Absorption spectra and photolysis of methyl peroxide in liquid and frozen water.

Methyl peroxide (CH(3)OOH) is commonly found in atmospheric waters and ices in significant concentrations. It is the simplest organic peroxide and an important precursor to hydroxyl radical. Many studies have examined the photochemical behavior of gaseous CH(3)OOH; however, the photochemistry of liquid and frozen water solutions is poorly understood.

Continuous apple consumption induces oral tolerance in birch-pollen-associated apple allergy.

Background: Patients with birch pollen allergy (major allergen: Bet v 1) have often an associated oral allergy syndrome (OAS) to apple, which contains the cross-reactive allergen Mal d 1. As successful birch pollen immunotherapy does not consistently improve apple related OAS symptoms, we evaluated whether regular apple consumption has an effect on OAS and immune parameters of Mal d 1 or Bet v 1 allergy.

Methods: A total of 40 patients with a clear history of birch pollen rhinoconjunctivitis and associated OAS to apple were included in an open, randomized, controlled clinical trial: 27 patients consumed daily defined amount of apple (1-128 g), doubling the amount every two to three weeks, while 13 patients remained untreated.

Independent and combined effects of exercise training and metformin on insulin sensitivity in individuals with prediabetes.

Objective: Physical activity or metformin enhances insulin sensitivity and opposes the progression from prediabetes to type 2 diabetes. The combination may be more effective because each treatment stimulates AMP-activated protein kinase activity in skeletal muscle. We evaluated the effects of exercise training plus metformin on insulin sensitivity in men and women with prediabetes, compared with each treatment alone.

Dupuytren's contracture: a retrospective database analysis to determine hospitalizations in the Netherlands.

Background: Dupuytren's contracture is a condition of the palmar fascia involving contractures of the fascia and skin in the hand. Current treatment for Dupuytren's contracture is mainly limited to surgery. In the Netherlands, little is known about the prevalence of Dupuytren's contracture.

Stability of noble-gas hydrocarbons in an organic liquid-like environment: HXeCCH in acetylene.

Noble-gas hydrides such as HXeCCH are prepared in cryogenic noble-gas matrices where they are stable. Molecular dynamics simulations reported here predict that HXeCCH is chemically stable in clusters of acetylene, and that stability prevails for temperatures of at least 150 K, at which the clusters are liquid-like. The HXeCCH(C(2)H(2))(n) clusters are studied for sizes up to n = 7.

Negishi cross-coupling reactions catalyzed by an aminophosphine-based nickel system: a reliable and general applicable reaction protocol for the high-yielding synthesis of biaryls.

Treatment of NMP solutions of NiCl(2) with 1,1',1''-(phosphanetriyl)tripiperidine (≈2.05 equiv), dissolved in THF, in air at 25 °C forms a highly active catalytic system for the cross-coupling of a large variety of electronically activated, non-activated, deactivated, and ortho-substituted, heterocyclic, and functionalized aryl bromides and aryl chlorides with diarylzinc reagents. Very high levels of conversion and yields were obtained within 2 h at 60 °C in the presence of only 0.

Proton transfer and dissociation of GlyLysH+ following O-H and N-H stretching mode excitations: dynamics simulations.

Proton transfer and dissociation processes following excitation of the OH or NH stretching modes of the proton-bound complex GlyLysH(+) are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are sampled to correspond to the v=1 excited state of the OH or NH stretching modes.

Unité Rhumatologique des Affections de la Main (URAM) scale: development and validation of a tool to assess Dupuytren's disease-specific disability.

Objective: To our knowledge, no functional outcome measure has been developed and validated for Dupuytren's disease. We aimed to develop and validate a patient-reported functional outcome measure for Dupuytren's disease.

Methods: Patients with Dupuytren's disease (n = 9) and medical experts (n = 7) provided input and opinions about limiting activities that were difficult to perform because of Dupuytren's disease for item generation.

Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium. biaryl formation via cationic pincer-type Pd(IV) intermediates.

The aliphatic, phosphine-based pincer complex [(C(10)H(13)-1,3-(CH(2)P(Cy(2))(2))Pd(Cl)] (1) is a highly active Negishi catalyst, enable to quantitatively couple various electronically activated, non-activated, deactivated, sterically hindered and functionalized aryl bromides with various diarylzinc reagents within short reaction times and low catalyst loadings. Experimental observations strongly indicate that a molecular mechanism is operative with initial chloride dissociation of 1 and formation of the cationic T-shaped 14e(-) complex [(C(10)H(13)-1,3-(CH(2)P(C(6)H(11))(2))(2))Pd](+) (B), which undergoes oxidative addition of an aryl bromide (Ar'Br) to yield the cationic, penta-coordinated aryl bromide pincer complexes of type [(C(10)H(13)-1,3-(CH(2)P(Cy(2))(2))Pd(Br)(aryl')](+) (C) with the metal center in the oxidation state of +IV and the aryl unit in cis position relative to the aliphatic pincer core. Subsequent transmetalation with Zn(aryl)(2) result in the cationic diaryl pincer complexes of type [(C(10)H(13)-1,3-(CH(2)P(Cy(2))(2))Pd(aryl)(aryl')](+) (D), which reductively eliminate the coupling products, thereby regenerating the catalyst.

Raman spectra of long chain hydrocarbons: anharmonic calculations, experiment and implications for imaging of biomembranes.

