An old workhorse for new applications: Fe(dpm)3 as a precursor for low-temperature PECVD of iron(III) oxide.

An iron(III) ß-diketonate complex, Fe(dpm)3 (Hdpm = 2,2,6,6-tetramethyl-3,5-heptanedione), has been investigated as a potential precursor for plasma enhanced chemical vapor deposition (PECVD) of iron(III) oxide nanomaterials. Thanks to the combined experimental-theoretical approach, spectroscopic properties, spin state, thermal behavior and fragmentation pathways of Fe(dpm)3 have been carefully analysed, obtaining an excellent agreement between simulation and experiment. Preliminary PECVD tests evidenced the possibility of obtaining pure and homogeneous Fe2O3 deposits with controlled nano-organization at temperatures as low as 100 °C, even on flexible plastic substrates. The present results open up intriguing perspectives for the exploitation of Fe(dpm)3 as an efficient molecular source for the preparation of nanostructured iron(III) oxides to be used in energetics and gas sensing applications.

Modelling of contact regimes in wire sawing with dissipative particle dynamics.

Optimization of the wire sawing process of silicon ingots requires a profound understanding of the dynamic interaction of wire, slurry and silicon material. In this paper, the influence of wire velocity and applied wire stress on the process is investigated using dissipative particle dynamics and discrete element simulations for modelling the fluid and the grains in the abrasive suspension. In our simulations, different contact regimes occur depending on grain shape and a stress balance within the system. We observed semi-contact for high wire stress and low wire velocity and non-contact for low stress and high velocities in agreement with predictions from elasto-hydrodynamic modelling. Our simulations suggest the usage of sharp grains, since in this case, stress localization on the base of the sawing groove occurs even in the non-contact regime. These insights are likely to provide a scientific base for the optimization of sawing rates and reduction of kerf loss.

Understanding of the phase transformation from fullerite to amorphous carbon at the microscopic level.

We study the shock-induced phase transformation from fullerite to a dense amorphous carbon phase by tight-binding molecular dynamics. For increasing hydrostatic pressures P, the C60 cages are found to polymerize at P<10 GPa, to break at P approximately 40 GPa, and to slowly collapse further at P>40 GPa. By contrast, in the presence of additional shear stresses, the cages are destroyed at much lower pressures (P<30 GPa). We explain this fact in terms of a continuum model, the snap-through instability of a spherical shell. Surprisingly, the relaxed high-density structures display no intermediate-range order.

High interleukin-13 production by phytohaemagglutinin- and Der p 1-stimulated cord blood mononuclear cells is associated with the subsequent development of atopic dermatitis at the age of 3 years.

OBJECTIVE: The aim of our study was to conduct a prospective investigation into the potential association of cord blood proliferative response and cytokine production in response to various stimuli on the development of atopic dermatitis (AD) at the age of 3 years. METHODS: Cord blood mononuclear cells (CBMC) from 40 healthy term neonates were isolated. The proliferative response of CBMC stimulated with IL-2, betalactoglobulin (BLG) and house dust mite allergen (Der p 1) was assessed by liquid scintillation counting and the stimulation index (SI) was calculated. The cytokines interleukin (IL-)13, interferon (IFN-)gamma, IL-10 and IL-18 in the cell culture supernatants in response to phytohaemagglutinin (PHA), Der p 1 and BLG were measured using the ELISA technique. After 3 years, symptoms of AD were obtained with a questionnaire completed by the parents. RESULTS: We observed significantly higher IL-13 levels in response to PHA in children who subsequently developed symptoms of AD (S: median, 291 pg/mL) compared with asymptomatic children (No-S: 149 pg/mL; P=0.021, Wilcoxon test). Similarly, in response to Der p 1 significantly higher IL-13 levels were observed in symptomatic children (S: 168.6; No-S: 61.6 pg/mL; P=0.0084). In response to BLG, IL-13 levels were 287.2 (S) and 123.6 pg/mL (No-S; P=0.19). No significant differences were found when comparing the IFN-gamma levels in CBMC cultures stimulated with PHA (S: 10.2; No-S: 17.6 IU/L; P=0.78), Der p 1 (S: 307.6; No-S: 616.2 IU/L; P=0.2) or BLG (S: 18; No-S: 28.5 IU/L; P=0.83; Fig. 2). The IL-18 and IL-10 levels and the stimulation index in response to IL-2, BLG and Der p 1 showed no significant difference between children who subsequently developed symptoms of AD and asymptomatic children. CONCLUSION: Our data suggest that enhanced IL-13 levels at birth are associated with the subsequent development of atopic symptoms at the age of 3 years.

