Photoresist-based integration of enzyme functionality into MEMS

We demonstrate the direct immobilization of glucose oxidase and lactate oxidase onto photoresists commonly used in microfabrication. The method allows for a cost-effective, facile inclusion of enzyme functionality into novel MEMS devices because it does not require any chemical or physical pre-treatment of surfaces, and it is largely compatible with existing fabrication technologies. We used fluorescence imaging and absorbance spectrometry to confirm attachment of the enzymes onto the photoresists and to determine their activity. In addition, the procedure was used to successfully integrate enzyme functionality into a photoresist-based biosensor. This further demonstrates the effectiveness of the approach, and opens a path towards other novel applications in MEMS research.     

Microstructural characterization of hematite during wet and dry millings using Rietveld and XRD line profile analyses

The effects of extended milling in a stirred media mill and a tumbling mill on the structural changes in hematite have been examined using a combination of particle size analysis, BET surface areas, X-ray diffraction (XRD), thermal (TG and DSC) and FTIR measurements. Rietveld's whole profile fitting based on crystal structure refinement and the Warren-Averbach's method of X-ray line profile analysis were applied to monitor the microstructural evolution of the hematite phase.It is found that the BET surface area, X-ray amorphization phase content and XRD line breadths increase over the specific energy input. The use of stirred media mill exhibits larger surface areas, smaller particle sizes, more XRD line broadening and subsequently greater structural distortions compared to the tumbling mill for a given energy input; although the X-ray amorphous phase content remains unaffected by the grinding environments. The maximum X-ray amorphization degree of about 80 and 95% were calculated at a specific energy of 22,400 and 82,000 kJ/kg in the tumbling and stirred media mills respectively. The maximum specific BET surface area in the stirred media and tumbling milling increases to about 72.5 and 6.8 m²/g after 82,000 and 22,400 kJ/kg energy consumption respectively. As a result of structural refinement during milling, the surface-weighted crystallite size in ground hematite are 17 and 4 nm after consuming 22,400 and 82,000 kJ/kg in the tumbling and stirred media mills respectively, corresponding to the volume-weighted crystallite size of 17 and 11 nm. For the same energy consumption in the mills, in turn, the root mean square strain, , increases to about 4.4 × 10^− 3 and 4.9 × 10^− 3. The results of the two applied methods are compared and discussed in details.In addition, thermogravimetric analysis of the wet ground samples reveals that the TG curves represent two weight loss steps. A weight loss is observed around 100 °C in the sample which is attributed to the removal of adsorbed water due to the wet milling operations. A strong weight loss step starting from 100 to 400 °C is attributed to surface/bulk dehydroxilation of iron hydroxides. The weight loss increases with extending of the milling. In contrast, the dry milled samples yield negligible weight losses comparing with the wet ground samples.     

Emotion classification during music listening from forehead biosignals

Emotion recognition systems are helpful in human–machine interactions and clinical applications. This paper investigates the feasibility of using 3-channel forehead biosignals (left temporalis, frontalis, and right temporalis channel) as informative channels for emotion recognition during music listening. Classification of four emotional states (positive valence/low arousal, positive valence/high arousal, negative valence/high arousal, and negative valence/low arousal) in arousal–valence space was performed by employing two parallel cascade-forward neural networks as arousal and valence classifiers. The inputs of the classifiers were obtained by applying a fuzzy rough model feature evaluation criterion and sequential forward floating selection algorithm. An averaged classification accuracy of 87.05 % was achieved, corresponding to average valence classification accuracy of 93.66 % and average arousal classification accuracy of 93.29 %.     

The effect of milling energy input and molar ratio on the dehydrogenation and thermal conductivity of the (LiNH2 + nMgH2) (n = 0.5, 0.7, 0.9, 1.0, 1.5 and 2.0) nanocomposites