First-principles anharmonic vibrational calculations are carried out for the Raman spectrum of the C-H stretching bands in dodecane, and for the C-D bands in the deuterated molecule. The calculations use the Vibrational Self-Consistent Field (VSCF) algorithm. The results are compared with liquid-state experiments, after smoothing the isolated-molecule sharp-line computed spectra.

Isotopic hydration of cellobiose: vibrational spectroscopy and dynamical simulations.

The conformation and structural dynamics of cellobiose, one of the fundamental building blocks in nature, its C4' epimer, lactose, and their microhydrated complexes, isolated in the gas phase, have been explored through a combination of experiment and theory. Their structures at low temperature have been determined through double resonance, IR-UV vibrational spectroscopy conducted under molecular beam conditions, substituting D(2)O for H(2)O to separate isotopically, the carbohydrate (OH) bands from the hydration (OD) bands. Car-Parrinello (CP2K) simulations, employing dispersion corrected density functional potentials and conducted "on-the-fly" from ∼20 to ∼300 K, have been used to explore the consequences of raising the temperature.

Dupuytren's contracture: a retrospective database analysis to assess clinical management and costs in England.

Background: Dupuytren's disease is a fibro-proliferative disorder affecting ~3-5% of the UK population. Current surgical treatments for Dupuytren's contracture (DC) include fasciectomy and fasciotomy. We assessed the clinical management of DC in England over a 5-year period; associated NHS costs were assessed for a 1-year period.

A new hybrid algorithm for finding the lowest minima of potential surfaces: approach and application to peptides.

A new algorithm is presented for finding the global minimum, and other low-lying minima, of a potential energy surface (PES) of biological molecules. The algorithm synergetically combines three well-known global optimization methods: the diffusion equation method (DEM), which involves smoothing the PES; a simulated annealing (SA) algorithm; and evolutionary programming (EP), whose population-oriented approach allows for a parallel search over different regions of the PES. Tests on five peptides having between 6 and 9 residues show that the code implementing the new combined algorithm is efficient and is found to outperform the constituent methods, DEM and SA.

Vibrational spectra of α-glucose, β-glucose, and sucrose: anharmonic calculations and experiment.

The anharmonic vibrational spectra of α-D-glucose, β-D-glucose, and sucrose are computed by the vibrational self-consistent field (VSCF) method, using potential energy surfaces from electronic structure theory, for the lowest energy conformers that correspond to the gas phase and to the crystalline phase, respectively. The results are compared with ultraviolet-infrared (UV-IR) spectra of phenyl β-D-glucopyranoside in a molecular beam, with literature results for sugars in matrices and with new experimental data for the crystalline state. Car-Parrinello dynamics simulations are also used to study temperature effects on the spectra of α-D-glucose and β-D-glucose and to predict their vibrational spectra at 50, 150, and 300 K.

The efficacy and safety of fasciectomy and fasciotomy for Dupuytren's contracture in European patients: a structured review of published studies.

A structured review of published papers was done to assess the efficacy and safety of fasciectomy and fasciotomy in European patients with Dupuytren's contracture. The outcomes varied across 48 studies. For fasciectomy, outcomes and results were as follows: the proportions of patients with a 100% correction in contracture angle ranged from 61 to 97%, the mean improvement in contracture angle ranged from 58 to 79%, and cases judged excellent/good ranged from 63 to 90%.

Long-term follow-up of multivessel percutaneous coronary intervention with drug-eluting stents for de novo lesions with correlation to the SYNTAX score.

Background: Stent thrombosis (ST) and restenosis are concerns after percutaneous coronary intervention (PCI). Limited information exists concerning clinical and angiographic outcomes following multiple stent insertion. We therefore present the long-term outcome from drug-eluting stent (DES) insertion and correlate this with the Syntax score.

Influence of sex on long-term outcomes after percutaneous coronary intervention with the paclitaxel-eluting coronary stent: results of the "TAXUS Woman" analysis.

Objectives: We conducted the "TAXUS Woman" analysis to assess the influence of sex on long-term outcomes after percutaneous coronary intervention using paclitaxel-eluting stents (PES) in a broad spectrum of patients.

Background: Previous studies indicate that the sex gap suggesting worse outcomes in women has narrowed. However, limited data are available on long-term sex-based outcomes with drug-eluting stents despite their extensive use in current practice.

Local pain and spreading hyperalgesia induced by intramuscular injection of nerve growth factor are not reduced by local anesthesia of the muscle.

Objectives: Injections with local anesthesia for therapeutic and diagnostic purposes are common clinical practice. This double-blind placebo controlled study explores the rational of local anesthetic blocks for the detection of muscle pain as the primary generator in spreading hyperalgesic conditions.

Methods: Experimental muscle pain was induced by injections of nerve growth factor (NGF) in the left and right supraspinatus muscle of 11 healthy volunteers.

Conformational transitions of glycine induced by vibrational excitation of the O-H stretch.

Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the ν=1 excitation of the OH stretch.

Adherence to aldosterone-blocking agents in patients with heart failure.

The use of aldosterone blockers in the pharmacologic therapy for heart failure (HF) in patients with left ventricular systolic dysfunction has been shown to significantly reduce overall mortality, sudden cardiac death, and hospitalization. Patient adherence to polypharmaceutical regimens including aldosterone blockade and other key medication components is a concern for clinicians and their patients. A retrospective cohort study was conducted using integrated US pharmacy/medical claims covering 44.