Nature and strength of group-14 A-A' bonds.

We have quantum chemically investigated the nature and stability of C-C and Si-Si bonds in R3A-AR3 (A = C, Si; R3 = H3, Me3, Me2Ph, MePh2, Ph3, t-Bu3) using density functional theory (DFT). Systematic increase of steric bulk of the substituents R has opposite effects on C-C and Si-Si bonds: the former becomes weaker whereas the latter becomes stronger. Only upon going further, from R = Ph to the bulkiest R = t-Bu, the R3Si-SiR3 bond begins to weaken. Our bonding analyses show how different behavior upon increasing the steric bulk of the substituents stems from the interplay of (Pauli) repulsive and (dispersion) attractive steric mechanisms. Extension of our analyses to other model systems shows that C-Si bonds display behavior that is in between that of C-C and Si-Si bonds. Further increasing the size of the group-14 atoms from C-C and Si-Si to Ge-Ge, Sn-Sn and Pb-Pb leads to a further decrease in the sensitivity of the bond strength with respect to the substituents' bulkiness. Our findings can be used as design principles for tuning A-A and A-A' bond strengths.

Methyl Substitution Destabilizes Alkyl Radicals.

We have quantum chemically investigated how methyl substituents affect the stability of alkyl radicals Mem H3-m C⋅ and the corresponding Mem H3-m C-X bonds (X = H, CH3 , OH; m = 0 - 3) using density functional theory at M06-2X/TZ2P. The state-of-the-art in physical organic chemistry is that alkyl radicals are stabilized upon an increase in their degree of substitution from methyl

The Chemical Bond: When Atom Size Instead of Electronegativity Difference Determines Trend in Bond Strength.

We have quantum chemically analyzed element-element bonds of archetypal Hn X-YHn molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C-C to C-F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C-F to C-I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance.

Information technology improves Emergency Department patient discharge instructions completeness and performance on a national quality measure: a quasi-experimental study.

OBJECTIVE: To compare the completeness of Emergency Department (ED) discharge instructions before and after introduction of an electronic discharge instructions module by scoring compliance with the Centers for Medicare and Medicaid Services (CMS) Outpatient Measure 19 (OP-19). METHODS: We performed a quasi-experimental study examining the impact of an electronic discharge instructions module in an academic ED. Three hundred patients discharged home from the ED were randomly selected from two time intervals: 150 patients three months before and 150 patients three to five months after implementation of the new electronic module. The discharge instructions for each patient were reviewed, and compliance for each individual OP-19 element as well as overall OP-19 compliance was scored per CMS specifications. Compliance rates as well as risk ratios (RR) and risk differences (RD) with 95% confidence intervals (CI) comparing the overall OP-19 scores and individual OP-19 element scores of the electronic and paper-based discharge instructions were calculated. RESULTS: The electronic discharge instructions had 97.3% (146/150) overall OP-19 compliance, while the paper-based discharge instructions had overall compliance of 46.7% (70/150). Electronic discharge instructions were twice as likely to achieve overall OP-19 compliance compared to the paper-based format (RR: 2.09, 95% CI: 1.75 - 2.48). The largest improvement was in documentation of major procedures and tests performed: only 60% of the paper-based discharge instructions satisfied this criterion, compared to 100% of the electronic discharge instructions (RD: 40.0%, 95% CI: 32.2% - 47.8%). There was a modest difference in medication documentation with 92.7% for paper-based and 100% for electronic formats (RD: 7.3%, 95% CI: 3.2% - 11.5%). There were no statistically significant differences in documentation of patient care instructions and diagnosis between paper-based and electronic formats. CONCLUSION: With careful design, information technology can improve the completeness of ED patient discharge instructions and performance on the OP-19 quality measure.

Separation of coal-tar constituents from soil particles in a two-liquid-phase slurry system.

An evaluation has been made of the capability of rapeseed oil to dissolve polycyclic aromatic hydrocarbon (PAH) crystals in a biphasic system and of its capability to extract PAHs from polluted soil in a two-liquid-phase (TLP) slurry system. Up to 220 g l(-1) of the crystalline hydrocarbons could be dissolved in the organic phase, indicating oil/water-partitioning coefficients of 10(5). When soil from a former gasworks site was treated in a TLP slurry system, it was found that a certain critical amount of vegetable oil had to be added in order to form a free oil phase. Single and multiple extractions gave similar results for multiple short-term and single long-term treatments, with a maximum of 87% for pyrene release. Following a 30-day bioslurry treatment, the total concentration of the 16 EPA PAHs in the soil decreased from 2740 mg kg(-1) to 1366 mg kg(-1). This was followed by one of three different 12-day post-bioslurry treatments. Further bioslurry treatment reduced the final concentration to 1002 mg kg(-1). Abiotic treatment with a surfactant (Brij 30) achieved a reduction to 797 mg kg(-1). Treatment with rapeseed oil gave the best reduction to 343 mg kg(-1).

Inflammatory variant of epidermolysis bullosa acquisita with IgG autoantibodies against type VII collagen and laminin alpha3.