Supported magnetic nanoclusters: soft landing of Pd clusters on a MgO surface.

Low-energy deposition of neutral Pd(N) clusters (N=2-7 and 13) on a MgO(001) surface F center (FC) was studied by spin-density-functional molecular dynamics simulations. The incident clusters are steered by an attractive "funnel" created by the FC, resulting in adsorption of the cluster, with one of its atoms bonded atop of the FC. The deposited Pd2-Pd6 clusters retain their gas-phase structures, while for N>6 surface-commensurate isomers are energetically more favorable. Adsorbed clusters with N>3 are found to remain magnetic at the surface.

Optical response of two-dimensional electron fluids beyond the kohn regime: strong nonparabolic confinement and intense laser light.

We investigate the linear and nonlinear optical response of two-dimensional interacting electron fluids confined by a strong nonparabolic potential. We show that such fluids may exhibit higher-harmonic spectra under realistic experimental conditions. Higher harmonics arise as the electrons explore anharmonicities of the confinement potential (electron-electron interactions reduce this nonlinear effect). This opens the possibility of controlling the optical functionality by engineering the confinement potential. Our results were obtained within time-dependent density-functional theory. A classical hydrodynamical model is in good agreement with the quantum-mechanical results.

Allergen-specific T cell reactivity in cord blood: the influence of maternal cytokine production.

BACKGROUND: Successful pregnancy is dependent upon T helper (Th)2-type-dominated immunological responsiveness in gestation-associated compartments. OBJECTIVE: In our study we observed the influence of the maternal Th2-associated cytokine pattern on the naive fetal T cell phenotype and asked if circulating Th2 cytokines of atopic mothers affects the Th1/Th2 differentiation of the fetus. METHODS: Cord blood mononuclear cells (CBMC) and peripheral blood mononuclear cells (PBMC) of the corresponding mothers were isolated. The proliferative response of CBMC and PBMC to Betalactoglobulin (BLG) was assessed by liquid scintillation counting. The cytokines interferon (IFN)-gamma, and interleukin (IL)-5, IL-10 and IL-13 in the cell culture supernatants were measured using the ELISA technique. We then defined two subgroups based on maternal levels of specific IgE against aeroallergens: sensitized mothers (MA(+)) and their neonates (NMA(+)) (n = 18) and non-sensitized mothers (MA(-)) and their neonates (NMA(-)) (n = 29). RESULTS: Nearly all mothers (98%) and neonates (92%) had a positive proliferation response after stimulation with BLG (mean stimulation index (10-90 percentile): neonates: 7 (2-15); mothers 14 (5-29)). In supernatants of BLG-stimulated cell cultures, sensitized mothers showed a significantly lower IFN-gamma concentration in comparison to non-sensitized mothers (MA(+) = 25; MA(-) = 123 IU/L; P < 0,05), whereas the neonates did not differ significantly (NMA(+) = 306; NMA(-) = 224 IU/L; n. s.). Nor was any difference found in the IL-13 concentration between the two groups of sensitized and non-sensitized mothers (MA(+) = 48; MA(-) = 125 pg/mL; n. s.). CBMC of neonates with a sensitized mother showed significantly higher IL-13 concentrations in response to BLG than neonates of non-sensitized mothers (NMA(+) = 1442, NMA(-) 738 pg/mL; P < 0.05). The IL-5 and IL-10 concentrations did not differ significantly within the neonatal and the maternal subgroups. CONCLUSIONS: Our data suggests that maternal sensitization to allergens is associated with the reduced maternal production of the Th2 antagonist IFN-gamma and elevated production of the Th2 cytokine IL-13 in the offspring.

