Computational study of the reaction between biogenic stabilized Criegee intermediates and sulfuric acid

We have postulated a mechanism for the reaction of sulfuric acid with stabilized Criegee intermediates (sCIs). We have computed Gibbs free energies for the reaction of sulfuric acid with two biogenic sCIs and three smaller model species. We have also calculated Gibbs free energies for two competing sink reactions. Due to the large size of the biogenic sCIs, the computations have been performed at the relatively modest B3LYP/6-31G(d,p) and B3LYP/6-311+G(2d,p) levels. However, single-point RI-CC2/def2-QZVPP calculations for the (CH3)(2)COO model species are in good agreement with the B3LYP results. The reaction is found to be strongly exothermic for all studied species. Activation barrier calculations on the (CH3)(2)COO model species further indicate that the reaction with sulfuric acid may proceed significantly faster than the sink reaction with water. If the same applies to the biogenic sCIs, the proposed reactions could account for some part of the organically assisted new particle formation events observed in the atmosphere.     

Auditory and nonauditory factors affecting speech reception in noise by older listeners

Speech reception thresholds (SRTs) for sentences were determined in stationary and modulated background noise for two age-matched groups of normal-hearing (N = 13) and hearing-impaired listeners (N = 21). Correlations were studied between the SRT in noise and measures of auditory and nonauditory performance, after which stepwise regression analyses were performed within both groups separately. Auditory measures included the pure-tone audiogram and tests of spectral and temporal acuity. Nonauditory factors were assessed by measuring the text reception threshold (TRT), a visual analogue of the SRT, in which partially masked sentences were adaptively presented. Results indicate that, for the normal-hearing group, the variance in speech reception is mainly associated with nonauditory factors, both in stationary and in modulated noise. For the hearing-impaired group, speech reception in stationary noise is mainly related to the audiogram, even when audibility effects are accounted for. In modulated noise, both auditory (temporal acuity) and nonauditory factors (TRT) contribute to explaining interindividual differences in speech reception. Age was not a significant factor in the results. It is concluded that, under some conditions, nonauditory factors are relevant for the perception of speech in noise. Further evaluation of nonauditory factors might enable adapting the expectations from auditory rehabilitation in clinical settings.     

Acid‐Mediated Formation of Radicals or Baeyer–Villiger Oxidation from Criegee Adducts

The acid‐mediated reaction of ketones with hydroperoxides generates radicals, a process with reaction conditions similar to those of the Baeyer–Villiger oxidation but with an outcome resembling the formation of hydroxyl radicals via ozonolysis in the atmosphere. The Baeyer–Villiger oxidation forms esters from ketones, with the preferred use of peracids. In contrast, alkyl hydroperoxides and hydrogen peroxide react with ketones by condensation to form alkenyl peroxides, which rapidly undergo homolytic O? O bond cleavage to form radicals. Both reactions are believed to proceed via Criegee adducts, but the electronic nature of the peroxide residue determines the subsequent reaction pathways. DFT calculations and experimental results support the idea that, unlike previously assumed, the Baeyer–Villiger reaction is not intrinsically difficult with alkyl hydroperoxides and hydrogen peroxide but rather that the alternative radical formation is increasingly favored.     

The role of magnetization compensation point for efficient ultrafast control of magnetization in Gd<Subscript>24</Subscript>Fe<Subscript>66.5</Subscript>Co<Subscript>9.5</Subscript> alloy

The ability of a femtosecond laser pulse to manipulate and reverse the magnetization in a ferrimagnetic Gd₂₄Fe_66.5Co_9.5 thin film was studied experimentally as a function of temperature. For a fixed energy of the laser pulse, the dynamics of magnetization showed different behavior depending on whether the sample temperature was below or above the magnetization compensation point (T _M ). The conditions for full ultrafast demagnetization and magnetization reversal were easily achieved below T _M , while the same laser excitation caused just 50% demagnetization above T _M . This interesting change in magnetization dynamics is qualitatively explained in terms of effective changes in the magnitudes of magnetizations of atomic sublattices.     

Crosslinking of trimethylene carbonate and D, L-lactide (co-) polymers by gamma irradiation in the presence of pentaerythritol triacrylate

High‐molecular‐weight (co)polymers of trimethylene carbonate and D ,L ‐lactide are efficiently crosslinked using PETA during gamma irradiation. Form‐stable networks with gel contents of 86 ± 5 to 96 ± 1 are obtained from non‐crystalline (co)polymers. Glass transition temperatures and elastic moduli of the networks can be varied by adjusting the copolymer composition. The PETA‐containing (co)polymer networks are not cytotoxic. Upon incubation in macrophage cultures for 14 d, all (co)polymer films and PETA‐containing network films erode to varying extents, showing that these materials can be degraded by cell‐mediated erosion processes. This method is very useful for the facile preparation of TMC‐ and DLLA‐containing form‐stable networks from high‐molecular‐weight polymers.

     

Development and validation of real-time PCR screening methods for detection of cry1A.105 and cry2Ab2 genes in genetically modified organisms

Primers and probes were developed for the element-specific detection of cry1A.105 and cry2Ab2 genes, based on their DNA sequence as present in GM maize MON89034. Cry genes are present in many genetically modified (GM) plants and they are important targets for developing GMO element-specific detection methods. Element-specific methods can be of use to screen for the presence of GMOs in food and feed supply chains. Moreover, a combination of GMO elements may indicate the potential presence of unapproved GMOs (UGMs). Primer-probe combinations were evaluated in terms of specificity, efficiency and limit of detection. Except for specificity, the complete experiment was performed in 9 PCR runs, on 9 different days and by testing 8 DNA concentrations. The results showed a high specificity and efficiency for cry1A.105 and cry2Ab2 detection. The limit of detection was between 0.05 and 0.01 ng DNA per PCR reaction for both assays. These data confirm the applicability of these new primer-probe combinations for element detection that can contribute to the screening for GM and UGM crops in food and feed samples.     

