounds.

Spin-orbit interaction mediated molecular dissociation.

The effect of the spin-orbit interaction to photofragmentation is investigated in the mercury(II) bromide (HgBr2) molecule. Changes in the fragmentation between the two spin-orbit components of Hg 5d photoionization, as well as within the molecular-field-splitted levels of these components are observed. Dissociation subsequent to photoionization is studied with synchrotron radiation and photoelectron-photoion coincidence spectroscopy. The experimental results are accompanied by relativistic ab initio analysis of the photoelectron spectrum.

Heterozygous frameshift mutation in keratin 5 in a family with Galli-Galli disease.

BACKGROUND: Reticulate pigmentary disorders include the rare autosomal dominant Galli-Galli disease (GGD) and Dowling-Degos disease (DDD). Clinical diagnosis between some of the subtypes can be difficult due to a degree of overlap between clinical features, therefore analysis at the molecular level may be necessary to confirm the diagnosis. OBJECTIVES: To identify the underlying genetic defect in a 48-year-old Asian-American woman with a clinical diagnosis of GGD. METHODS: Histological analysis was performed on a skin biopsy using haematoxylin-eosin staining. KRT5 (the gene encoding keratin 5) was amplified from genomic DNA and directly sequenced. RESULTS: The patient had a history of pruritus and hyperpigmented erythematous macules and thin papules along the flexor surfaces of her arms, her upper back and neck, axillae and inframammary areas. Hypopigmented macules were seen among the hyperpigmentation. A heterozygous 1-bp insertion mutation in KRT5 (c.38dupG; p.Ser14GlnfsTer3) was identified in the proband. This mutation occurs within the head domain of the keratin 5 protein leading to a frameshift and premature stop codon. CONCLUSIONS: From the histological findings and mutation analysis the individual was identified as having GGD due to haploinsufficiency of keratin 5.

Predictors of delayed social maturation and mental health disorders in young adults chronically ill since childhood.

To ascertain the influence of juvenile-onset chronic physical diseases and associating factors of social environment on delayed social maturation and mental health disorders in young adults, we analysed a group of 407 (184 female, 223 male) subjects with these conditions and compared the results with those of 123 (63 female, 60 male) healthy controls studied at the age of 19-25 years. The social maturation index was formed on the basis of a demographic interview, which also reviewed the state of social development and the family situation during childhood. Mental health disorders were assessed with a Present State Examination (PSE) interview analysed with the CATEGO program. With regard to social maturation at least half of the patients and controls were doing well, whereas for 29% (CI(95), 25%-33%) of the patients and 17% (CI(95), 10%-24%) of the controls the index showed delayed maturation. Subjects with poor social maturation were found most often among the disabled patients but also among the patients without severe diseases. The prevalence of PSE-CATEGO-identified psychiatric syndromes was equal in the patients and the controls (22% versus 20%). However, the patients with severe or disabling diseases had more severe psychiatric syndromes. The prevalences of depressive syndromes were also equal, but the depression of the patients was more often a profound affective disorder. Male sex, poor scholastic and vocational success, and social problems in the family during childhood were significantly associated with poor social maturation. On the other hand, the most significant predictors of mental health problems in young adults were female sex, family distress during childhood, and a severe disease. Juvenile-onset physical disease was considered to delay social maturation in some subjects and to deepen or modulate the clinical picture of mental health disorders. It is concluded that juvenile-onset physical diseases combined with family-related factors affect in different ways the social growth and psychiatric well-being. The results suggest that the subjects with chronic diseases during childhood should be thoroughly assessed by a child psychiatrist to evaluate the orientation of psychological development and the impact of the child's disease on the family and to ensure balanced psychological and social growth.

Do neurological disorders in childhood pose a risk for mental health in young adulthood?

To assess whether juvenile-onset epilepsy or motor disability is complicated by an increased number of mental health disorders or experience of psychosomatic symptoms in young adulthood, we studied 81 subjects with epilepsy and 52 with motor disabilities at the age of 19 to 25 years and compared them with 211 controls. The main diagnostic tool, the Present State Examination, was administered to those attending the interviews in person who were of normal intelligence; there were 62, 38, and 123 subjects in the three categories, respectively. Compared with the controls, the subjects with epilepsy showed an equal prevalence of psychiatric disorders whereas those with motor disabilities had a significantly higher prevalence, particularly of depressive disorders. The reported prevalence of psychosomatic symptoms confirmed this main result. Psychological illness affected everyday life of two out of five subjects with motor disabilities, but only half of those in the other two groups. It is concluded that motor disability since childhood, but not epilepsy, could be a factor that increases susceptibility to psychiatric morbidity, especially depression, and causes a large number of psychosomatic symptoms. The results challenge staff of clinics working with such adolescents to find individual approaches in preventing the negative influence of psychological disorders on social life.

Psychosocial outcome of young adults with epilepsy in childhood.

OBJECTIVE: To evaluate social maturation and psychiatric morbidity in young adults treated for epilepsy during their childhood. METHODS: Eighty one young adults (43 women, 38 men, mean age 22.3 years) with epilepsy during their childhood were interviewed about their social development and psychiatric symptoms. The results were compared with those from 211 randomly selected controls (106 women, 105 men, mean age 23.2 years). RESULTS: Compared with the controls the patients had more often not succeeded in passing the normal comprehensive school (20% v 2%) or had left school at the secondary level (53% v 46%) and remained without any vocational education (27% v 11%). There was no significant difference in the employment status of those with work between the patients and the controls. The patients were significantly more often labelled with poor social maturation and dependent lifestyle factors such as living with their parents. However, risk analysis showed that neither the disease itself nor antiepileptic medication were significant predisposing factors for poor social adjustment but low or borderline mental capacity or learning disabilities relating to epilepsy were. Psychiatric morbidity was similar in both groups. CONCLUSIONS: The social handicap found in a certain group of young adults with epilepsy during childhood is largely associated with neurological and cognitive impairments other than epilepsy itself. With the present mode of treatment epilepsy itself does not seem to disturb adolescent social and psychological development.