Photoabsorption spectra of Na(+)(n) clusters: thermal line-broadening mechanisms.

Photoabsorption cross sections of small sodium cluster cations ( Na(+)(n), n = 3, 5, 7, and 9) were calculated at various temperatures with the time-dependent local-density approximation in conjunction with ab initio molecular dynamics simulations, yielding spectra that agree with measured ones without ad hoc line broadening or renormalization. Three thermal line-broadening mechanisms are revealed: (I) lifting of level degeneracies caused by symmetry-breaking ionic motions, (II) oscillatory shifts of the entire spectrum caused by breathing vibrations, and (III) cluster structural isomerizations.

Structure and magnetism of neutral and anionic palladium clusters.

The properties of neutral and anionic Pd(N) clusters were investigated with spin-density-functional calculations. The ground-state structures are three dimensional for N>3 and they are magnetic with a spin triplet for 2 < or = N < or = 7 and a spin nonet for N = 13 neutral clusters. Structural and spin isomers were determined and an anomalous increase of the magnetic moment with temperature is predicted for a Pd7 ensemble. Vertical electron detachment and ionization energies were calculated and the former agrees well with measured values for Pd(-)(N).

Preventive effect of 2 and 10 mg of sodium cromoglycate on exercise-induced bronchoconstriction.

UNLABELLED: This double-blind, randomised and cross-over study was designed to compare the preventive effect against exercise-induced bronchoconstriction (EIB), defined as the percentage decrease in FEV1 > or = 15% after 6 min of exercise, of 2 mg and 10 mg of sodium cromoglycate (SCG), administered through a metered dose inhaler via spacer, in asthmatic children. Each of the 30 subject (age 11.6 +/- 3.2 years) was tested on five occasions. For inclusion, EIB in test1 was required. In tests 2 to 5, all subjects inhaled 2 mg or 10 mg of SCG 20 min and 120 min before exercise in a randomised order. In order to assess excretion of eosinophil protein X (EPX) accompanying EIB, urine samples were collected before and after exercise. The mean percentage fall in FEV1 (+/- SD) in test 1 was 26.8 +/- 9.8%. Inhalation of 2 mg and 10 mg of SCG 20 min before exercise provided a significant preventive effect in 83% and 77% and inhalation 120 min before exercise provided a preventive effect in 63% and 70%, respectively (n = 30). Variance analysis did not reveal a statistically different absolute fall in FEV1 after exercise when both doses (120 min before exercise) were compared (P = 0.356). In an unselected subgroup of 12 children, urinary EPX increased after the challenge without SCG premedication (test 1) (mean change: +48.7 micrograms/mmol creatinine, P = 0.034), whereas no significant increase was found in case of SCG premedication (mean change in microgram/mmol creatinine): 2 mg/20 min: +12.1; 2 mg/120 min: +8.5; 10 mg/20 min: -10.4 and 10 mg/120 min: -23.5; P > 0.1). CONCLUSION: Administration of 10 mg of sodium cromoglycate is no more effective in preventing exercise-induced bronchoconstriction than 2 mg regardless of whether the medication is given 20 or 120 min before exercise. The preventive effect of sodium cromoglycate on exercise-induced bronchoconstriction in asthmatic children is associated with the inhibition of urinary eosinophil protein X excretion.

Formation, stability, and breakup of nanojets

Atomistic molecular dynamics simulations reveal the formation of nanojets with velocities up to 400 meters per second, created by pressurized injection of fluid propane through nanoscale convergent gold nozzles with heating or coating of the nozzle exterior surface to prevent formation of thick blocking films. The atomistic description is related to continuum hydrodynamic modeling through the derivation of a stochastic lubrication equation that includes thermally triggered fluctuations whose influence on the dynamical evolution increases as the jet dimensions become smaller. Emergence of double-cone neck shapes is predicted when the jet approaches nanoscale molecular dimensions, deviating from the long-thread universal similarity solution obtained in the absence of such fluctuations.

Pulmonary function in children of school age is related to the number of siblings in their family.