Hydride nanocomposites in the (LiNH₂ + nMgH₂) system have been synthesized by ball milling with varying input of milling energy injected into powder particles, Q_TR (kJ/g). The grain (crystallite) size of LiNH₂ and MgH₂ decreases rapidly with increasing Q_TR up to approximately 150–200 kJ/g and subsequently more or less saturates at the value of 10–20 nm. For the injected energy Q_TR ≈ 250–350 kJ/g the specific surface area (SSA) increases from the initial 2.4 m²/g for powder mixtures before milling to 30–37 m²/g for nanocomposites after milling. After injecting Q_TR ≈ 550 kJ/g there is a further increase of SSA to 52 m²/g which is over 20-fold increase of SSA from its initial value. That clearly indicates that a profound reduction of particle size has occurred. The hydride phases formed during ball milling with relatively low Q_TR are identified as a-Mg(NH₂)₂ (amorphous magnesium imide) and LiH. The ball milled (LiNH₂ + nMgH₂) nanocomposite system with n = 0.5–0.9 can effectively desorb about 4–5 wt.% H₂ with a reasonable rate at the temperature range close to 200 °C. Within a low temperature range up to ∼250 °C, regardless of the molar ratio n and the injected energy Q_TR the thermal desorption of the (LiNH₂ + nMgH₂) nanocomposites occurs without any release of ammonia, NH₃. For all molar ratios, n, the hydride nanocomposites are fully reversible at 175 °C under a relatively mild pressure of 50 bar H₂. The quantity of H₂ desorbed decreases with increasing molar ratio n, due to increasing fraction of inactive, retained MgH₂. However, at 125 °C the dehydrogenation rate is very sluggish and the quantity of released H₂ is minimal. At the temperature range lower than ∼250 °C dehydrogenation of ball milled nanocomposites occurs through formation of the Li₂Mg(NH)₂ hydride phase. The value of the measured dehydrogenation enthalpy change of 46.7 kJ/molH₂ is relatively low and apparently, it is not responsible for sluggish dehydrogenation at 125 °C. The measurements of thermal conductivity for non-milled powders and ball milled nanocomposites show a dramatic reduction of thermal conductivity after ball milling. It seems that this could be a principal factor responsible for such a low dehydrogenation rate at low temperatures.     

The effects of the nanometric interstitial compounds TiC,ZrC and TiN on the mechanical and thermal dehydrogenation and rehydrogenation of the nanocomposite lithium alanate (LiAlH4) hydride

Profuse mechanical dehydrogenation occurs during controlled high energy ball milling of LiAlH₄ containing 5 wt.% of the nanometric interstitial compounds such as n-TiC, n-TiN and n-ZrC which involves a gradual decomposition of LiAlH₄ to the mixture of Li₃AlH₆ and Al (Stage I) followed by a further decomposition of Li₃AlH₆ to the mixture of Al and LiH (Stage II). XRD reveals that the interstitial compounds remain stable in the hydride matrix during entire ball milling duration. The effectiveness of the nanometric interstitial compound additives for mechanical dehydrogenation increases on the order of n-TiN > n-TiC > n-ZrC. X-ray diffraction (XRD) reveals that there is no measurable change in a unit cell volume of LiAlH₄ after ball milling which indicates that an accelerated mechanical dehydrogenation of LiAlH₄ containing the nanometric interstitial compounds is unrelated to the lattice expansion as we have already reported for the nanometric metal Fe (n-Fe). In addition, the observed strong catalytic activity of the nanometric interstitial compounds for mechanical dehydrogenation is not related to their valence electron concentration (VEC) number. However, the n-TiN additive, which is the most effective one for mechanical dehydrogenation, has the smallest average particle size of 20 nm and the largest Specific Surface Area (SSA > 80 m²/g). For thermal dehydrogenation in Stage I the average apparent activation energy, E_A, for the interstitial compound additives is within the range of 87–96 kJ/mol whereas, for comparison, the nanometric metallic additives, n-Fe and n-Ni, exhibit drastically smaller apparent activation energy on the order of 55–70 kJ/mol. The average apparent activation energy for thermal dehydrogenation in Stage II is in the range of 63–80 kJ/mol in the order of E_A(n-ZrC) < E_A(n-Ti = n-TiC) and is lower than that for the nanometric metal additives n-Ni and n-Fe. In summary, the nanometric interstitial compounds do not substantially affect the apparent activation energy of Stage I but are able to reduce the apparent activation energy of thermal dehydrogenation in Stage II. XRD reveals that the interstitial compounds remain stable in the hydride matrix up to the dehydrogenation temperature of at least 165 °C. Ball milled LiAlH₄ containing 5 wt.% n-TiC, n-TiN and n-ZrC is able to slowly discharge large quantities of H₂ up to 5–6 wt.% during storage at 40 °C. Unfortunately, the results of rehydrogenation at 165 °C under 95 bar for 5 h indicate that LiAlH₄ containing the nanometric interstitial compounds exhibits no rehydrogenation.     

