Diffusion coefficient measurement in a microfluidic analyzer using dual-beam microscale-refractive index gradient detection. Application to on-chip molecular size determination

We report a microchip-based detection scheme to determine the diffusion coefficient and molecular mass (to the extent correlated to molecular size) of analytes of interest. The device works by simultaneously measuring the refractive index gradient (RIG) between adjacent laminar flows at two different positions along a microchannel. The device, referred to as a microscale molecular mass sensor (micro-MMS), takes advantage of laminar flow conditions where the mixing of two streams occurs essentially by diffusion across the boundary between the two streams. Two flows merge on the microchip, one containing solvent only, referred to as the mobile phase stream and one which contains the analyte(s) of interest in the solvent, i.e. the sample stream. As these two streams merge and flow parallel to each other down the microchannel a RIG is created by the concentration gradient. The RIG is further influenced by analyte diffusion from the sample stream into the mobile phase stream. Measuring the RIG at a position close to the merging point (upstream signal) and simultaneously a selected distance further down the microchannel (downstream signal) provides real-time data related to the extent a given analyte has diffused, which can be readily correlated to analyte molecular mass by taking the ratio of the downstream-to-upstream signals. For the dual-beam RIG measurements, a diode laser output is coupled to a single mode fiber optic splitter with two output fibers. Light from each fiber passes through a graded refractive index (GRIN) lens forming a collimated beam that then passes through the microchannel and then on to a position sensitive detector (PSD). The RIG at both detection positions deflects the two collimated probe beams. The deflection angle of each beam is then measured on two separate PSDs. The micro-MMS was evaluated using polyethylene glycols (PEGs), sugars, and as a detector for size-exclusion chromatography (SEC). Peak purity can be readily identified using the micro-MMS with SEC. The limit of detection was 0.9 ppm (PEG at 11 840 g/mol) at the upstream detection position corresponding to a RI limit of detection (LOD) (3sigma) of 7-10(-8) RI. The pathlength for the RIG measurement was 200 microm and the angular LOD was 0.23 micro(rad) with a detection volume of 8 nl at both positions. The average molecular mass resolution was 9% (relative standard deviation) for a series of PEGs ranging in molecular mass from 106 to 22 800 g/mol. With this excellent mass resolution, small molecules such as monosaccharides, disaccharides, and so on, are readily distinguished. The sensor is demonstrated to readily determine unknown diffusion coefficients.     

Enhanced ethanol sensing properties of WO3 modified TiO2 nanorods

Pristine and WO₃ decorated TiO₂ nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO₂ NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO₂ NRs and thermally oxidised to obtain WO₃ nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO₂ NRs with WO₃.     

Flowerlike hybrid horseradish peroxidase nanobiocatalyst for the polymerization of guaiacol

In this study, the catalytic activity and stability of flowerlike hybrid horseradish peroxidase (HRP) nanobiocatalyst (HRP-Cu ²⁺ ) obtained from Cu ²⁺ ions and HRP enzyme in the polymerization reaction of guaiacol were analyzed. We demonstrated that HRP-Cu ²⁺ and hydrogen peroxide (H ₂ O ₂ ) initiator showed significantly increased catalytic activity and stability on the polymerization of guaiacol compared to that of free HRP enzyme. Poly(guaiacol) was observed with quite high yields (88%) and molecular weights (38,000 g/mol) under pH 7.4 phosphate-buffered saline (PBS) conditions at 60 °C with 5 weight% of HRP-Cu ²⁺ loading. HRP-Cu ²⁺ also shows very high thermal stability and works even at 70 °C reaction temperature; free HRP enzyme denatures at that temperature. Furthermore, HRP-Cu ²⁺ provided considerable repeated use and showed some degree of catalytic activity, even after the fourth recycle, in the polymerization of guaiacol.     