It has been suggested that the number of siblings in a family is a surrogate variable for exposure to early infections. Since there may be an association between early respiratory infections and impaired lung function in later life, the aim of this study was to elucidate the relationship between the number of siblings and pulmonary function. We analyzed pulmonary function data from 677 schoolchildren living in 431 nuclear families. Our results show that forced vital capacity (FVC) and forced expiratory volume in 1 second (FEV(1)) expressed as a percentage of deviation from the predicted values (FVC%, FEV(1)%) increase significantly in line with the number of siblings in a family (FVC%: no sibling = reference, 1 sibling = +1.3%, 2 siblings = +1.9%, 3 siblings = +4.0%, 4 or more siblings = +5.1%; P-value for trend = 0.01; FEV(1)%: no sibling = reference, 1 sibling = +1.6%, 2 siblings = +2.0%, 3 siblings = +4.3%, 4 or more siblings = +6.5%; P-value for trend = 0.007). Pulmonary function values were no more strongly related to the number of older siblings than to the number of younger siblings (difference between the trend for older and younger siblings for FCV%: P = 0.7; FEV(1)%: P = 0.9). The association between pulmonary function and number of siblings can be explained neither by the child's atopic status, prevalence of asthma, or history of pneumonia, nor by former or current cigarette smoke exposure. This suggests that pulmonary function status of the child appears to be related to the number of siblings, and is unlikely to be explained solely by exposure to infections early in life. Our data therefore adds strength to the hypothesis that factors which cause the size of a sibship to influence a child's respiratory health have not yet been adequately explained.

Circadian variation of urinary eosinophil protein X in asthmatic and healthy children.

BACKGROUND: It is suggested that urinary eosinophil protein X (EPX) is a noninvasive tool to monitor bronchial inflammation in asthmatic children. However, circadian variation of the number and activation of eosinophils might possibly influence urinary EPX excretion. OBJECTIVE: Measurements of urinary EPX (radioimmunoassay) were used to investigate circadian variation of eosinophilic activation and to monitor bronchial inflammation in children with asthma before and after treatment with corticosteroids. METHODS: Urinary EPX excretion (microg/mmol creatinine) was measured in the morning and afternoon in 22 stable asthmatics and in 16 nonatopic, nonasthmatic controls to investigate circadian variation. Additionally, EPX excretion in the afternoon was analysed in 21 children with chronic asthma before and after 6 weeks of treatment with inhaled corticosteroids, and in seven children within 24 h of admission due to an asthma exacerbation and again 3 months after discharge. RESULTS: EPX excretion in the first morning urine sample of the day compared with the afternoon urine sample was significantly higher both in children with asthma (n = 22; mean +/- standard deviation: 179.7 +/- 97.3 vs 60.9 +/- 40.7 microg/mmol creatinine, P = 0.0001) and in nonatopic nonasthmatic controls (n = 16; 114.5 +/- 57.1 vs 53.4 +/- 29.0 microg/mmol creatinine, P = 0.0001). EPX excretion decreased significantly after 6 weeks of anti-inflammatory treatment in the group of children with chronic asthma (n = 21; 124.7 +/- 84.6 vs 87. 5 +/- 61.9 microg/mmol creatinine, P = 0.02) and in the group of children with an acute asthma exacerbation 3 months after discharge (n = 7; 233.2 +/- 174.5 vs 75.8 +/- 59.5 microg/mmol creatinine, P = 0.02). CONCLUSION: This study suggests a circadian variation of EPX excretion in children with asthma and in nonatopic, nonasthmatic controls. Measurement of EPX excretion is helpful monitoring therapy in asthmatic children if circadian variation is considered.

Genetic linkage of HLA-class II locus to mite-specific IgE immune responsiveness.