Psychological and somatic symptoms in young adults with chronic physical diseases.

To find out whether a long-term physical illness since childhood increases the risk of experiencing psychological and somatic symptoms, we interviewed a group of 487 patients aged 20-25 years and compared these findings to 211 controls. Both somatic (chi 2 = 9.11, d.f. = 6, p < 0.001) and psychological (chi 2 = 11.0, d.f. = 6, p < 0.001) symptom indexes varied significantly between the patient groups. Female sex, family conflicts during childhood, poor scholastic performance and depressive mental disorders were especially observed to be significant risk factors related to an excessive occurrence of these symptoms. The results suggest that a disabling disease lasting from childhood unit adulthood is complicated by a significant incidence of both psychological and somatic symptoms.

Prevalence of mental disorders in young adults with chronic physical diseases since childhood as identified by the Present State Examination and the CATEGO program.

To find out whether long-term physical disorders in childhood increase the risk for mental disorder, we interviewed 407 young adults and compared their findings to a control group of 123 age-matched controls. The overall prevalence of mental disorders according to ICD-8 classification exceeded 20% in both groups. Depression and phobic disorders were the most common diagnostic syndromes, being most prevalent in women with motor handicaps or short stature. Only 7 patients had received psychotherapy, 5 for psychotic symptoms. In conclusion, only a severe physical disease, visible and disabling for years in everyday life, seems to increase the risk for mental problems. The results demonstrate the need to improve the approach towards psychological problems in the somatic clinics treating patients with long-term physical diseases.

311 nm UVB lamps in the treatment of psoriasis with the Ingram regimen.

A new experimental fluorescent lamp emitting UVB mainly in a narrow peak around 311 nm was compared with a conventional broad band UVB lamp in the treatment of psoriasis with the Ingram regimen. In 20 patients one arm was treated with the new lamps and the other arm with conventional lamps. In 12 patients the results were same, but the new lamp was more effective in 8 patients. In another trial, 53% of 17 patients treated with the new lamp showed good results compared with 30% of 23 patients treated with conventional lamps. In conclusion, the 311 nm UVB lamp is at least as effective as the conventional broad band UVB lamps in the treatment of psoriasis with the Ingram regimen.

Acetylsalicylic acid inhibits non-immunologic contact urticaria.

To investigate the mechanisms of non-immunologic contact urticaria (NICU), the effects of 1g + 1g of acetylsalicylic acid (ASA) on contact reactions to methyl nicotinate, diethyl fumarate, benzoic acid, cinnamic acid, cinnamic aldehyde and dimethyl sulfoxide were studied in 21 test subjects. Erythema and edema reactions were observed visually, and the changes in the skin blood flow were monitored using laser-Doppler flowmetry. ASA had a significant inhibitory effect on erythema from all 6 agents and also on edema from all substances except dimethyl sulfoxide. The mechanism of the effect may be a result of the inhibitory influence of ASA on prostaglandin bioformation. Thus, to avoid false negative test results, non-steroidal anti-inflammatory drugs should not be used during NICU tests.

Ultraviolet light therapy in chronic urticaria.

Fifteen patients with chronic urticaria were treated with ultraviolet light B (UVB) for 1-3 months during the spring 1984 and a follow-up study was performed in November 1984-January 1985. Patients with cold urticaria, cholinergic urticaria and dermographism became clearly better or got rid of their symptoms more often than those with "non-specific" chronic urticaria. The good results achieved during the phototherapy held during the summer but in the autumn urticaria became worse in one third of the cases. The result suggests that UV-therapy might be worth trying in many patients with chronic urticaria.

Differential inhibition of fetal vascular prostacyclin and platelet thromboxane synthesis by nonsteroidal anti-inflammatory drugs in humans.

To study the synthesis of proaggregatory, vasoconstricting thromboxane A2 (TxA2) by human fetal platelets we evaluated the formation of its stable metabolite thromboxane B2 (TxB2) during thrombin-induced spontaneous clotting of blood from the umbilical vein of 13 healthy infants. We further compared the effects of acetylsalicylic acid, indomethacin, naproxen sodium and diclofenac sodium on platelet TxA2 production in response to thrombin-induced aggregation during spontaneous clotting, and on prostacyclin (PGI2) production by umbilical arteries in a superfusion system by measuring the 6-keto-prostaglandin F1 alpha (6-keto-PGF1 alpha) concentration in the superfusate. For every drug four concentrations covering the clinically significant range were studied. The basal production of TxB2 by fetal platelets (181.5 +/- 22.5 ng/ml, mean +/- SEM) was comparable with that of adults (216.1 +/- 11.5 ng/ml). The concentrations of the drugs needed for 50% inhibition of TxB2 generation were 19.0 mumol/l for acetyl-salicylic acid, 0.09 mumol/l for indomethacin, 0.06 mumol/l for diclofenac sodium and 4.2 mumol/l for naproxen sodium. The basal production of 6-keto-PGF1 alpha by umbilical arteries was 24.5 +/- 3.2 ng/min/g. The concentrations of the drugs needed for 50% inhibition of 6-keto-PGF1 alpha production were 360.0 mumol/l for acetylsalicylic acid, 4.0 mumol/l for indomethacin, 2.3 mumol/l for diclofenac sodium and 15.0 mumol/l for naproxen sodium. Thus fetal platelet cyclo-oxygenase was 4-44 times more sensitive to these prostaglandin synthesis inhibitors than umbilical artery cyclo-oxygenase.