BACKGROUND: The inflammatory variant of epidermolysis bullosa acquisita (EBA) may clinically closely resemble bullous or cicatricial pemphigoid. Patients with inflammatory EBA have IgG autoantibodies against type VII collagen. Patients with anti-epiligrin cicatricial pemphigoid have IgG autoantibodies against laminin 5. OBSERVATION: We describe a patient with inflammatory EBA exhibiting nonscarring oral and vaginal involvement. Indirect immunofluorescence using skin substrate lacking an epidermal basement membrane molecule, direct immunoelectron microscopy, immunoblot, and immunoprecipitation studies revealed the simultaneous presence of circulating IgG autoantibodies against type VII collagen and laminin alpha3. A final diagnosis of EBA was based on the sublamina densa level of blister formation. CONCLUSION: This case illustrates the clinical and immunological overlap between EBA and anti-epiligrin cicatricial pemphigoid, a unique finding that may have developed as a consequence of epitope spreading.

Irritancy of antiseptics tested by repeated open exposures on the human skin, evaluated by non-invasive methods.

The aim of the study was to test the irritancy of 6 antiseptics in an open exposure model. The following agents were tested in their normal use concentrations using open exposures, 2x daily for 4 days in 20 subjects: chlorhexidine 4% (CH), chlorhexidine 0.5% in ethanol 70% (CE), ethanol 70% (ET), iodine 1% in ethanol 70% (IE), povidone-iodine 10% (PI) and sodium hypochlorite 0.25% (SH). Responses were evaluated by visual scoring, subjective irritancy scoring, stratum corneum hydration (Corneometer), transepidermal water loss and laser Doppler flowmetry. Exposure to SH had to be discontinued after 4 applications because of severe subjective irritation. The same held true for IE (7 applications), whereas the other agents were exposed 8x. All evaluation methods showed SH to be significantly more irritating than IE, which was in turn more irritating than CH, CE, ET and PI. Thus, it can be concluded that CH, CE, ET and PI were non-irritating in this open exposure model.

Infrared Spectra Simulation of Substituted Benzene Derivatives on the Basis of a 3D Structure Representation.

The identification of chemical compounds from their infrared spectra faces new challenges from novel experimental techniques such as combinatorial chemistry. To rapidly provide estimates for the infrared spectra of candidate structures, an empirical approach to the modeling of the relationships between the 3D structure of a molecule and its infrared spectrum has been developed. This method is based on a novel 3D structure representation and a powerful modeling technique, a counterpropagation neural network. A dataset of 871 mono-, di-, and trisubstitued benzene derivatives is analyzed with this approach.

Acute cardiorespiratory failure as presenting symptom of chronic lymphocytic leukemia.

A patient with acute cardiorespiratory failure caused by hyperleukocytosis due to chronic lymphocytic leukaemia (CLL) is described. Although acute pulmonary failure due to leukostasis is a known and often postmortem finding in patients with acute myelocytic leukaemia (AML) or chronic myelocytic leukaemia (CML) in blastic crises, it is rare in CLL.

Shifts and awakenings: valuable indicators of the quality of sleep: do these parameters react differently to hypnotics?

In order to test the assumption that the sleep stability increases as the number of shifts and awakenings decreases, all-night sleep recordings (registered at home) were reanalyzed. The registrations belong to 10 young good sleepers, 10 adult good sleepers, 10 insomnia patients without treatment, 10 treated with a benzodiazepine and 10 treated with a nonbenzodiazepine hypnotic, 10 patients with proven narcolepsy, and 10 with obstructive sleep apnea syndrome (OSAS). For each of the categories NREM-1-2, NREM 3-4, and REM sleep, indices were defined as the number of shifts and awakenings that occurred per hour. Our results show that the indices of awakenings for the good as well for the bad sleepers were similar, whereas the indices of awakenings were very group dependent. We interpreted these results as showing that awakenings are valuable indicators for studying the quality of sleep, whereas shifts are not.

Effects of delta sleep-inducing peptide on sleep of chronic insomniac patients. A double-blind study.

The influence of delta sleep-inducing peptide (DSIP) on sleep was studied in 16 chronic insomniac patients according to a double-blind matched-pairs parallel-groups design. Subjects slept for 5 consecutive nights in the laboratory. Night 1 was used for adaptation, night 2 for baseline measurements. In the afternoon before the 3rd, 4th and 5th night, half of the patients received intravenously 25 nmol/kg body weight DSIP, and half of the patients a glucose solution (placebo). Measures for sleep structure, objective (polysomnography) and subjective sleep quality and for subjective tiredness were assessed. The results for objective sleep quality indicated higher sleep efficiency and shorter sleep latency with DSIP as compared to placebo. One measure of subjectively estimated tiredness decreased within the DSIP group. Data analysis suggested, however, that the statistically significant effects were weak and in part could be due to an incidental change in the placebo group. As none of the other measures, including subjective sleep quality, showed any change, it was concluded that short-term treatment of chronic insomnia with DSIP is not likely to be of major therapeutic benefit.