BACKGROUND: IgE response to common inhalant allergens seems to be the major determinant of the development of atopic rhinitis and asthma but it has been difficult to demonstrate genetic control of the IgE response. OBJECTIVE: To investigate genetic linkage between specific IgE reactions to purified aero-allergens (grass, birch, cat, mite) and the HLA-class II locus. METHODS: DNA-based HLA-class II typing was performed for determination of DRB1, DQB1 and DPB1 alleles. Linkage was studied by the affected sibpair method and the extended transmission disequilibrium test in 100 children from 40 nuclear families selected from a homogeneous population in south-western Germany. RESULTS: Significant linkage of mite-specific IgE response to HLA-DPB (P = 0.00001), HLA-DRB (0.02) and HLA-DQB (P = 0.001) was revealed by sibpair analysis of MHC class II alleles and confirmed by the extended transmission disequilibrium test for HLA-DRB (P = 0.01) and HLA-DPB (P = 0.04). No consistent significant linkage between the HLA-class II locus and IgE response to grass pollen, birch pollen, and cat dander could be demonstrated. CONCLUSION: The findings are consistent with the existence of one or more genes in the HLA-class II region modifying the IgE immune response to common environmental allergens.

Linkage and allelic association of atopy and markers flanking the IL4-receptor gene.

BACKGROUND: Atopy, a clinical syndrome characterized by heightened IgE responsiveness, is largely determined by genetic factors. The disease may well be heterogeneous but the mode of inheritance is unknown. Several genes have been named which affected IgE responsiveness. However, results are conflicting reflecting heterogeneity and a complicated inheritance pattern of the atopic syndrome. In 1994 linkage of the 5q32 gene region and elevated total IgE levels were reported, leaving the IL4 gene as a prominent candidate. OBJECTIVES: We were interested in a possible involvement of the IL4-receptor gene in the development of atopy. METHODS: We employed sib-pair linkage analysis using highly polymorphic microsatellite markers within and flanking the IL4 receptor gene in atopic families, characterized for specific sensitization to inhalant allergens and elevated total serum IgE. Allele sizes were determined for all microsatellite probes to allow transmission disequilibrium analysis. RESULTS: We found significant sharing of maternal but not paternal alleles in affected sibs from two independent populations, both of which presented enhanced IgE responsiveness. Linkage and maternal inheritance could be confirmed by transmission disequilibrium analysis. CONCLUSIONS: We conclude from our findings that maternal inheritance of a gene in the chromosome 16p12 region increases the risk for enhanced IgE responsiveness. The most prominent candidate in this region is represented by the IL4 receptor gene.

Accumulation of atopic disorders within families: a sibling effect only in the offspring of atopic fathers.

BACKGROUND: Several studies have reported an association between a child's risk of atopic disorders and family size. However, the inverse association might not be the same in populations with a different genetic disposition for atopic disorders. OBJECTIVE: This longitudinal study was designed to assess risk factors of atopy. METHODS: Lifetime prevalence of asthma, hay fever and eczema of 1440 families including 3165 offspring was ascertained by means of standardized questionnaires. RESULTS: After possible confounders had been controlled for, an inverse association between atopic disorders and the number of older siblings was found only in the offspring of atopic fathers (trend for older siblings: chi2 = 13.38, degrees of freedom [d.f.] = 1, P= 0.0002; odds ratio 'no older sibling'= 2.87 (95% confidence interval 2.18-3.78); '1 older sibling' = 2.11 [1.52-2.92], '2 older siblings' = 1.29 [0.74-2.23]; '3 or more older siblings' = 0. 15 [0.02-0.981). No such relationship was found for children without a history of paternal atopy (trend for older siblings: chi2 = 1.5 1, d.f. = 1, P = 0.22; odds ratio 'no older sibling' = 1 [reference]; '1 older sibling' =0.82 [0.63-1.06]; '2 older siblings' = 0.97 [0.67-1.40]; '3 or more older siblings' = 0.64 [0.31-1.33]). The trend for older siblings in the case of paternal atopy was significantly different from the trend for older siblings without a history of paternal atopy (chi2 = 8.68, d.f. = 1, P = 0.003). The number of younger siblings was not related to child's risk of atopy (trend for younger siblings: chi2 = 0.001, d.f. = 1, P = 0.97). CONCLUSIONS: Data from this study suggest a protective effect of sibship size only in children with a history of paternal atopy and if older siblings are present. The reason for this combined effect remains unclear. Thus, further investigations are needed to interpret the biological cause of the so called 'sibling effect'.

