Simultaneous measurements of As, Mo, Sb, V and W using a ferrihydrite diffusive gradients in thin films (DGT) device

The ferrihydrite-backed DGT (diffusive gradients in thin films), recently developed for arsenic and phosphate measurements was, for the first time, characterized with respect to molybdate, antimonate, vanadate and tungstate determination. Arsenate was included in the characterization to allow comparison with literature data and thus provide quality control of the measurements. In addition to laboratory experiments, field measurements were carried out in a natural stream in northern Sweden affected by mine drainage. It was shown that ferrihydrite-DGT is suitable for simultaneous determination of labile arsenic, molybdate, antimonate, vanadate and tungstate over a wide pH range. Diffusion coefficients were estimated using two different methods; diffusion cell and direct uptake to DGT devices in synthetic solutions. Estimations of the coefficients using the direct uptake method were performed between pH 4 and 8. The results from the two methods agreed well irrespective of pH, except for molybdate and antimonate that showed decreased values at pH 8. Adsorption of the analytes to ferrihydrite gel-discs was rapid at all pH values. However, there was a tendency toward lower adsorption affinity for antimonate compared to the other anions. 100% recovery of accumulated analytes was achieved through complete dissolution of the ferrihydrite adsorbent using 1.4 molL(-1) HNO(3) with 0.1 molL(-1) HF. From field sampling it was concluded that the opportunities for accurate antimonate and molybdate determination decrease at pH≥8.7. DGT-labile concentrations were generally lower than dissolved concentrations. Relatively lower DGT concentrations, compared to dissolved (<0.45 μm), were observed under a period when ferric oxide precipitations were detected on the DGT protective filter.     

A single-channel microparticle sieve based on Brownian ratchets

We present a novel device for the separation of microparticles in a single channel, which is made of inversely asymmetric Brownian ratchets. It enables separation into two different fractions with an adjustable threshold and can be modeled with good agreement. This device serves as proof of concept for an extremely compact class of microsieves.     

3 d metal ions in highly unusual eight-coordination: the phosphate-capped dodecapalladate(II) nanocube

Trapped in a noble cube: A novel family of noble metalates has been discovered in which a 3d metal ion M (M = Mn(II), Fe(III), Co(II), Cu(II), Zn(II)) is encapsulated by a 12 palladium-oxo cage {Pd(12)O(32)}, which is capped by eight phosphate groups. Such discrete nanocubes were further investigated by EPR spectroscopy, electrochemistry, and in homogeneous hydrogenation catalysis.     

Partial Hydrolysis of Poly(2‐ethyl‐2‐oxazoline) and Potential Implications for Biomedical Applications?

The hydrolysis of PEtOx is studied to evaluate the potential toxicity of partially hydrolyzed polymers that might interfere with its increasing popularity for biomedical applications. The hydrolysis of PEtOx is studied in the presence of digestive enzymes (gastric and intestinal) and at 5.8 M hydrochloric acid as a function of temperature (57, 73, 90, and 100 °C). It is found that PEtOx undergoes negligible hydrolysis at 37 °C and that thermal and solution properties are not altered when up to 10% of the polymer backbone is hydrolyzed. Mucosal irritation and cytotoxicity is also absent up to 10% hydrolysis levels. In conclusion, PEtOx will not decompose at physiological conditions, and partial hydrolysis will not limit its biomedical applications.

     

Input permutation method to detect active voxels in fMRI study

Correctly identifying voxels or regions of interest (ROI) that actively respond to a given stimulus is often an important objective/step in many functional magnetic resonance imaging (fMRI) studies. In this article, we study a nonparametric method to detect active voxels, which makes minimal assumption about the distribution of blood oxygen level-dependent (BOLD) signals. Our proposal has several interesting features. It uses time lagged correlation to take into account the delay in response to the stimulus, due to hemodynamic variations. We introduce an input permutation method (IPM), a type of block permutation method, to approximate the null distribution of the test statistic. Also, we propose to pool the permutation-derived statistics of preselected voxels for a better approximation to the null distribution. Finally, we control multiple testing error rate using the local false discovery rate (FDR) by Efron [Correlation and large-scale simultaneous hypothesis testing. J Am Stat Assoc 102 (2007) 93–103] and Park et al. [Estimation of empirical null using a mixture of normals and its use in local false discovery rate. Comput Stat Data Anal 55 (2011) 2421–2432] to select the active voxels.     

Combining piracetam and lithium salts: ionic co-crystals and co-drugs?

Mechanochemical reaction of solid piracetam with the inorganic salts LiCl and LiBr yields ionic co-crystals which are also co-drugs, characterized by markedly different thermal properties with respect to pure components, also depending on the method for preparation and/or conditions of measurements; single crystal and powder X-ray diffraction at variable temperatures, DSC, TGA, hot stage microscopy (HSM) and intrinsic dissolution rate have been used to fully characterize the solid products.     

Impedance study of thiolated polyaniline

Covalent attachment of thiolated probes to conducting polymers such as polyaniline (PANI) is a promising approach towards the development of electrochemical sensors and biosensors. However, thiolation alters the conjugated polymer backbone and influences the electrochemical behavior of the conducting polymer. PANI studied in this work was electropolymerized on glassy carbon (GC) electrodes from a solution of 0.1 M aniline in 0.5 or 1.0 M H₂SO₄. The GC/PANI electrodes were then functionalized by covalent attachment of 2-mercaptoethanol to the PANI backbone. The progress of thiolation was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Thiolation of PANI was found to cause an initial decrease in electroactivity at 0–0.25 V and an increase in electroactivity at 0.25–0.6 V. However, prolonged thiolation caused a loss of electroactivity of PANI, which could be seen from EIS measurements as a dramatic decrease in the bulk redox capacitance of PANI.