Effect of pressure on heat transfer coefficient at the metal/mold interface of A356 aluminum alloy

The aim of this paper is to correlate interfacial heat transfer coefficient (IHTC) to applied external pressure, in which IHTC at the interface between A356 aluminum alloy and metallic mold during the solidification of casting under different pressures were obtained using the inverse heat conduction problem (IHCP) method. The method covers the expedient of comparing theoretical and experimental thermal histories. Temperature profiles obtained from thermocouples were used in a finite difference heat flow program to estimate the transient heat transfer coefficients. The new simple formula was presented for correlation between external pressure and heat transfer coefficient. Acceptable agreement with data in literature shows the accuracy of the proposed formula.     

The effects of the micrometric and nanometric iron (Fe) additives on the mechanical and thermal dehydrogenation of lithium alanate (LiAlH4), its self-discharge at low temperatures and rehydrogenation

LiAlH₄ containing 5 wt.% of nanometric Fe (n-Fe) shows a profound mechanical dehydrogenation by continuously desorbing hydrogen (H₂) during high energy ball milling reaching ∼3.5 wt.% H₂ after 5 h of milling. In contrast, no H₂ desorption is observed during low energy milling of LiAlH₄ containing n-Fe. Similarly, no H₂ desorption occurs during high energy ball milling for LiAlH₄ containing micrometric Fe (μ-Fe) and, for comparison, both the micrometric and nanometric Ni (μ-Ni and n-Ni) additive. X-ray diffraction studies show that ball milling results in a varying degree of the lattice expansion of LiAlH₄ for both the Fe and Ni additives. A volumetric lattice expansion larger than 1% results in the profound destabilization of LiAlH₄ accompanied by continuous H₂ desorption during milling according to reaction: LiAlH₄ (solid) → 1/3Li₃AlH₆ + 2/3Al + H₂. It is hypothesized that the Fe ions are able to dissolve in the lattice of LiAlH₄ by the action of mechanical energy, replacing the Al ions and forming a substitutional solid solution. The quantity of dissolved metal ions depends primarily on the total energy of milling per unit mass of powder generated within a prescribed milling time, the type of additive ion e.g. Fe vs. Ni and on the particle size (micrometric vs. nanometric) of metal additive. For thermal dehydrogenation the average apparent activation energy of Stage I (LiAlH₄ (solid) → 1/3Li₃AlH₆ + 2/3Al + H₂) is reduced from the range 76 to 96 kJ/mol for the μ-Fe additive to about 60 kJ/mol for the n-Fe additive. For Stage II dehydrogenation (1/3Li₃AlH₆ → LiH+1/3Al + 0.5H₂) the average apparent activation energy is within the range 77–93 kJ/mol, regardless of the particle size of the Fe additive (μ-Fe vs. n-Fe). The n-Fe and n-Ni additives, the latter used for comparison, provide nearly identical enhancement of dehydrogenation rate during isothermal dehydrogenation at 100 °C. Ball milled (LiAlH₄ + 5 wt.% n-Fe) slowly self-discharges up to ∼5 wt.% H₂ during storage at room temperature (RT), 40 and 80 °C. Fully dehydrogenated (LiAlH₄ + 5 wt.% n-Fe) has been partially rehydrogenated up to 0.5 wt.% H₂ under 100 bar/160°C/24 h. However, the rehydrogenation parameters are not optimized yet.     

Spectrophotometric and chemometric studies on the simultaneous determination of two benzodiazepines in human plasma

A numerical simple, accurate and precise method based on spectrophotometric data coupled with multivariate calibration methods, PLS and MLR, combined with GA was developed for the simultaneous determination of two benzodiazepines, Clobazam and Flurazepam. A data set of absorption spectra obtained from a calibration set of mixtures containing the compounds was used to build GA-PLS and GA-MLR models. The models were tested using a dataset constructed from the compound synthetic solutions. The better model was also applied to plasma samples. The proposed method requires no preliminary separation steps and can be used for these drugs analysis in quality control laboratories.