Dried blood spot UHPLC-MS/MS analysis of oseltamivir and oseltamivircarboxylate—a validated assay for the clinic

The neuraminidase inhibitor oseltamivir (Tamiflu®) is currently the first-line therapy for patients with influenza virus infection. Common analysis of the prodrug and its active metabolite oseltamivircarboxylate is determined via extraction from plasma. Compared with these assays, dried blood spot (DBS) analysis provides several advantages, including a minimum sample volume required for the measurement of drugs in whole blood. Samples can easily be obtained via a simple, non-invasive finger or heel prick. Mainly, these characteristics make DBS an ideal tool for pediatrics and to measure multiple time points such as those needed in therapeutic drug monitoring or pharmacokinetic studies. Additionally, DBS sample preparation, stability, and storage are usually most convenient. In the present work, we developed and fully validated a DBS assay for the simultaneous determination of oseltamivir and oseltamivircarboxylate concentrations in human whole blood. We demonstrate the simplicity of DBS sample preparation, and a fast, accurate and reproducible analysis using ultra high-performance liquid chromatography coupled to a triple quadrupole mass spectrometer. A thorough validation on the basis of the most recent FDA guidelines for bioanalytical method validation showed that the method is selective, precise, and accurate (≤15% RSD), and sensitive over the relevant clinical range of 5–1,500 ng/mL for oseltamivir and 20–1,500 ng/mL for the oseltamivircarboxylate metabolite. As a proof of concept, oseltamivir and oseltamivircarboxylate levels were determined in DBS obtained from healthy volunteers who received a single oral dose of Tamiflu®.     

Local Sharply Transitive Actions on Finite Generalized Quadrangles

We classify the finite generalized quadrangles containing a line L such that some group of collineations acts sharply transitively on the ordered pentagons which start with two points of L. This can be seen as a generalization of a result of Thas and the second author [22] classifying all finite generalized quadrangles admitting a collineation group that acts transitively on all ordered pentagons, although the restriction to sharp transitivity is essential in our arguments. However, the conclusion is exactly the same family of classical generalized quadrangles (the orthogonal quadrangles and their duals). Our main result thus provides a local group theoretic characterization of these classical quadrangles.     

The Effect of Oxandrolone on Voice Frequency in Growth Hormone-Treated Girls With Turner Syndrome

Objectives/Hypothesis

Oxandrolone (Ox) increases height gain but may also cause voice deepening in growth hormone (GH)-treated girls with Turner syndrome (TS). We assessed the effect of Ox on objective and subjective speaking voice frequency in GH-treated girls with TS.

Study Design

A multicenter, randomized, placebo (Pl)-controlled, double-blind study was conducted.

Methods

One hundred thirty-three patients were included and treated with GH (1.33 mg/m²/d) from baseline, combined with Pl or Ox in a low (0.03 mg/kg/d) or conventional (0.06 mg/kg/d) dose from the age of 8 years and estrogens from the age of 12 years. Yearly from starting Ox/Pl until 6 months after discontinuing GH + Ox/Pl, voices were recorded and questionnaires were completed.

Results

At start, mean (±standard deviation [SD]) voice frequency SD score (SDS) was high for age (1.0 ± 1.2, P < 0.001) but normal for height. Compared with GH + Pl, voices tended to lower on GH + Ox 0.03 (P = 0.09) and significantly lowered on GH + Ox 0.06 (P = 0.007). At the last measurement, voice frequency SDS was still relatively high in GH + Pl group (0.6 ± 0.7, P = 0.002) but similar to healthy girls in both GH + Ox groups. Voice frequency became lower than −2 SDS in one patient (3%) on GH + Ox 0.03 and three patients (11%) on GH + Ox 0.06. The percentage of patients reporting subjective voice deepening was similar between the dosage groups.

Conclusions

Untreated girls with TS have relatively high-pitched voices. The addition of Ox to GH decreases voice frequency in a dose-dependent way. Although most voice frequencies remain within the normal range, they may occasionally become lower than −2 SDS, especially on GH + Ox 0.06 mg/kg/d.     

Bridging flocculation of PEI-functionalized latex particles using nanocrystalline cellulose

Polystyrene microspheres were functionalized by covalent binding of 250 kDa linear PEI and ethanolamine, acting as a blocking agent, through bioconjugation with EDAC. The functionalized spheres were found to become less susceptible to salt-induced flocculation due to electrosteric stability, caused by the PEI chains at low NaCl concentrations, and at high salt concentration, by steric repulsion by the ethanolamine layer, which in combination with van der Waals attraction results in a shallow energy minimum and the formation of a few unstable aggregates. The latex aggregated in the presence of nanocrystalline cellulose (NCC) with varying efficiencies, depending on the ratio of NCC to latex particles in solution. Polyelectrolyte titration showed that each latex sphere contained about 15 grafted PEI chains. The fastest aggregation was detected when about half of these chains were covered by a single NCC particle.