The most common phenotypes of sensitization to inhalant allergens in childhood.

BACKGROUND: Atopic individuals are frequently sensitized to a limited number of certain allergens, although most of them are exposed to multiple inhalant allergens in daily life. OBJECTIVE: We investigated the hypothesis that observed common patterns of sensitization might occur with similar frequency within two independent study populations of school-children. METHODS: The results were derived from skin-prick tests conducted on two large samples of children (study 1: n = 583; study 2: n = 1099) examined with the same panel of six inhalant allergens. RESULTS: In order to ensure that the comparison was uniform, the younger subpopulation of study 1 (n = 147) was compared with the sample of study 2 (n = 374). The highest frequency for monosensitization was found for sensitization to Dermatophagoides pteronyssinus (study 1: 18.4%, study 2: 20.3%), followed by monosensitization to grass pollens (study 1: 12.2%; study 2: 8.8%). Using multiple logistic regression for each specific sensitization, a significantly increased relative risk of sensitization to hazel pollens (study 1 OR 5.9; study 2 OR: 24.3) appeared to be associated with sensitization to birch pollens. The same applied to dog dander (study 1 OR: 7.3; study 2 OR: 2.6), which showed an association with sensitization to cat dander. CONCLUSION: In summary, our data suggest that certain clusters of monosensitization and polysensitization to common inhalant allergens exist among a given population. This may well be a reflection of diversity in disposition to specific sensitization and/or antigen crossreactivity. From a practical point of view the data also might help in counselling parents of allergic children.

Effect of moderate NO2 air pollution on the lung function of children with asthmatic symptoms.

In the course of a 2 1/2-year longitudinal study, the influence of outdoor NO2 and of the heating device at home on lung function was investigated in 467 children of school age in the urban area of Freiburg. Data were gathered in three surveys using standardized interviews, lung function measurements, skin prick tests with inhalant allergens, and NO2 measurements from October to April near the child's home. Regarding the lung function of a subpopulation with asthmatic symptoms (n = 106) in the three consecutive surveys, multivariate regression analyses adjusted for confounders indicate negative associations between five dependent variables, FEV1%FVC (P = 0.004), FEV1% (P = 0.02), MEF75% (P = 0.038), MEF50% (P = 0.052), and MEF25% (P = 0.002), on the one hand, and outdoor NO2 for average NO2 concentrations exceeding 40 micrograms/m3 on the other. The use of individual room heaters is associated with decreased lung function and is significant only for FEV1%FVC (P = 0.033). Neither NO2 nor individual room heating is significantly associated with one of the lung function parameters in the subpopulation without asthmatic symptoms (n = 361). In conclusion, children with asthmatic symptoms are identified as being susceptible to having reduced lung function under outdoor air pollution where average NO2 concentrations exceed 40 micrograms/m3.

Sensitization to four common inhalant allergens within 302 nuclear families.

The coincidence of allergic sensitization was investigated in 302 school-aged children and their parents. Specific sensitization to four common inhalant allergens (grass and birch pollens, cat dander, Dermatophagoides pteronyssinus) was ascertained by means of skin-prick tests (SPT) carried out on the complete family unit at the beginning of a 22-month follow-up period. The same test procedure was then repeated on the children twice at 11-month intervals to provide cumulative prevalences of sensitization. A clinical history of atopy in the children (hay fever or asthma; n = 47), which was derived from an interview, is associated with sensitization (positive SPT in 89%). For three allergens (grass and birch pollens, cat dander) sensitization occurs significantly more frequently in the children of mothers who are sensitized to the same allergen (odds-ratios (ORs), 2.5-4.1). Additionally, in three of the four explanatory models related to a single antigen, maternal sensitization to one of the complementary allergens is of importance (ORs, 2.7-3.7). In contrast to this finding, none of the paternal sensitizations has statistical significance. Based on a reaction to at least one of the four allergens, the child's relative risk to be sensitized is increased in case of maternal (OR, 2.88; P = 0.001) but not of paternal (OR, 1.06; P = 0.83) sensitization. In conclusion, our data indicate that the maternal status is more predictive than that of the father with regard to the child's risk of sensitization.