On the Mediated Electron Transfer of Immobilized Galactose Oxidase for Biotechnological Applications

The use of enzymes as catalysts in chemical synthesis offers advantages in terms of clean and highly selective transformations. Galactose oxidase (GalOx) is a remarkable enzyme with several applications in industrial conversions as it catalyzes the oxidation of primary alcohols. We have investigated the wiring of GalOx with a redox polymer; this enables mediated electron transfer with the electrode surface for its potential application in biotechnological conversions. As a result of electrochemical regeneration of the catalytic center, the formation of harmful H₂O₂ is minimized during enzymatic catalysis. The introduced bioelectrode was applied to the conversion of bio-renewable platform materials, with glycerol as model substrate. The biocatalytic transformations of glycerol and 5-hydroxymethylfurfural (HMF) were investigated in a circular flow-through setup to assess the possibility of substrate over-oxidation, which is observed for glycerol oxidation but not during HMF conversion.     

Optimizing carbon coating parameters for obtaining SiO2/C anodes with improved electrochemical performance

In this work, we present a comprehensive and systematic study on the use of low-cost and highly abundant carbon precursors to obtain SiO₂/C anodes with superior electrochemical performance towards Li-ions. Different SiO₂/C composites are prepared by soaking silica nanoparticles in solutions containing 20 wt%, 40 wt%, or 60 wt% of glucose, sucrose, or cornstarch, followed by thermal decomposition of the carbohydrates at 850 °C or 1200 °C. Structural, microstructural, and textural differences on the composites derived from the different carbon coating treatments are related to the electrochemical performance of the anodes. Composites containing final carbon contents close to 15 wt% show a complete coverage of the SiO₂ particles with a nanometric carbon layer and exhibit the best electrochemical results. The increase in the annealing temperature from 850 to 1200 °C reduces the porosity of the carbon layer and increases its level of ordering, both having positive effects on the overall electrochemical performance of the electrodes. SiO₂/C composites coated with 40 wt% sucrose and heat treated at 1200 °C display the best electrochemical performance, delivering a reversible specific capacity of 723 mAhg⁻¹ at 50 mAg⁻¹ after 100 cycles, which is considerably higher than the reversible capacity of 233 mAhg⁻¹ obtained with the uncoated material cycled under the same conditions.

     

Simple linear asymmetrical complexes of silver(I): NC-Ag-NH3 and Br-Ag-NH3

The compounds Ag(CN)(NH(3)) and Ag(Br)(NH(3)) are remarkable in that they form solids containing the simple molecular units NC-Ag-NH(3) and Br-Ag-NH(3), rather than extended solids, and are the first examples of simple linear asymmetric complexes of silver(I).     

The AM05 density functional applied to solids

We show that the AM05 functional [Armiento and Mattsson, Phys. Rev. B 72, 085108 (2005)] has the same excellent performance for solids as the hybrid density functionals tested in Paier et al. [J. Chem. Phys. 124, 154709 (2006); 125, 249901 (2006)]. This confirms the original finding that AM05 performs exceptionally well for solids and surfaces. Hartree-Fock hybrid calculations are typically an order of magnitude slower than local or semilocal density functionals such as AM05, which is of a regular semilocal generalized gradient approximation form. The performance of AM05 is on average found to be superior to selecting the best of local density approximation and PBE for each solid. By comparing data from several different electronic-structure codes, we have determined that the numerical errors in this study are equal to or smaller than the corresponding experimental uncertainties.     

Combination of a liquid chromatography-ultraviolet method with a non-volatile eluent, peak trapping and a liquid chromatography-mass spectrometry method with a volatile eluent to characterise erythromycin related substances

The selectivity and sensitivity obtained with volatile liquid chromatographic (LC) methods are often inferior compared to non-volatile ones. However, the buffers often used in the non-volatile system are incompatible to mass spectrometry (MS). So, the characterisation of unknown peaks in a non-volatile system, based on data obtained from a volatile LC-MS method, is problematic. In this study, the unknown peaks in a non-volatile liquid chromatography coupled with ultraviolet detection (LC-UV) system were directly characterised by a volatile LC-MS system using a peak trapping technique. Each peak eluted from the non-volatile system was trapped by a switching valve and sent to a LC-MS system using a volatile mobile phase. Mass spectral data were acquired on an LCQ ion trap mass spectrometer equipped with electrospray ionisation (ESI) operated in the positive ion mode. Using this technique, the fragmentation behaviour of erythromycin and its related substances was studied and the components occurring in commercial samples were investigated. In total 25 compounds mentioned in the literature were traced. Fourteen more unknown impurities were also studied.     

Vocalizations produced by humpback whale (Megaptera novaeangliae) calves recorded in Hawaii

Although humpback whale (Megaptera novaeangliae) calves are reported to vocalize, this has not been measurably verified. During March 2006, an underwater video camera and two-element hydrophone array were used to record nonsong vocalizations from a mother-calf escort off Hawaii. Acoustic data were analyzed; measured time delays between hydrophones provided bearings to 21 distinct vocalizations produced by the male calf. Signals were pulsed (71%), frequency modulated (19%), or amplitude modulated (10%). They were of simple structure, low frequency (mean=220 Hz), brief duration (mean=170 ms), and relatively narrow bandwidth (mean=2 kHz). The calf produced three series of "grunts" when approaching the diver. During winters of the years 2001-2005 in Hawaii, nonsong vocalizations were recorded in 109 (65%) of 169 groups with a calf using an underwater video and single (omnidirectional) hydrophone. Nonsong vocalizations were most common (34 of 39) in lone mother-calf pairs. A subsample from this dataset of 60 signals assessed to be vocalizations provided strong evidence that 10 male and 18 female calves vocalized based on statistical similarity to the 21 verified calf signals, proximity to an isolated calf (27 of 28 calves), strong signal-to-noise ratio, and/or bubble emissions coincident to sound.     

Low frequency vocalizations attributed to sei whales (Balaenoptera borealis)

Low frequency (<100 Hz) downsweep vocalizations were repeatedly recorded from ocean gliders east of Cape Cod, MA in May 2005. To identify the species responsible for this call, arrays of acoustic recorders were deployed in this same area during 2006 and 2007. 70 h of collocated visual observations at the center of each array were used to compare the localized occurrence of this call to the occurrence of three baleen whale species: right, humpback, and sei whales. The low frequency call was significantly associated only with the occurrence of sei whales. On average, the call swept from 82 to 34 Hz over 1.4 s and was most often produced as a single call, although pairs and (more rarely) triplets were occasionally detected. Individual calls comprising the pairs were localized to within tens of meters of one another and were more similar to one another than to contemporaneous calls by other whales, suggesting that paired calls may be produced by the same animal. A synthetic kernel was developed to facilitate automatic detection of this call using spectrogram-correlation methods. The optimal kernel missed 14% of calls, and of all the calls that were automatically detected, 15% were false positives.     

Generic tripartite Bell nonlocality sudden death under local phase noise

We definitively show, using an explicit and broadly applicable model, that local phase noise that is capable of eliminating state coherence only in the infinite-time limit is capable of eliminating nonlocality in finite time in three two-level systems prepared in the Bell-nonlocal tripartite states of the generic entanglement class.