Chemical composition,antimicrobial, and lipase enzyme activity of essential oil and solvent extracts from Serapias orientalis subsp. orientalis

The volatile components of essential oil (EO), SPME, and SPME of solvent extracts ( n -hexane, methanol, and water) obtained from fresh Serapias orientalis subsp. orientalis ( Soo ) were analyzed by GC-FID/MS. EO of Soo gave 11 compounds in the percentage of 99.97%; capronaldehyde (37.01%), 2-( E )-hexenal (23.19%), and n -nonanal (19.05%) were found to be major constituents. SPME GC-FID/MS analyses of fresh plant and solvent extracts of Soo revealed 7, 12, 7, and 4 compounds within the range of 99.7% to 99.9%. Limonene (76.5%, 41.7%, and 61.3%) was the major compound in SPMEs of the n -hexane and methanol extracts. α -Methoxy- p -cresol (52.9%) was the main component in its water extract. The antimicrobial activity of EO and the solvent extracts of Soo were screened against 9microorganisms. EO showed the best activity against Mycobacterium smegmatis , with 79.5 µg/mL MIC value. The n -hexane, methanol, and water extracts were the most active against the Staphylococcus aureus within the range of 81.25–125.0 µg/mL (MIC). IC ₅₀ values for the lipase enzyme inhibitory activity of EO and solvent extracts ( n -hexane, methanol, and water) were determined to be 59.87 µg/mL, 64.03 µg/mL, 101.91 µg/mL, and 121.24 µg/mL, respectively.     

Development of an HPLC method for determination of pentachloronitrobenzene, hexachlorobenzene and their possible metabolites

Background

Pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) are highly toxic and widespread in every environmental compartment. Some of metabolic products such as amino/nitro containing chlorinated aromatic compounds can be determined by gas chromatography coupled with electron capture detector (GC-ECD). However, it is difficult to identify some of chlorophenolic and chloroquinolic intermediates produced from PCNB and HCB by the above mentioned technique. Therefore, for analysis of these compounds and their metabolites, we have developed a high performance liquid chromatography (HPLC) based method.

Results

The extraction of PCNB and HCB from soil and minimal salt medium was carried out with ethyl acetate and hexane respectively with good recoveries (98% for PCNB and 97% for HCB). The validation of the proposed extraction and HPLC method was done by analysis of PCNB and HCB biodegradation and their metabolites identification from anaerobic enriched soil samples.

Conclusion

A rapid, sensitive and simple HPLC based analytical method was developed for the analysis of PCNB, HCB and their possible intermediates.     

Decay rates of solutions to thermoviscoelastic plates with memory

We consider the thermoelastic plate under the presence of along range memory. We find uniform rates of decay (in time)of the energy, provided that suitable assumptions on the relaxationfunctions are given. Namely, if the relaxation decays exponentiallythen the first order energy also decays exponentially. Whenthe relaxation g satisfies -c₁g(t)^1+1/_p g'(t) -c_og(t)^1+1/_p; and g,g^1-1/_p L¹ (R) withp > 2 then the energy decays as 1/(1+t)^p. A new Liapunov functionalis built for this problem.     

Calculations of Isoelectronic Series of He Using Noninteger n‐Slater Type Orbitals in Single and Double Zeta Approximations

Using integer and noninteger n-Slater type orbitals in single- and double-zeta approximations, the Hartree-Fock-Roothaan calculations were performed for the ground states of first ten cationic members of the isoelectronic series of He atom. All the noninteger parameters and orbital exponents were fully optimized. In the case of noninteger n-Slater type orbitals in double zeta basis sets, the results of calculations obtained are more close to the numerical Hatree-Fock values and the average deviations of our ground state energies do not exceed 2×10^－6 hartrees of their numerical results.     

Transition Metal Ion-binding Properties of a 14-Membered N2O2S2- Macrobicyclic Ligand

The selective liquid–liquid extraction of various transition metal cations from the aqueous phase to the organic phase was carried out using a 14-membered N₂O₂S₂-macrobicycle. Metal picrates such as Pb²⁺, Co²⁺, Zn²⁺, Ni²⁺,Cu²⁺ and Cd²⁺ were used in this extraction studies. It was found that the ligand showed moderate selectivity towards Pb²⁺ only among the other metals. The extraction constant (log K _ex) was determined to be 13.8 for Pb²⁺ complex.     

A high voltage asymmetric waveform generator for FAIMS

High field asymmetric waveform ion mobility spectrometry (FAIMS) has been used increasingly in recent years as an additional method of ion separation and selection before mass spectrometry. The FAIMS electrodes are relatively simple to design and fabricate for laboratories wishing to implement their own FAIMS designs. However, construction of the electronics apparatus needed to produce the required high magnitude asymmetric electric field oscillating at a frequency of several hundred kilohertz is not trivial. Here we present an entirely custom-built electronics setup capable of supplying the required waveforms and voltages. The apparatus is relatively simple and inexpensive to implement. We also present data acquired on this system demonstrating the use of FAIMS as a gas-phase ion filter interface to an ion trap mass spectrometer.