Turbulence in microfluidics: Cleanroom-free,fast, solventless,and bondless fabrication and application in high throughput liquid-liquid extraction

This paper addresses an important breakthrough in the deployment of ultra-high adhesion strength microfluidic technologies to provide turbulence at harsh flow rate conditions. This paper is only, to our knowledge, the second reporting on the generation of high flow rate-assisted turbulence in microchannels. This flow solves a crucial bottleneck in microfluidics: the generation of high throughput homogeneous mixings. We focused on the fabrication of bulky polydimethylsiloxane (PDMS) microchips (without any interfaces) rather than the laborious surface modifications that were employed in the first reporting about turbulence-assisted microfluidics. The fabrication is cleanroom-free, simple, low-cost, fast, solventless, and bondless requiring only a laboratory oven. More specifically, our method relies on the shaping of a nylon scaffold, cure of PDMS with embedded nylon, and removal of this scaffold. The scaffold was obtained by manually wrapping nylon threads. The withdrawing out of the scaffold was completed in few seconds using only a plier. Such microchannels endured flow rates of up to 60.0 mL min⁻¹ with a strikingly low elastic deformation. The importance in producing turbulence into microscale channels was successfully shown in liquid-liquid extractions. The great energy dissipation rate relative to the turbulence created high throughput and efficient extractions in microfluidics for the first time. The residence time was only 0.01 s at 25.0 mL min⁻¹ (total flow rate of the immiscible phases). In addition, the partition coefficient determined in a single run was similar to that obtained by the conventional batch shake-flask method that was realized in triplicate.     

Neural Network Inference of Molar Mass Distributions of Peptides during Tailor-Made Enzymatic Hydrolysis of Cheese Whey: Effects of pH and Temperature

The fine-tuning of the enzymatic hydrolysis of proteins may provide a pool of peptides with predefined molar mass distributions. However, the complex mixture of molecules (peptides and amino acids) that results after the proteolysis of cheese whey turns unfeasible the assessment of individual species. In this work, a hybrid kinetic model for the proteolysis of whey by alcalase, multipoint-immobilized on agarose, is presented, which takes into account the influence of pH (8.0-10.4) and temperature (40-55 degrees C) on the activity of the enzyme. Five ranges of peptides' molar mass have their reaction rates predicted by neural networks (NNs). The output of NNs trained for constant pH and temperatures was interpolated, instead of including these variables in the input vector of a larger NN. Thus, the model complexity was reduced. Coupled to differential mass balances, this hybrid model can be employed for the online inference of peptides' molar mass distributions. Experimental kinetic assays were carried out using a pH-stat, in a laboratory-scale (0.03 L) batch reactor. The neural-kinetic model was integrated to a supervisory system of a bench-scale continually stirred tank reactor (0.5 L), providing accurate predictions during validation tests.     

Micellar electrokinetic chromatography and capillary electrochromatography of nitroaromatic explosives in seawater

The ability to separate nitroaromatic and nitramine explosives in seawater sample matrices is demonstrated using both MEKC and CEC. While several capillary-based separations exist for explosives, none address direct sampling from seawater, a sample matrix of particular interest in the detection of undersea mines. Direct comparisons are made between MEKC and CEC in terms of sensitivity and separation efficiency for the analysis of 14 explosives and explosive degradation products in seawater and diluted seawater. The use of high-salt stacking with MEKC results, on average, in a three-fold increase in the number of theoretical plates, and nearly double resolution for samples prepared in 25% seawater. By taking advantage of long injection times in conjunction with stacking, detection limits down to sub mg/L levels are attainable; however, resolution is sacrificed. CEC of explosive mixtures using sol-gels prepared from methyltrimethoxysilane does not perform as well as MEKC in terms of resolving power, but does permit extended injection times for concentrating analyte onto the head of the separation column with little or no subsequent loss in resolution. Electrokinetic injections of 8 min at high voltage allow for detection limits of explosives below 100 microg/L.     

Thiocolchicine-podophyllotoxin conjugates: dynamic libraries based on disulfide exchange reaction

A dynamic combinatorial library of thiocolchicine-podophyllotoxin derivatives based on the disulfide bond exchange reaction is described. The influence of a biological target on the composition of the reaction mixture has been demonstrated. Use of high-resolution ESI mass spectrometry to evaluate the composition of the mixture shows promise for the design of new large libraries. The biological evaluation demonstrates that formation of a divalent compound affords a new chemical entity whose biological activity is not merely the sum of the single ligands activities, thus reflecting a different interaction with the biological target.     

Cluster and periodic DFT calculations of MgO/Pd(CO) and MgO/Pd(CO)(2) surface complexes

The bonding and vibrational properties of Pd(CO) and Pd(CO)(2) complexes formed at the (100) surface of MgO have been investigated using the gradient-corrected DFT approach and have been compared to the results of infrared and thermal desorption experiments performed on ultrathin MgO films. Two complementary approaches have been used for the calculation of the electronic properties: the embedded cluster method using localized atomic orbital basis sets and supercell periodic calculations using plane waves. The results show that the two methods provide very similar answers, provided that sufficiently large supercells are used. Various regular and defect adsorption sites for the Pd(CO) and Pd(CO)(2) have been considered: terraces, steps, neutral and charged oxygen vacancies (F and F(+) centers), and divacancies. From the comparison of the computed and experimental results, it is concluded that the most likely site where the Pd atoms are stabilized and where carbonyl complexes are formed are the F(+) centers, paramagnetic defects consisting of a single electron trapped in an anion vacancy.     

Small-angle neutron scattering of ionic perfluoropolyether micellar solutions: role of counterions and temperature

This paper reports a small-angle neutron scattering (SANS) characterization of perfluoropolyether (PFPE) aqueous micellar solutions with lithium, sodium, cesium and diethanol ammonium salts obtained from a chlorine terminated carboxylic acid and with two perfluoroisopropoxy units in the tail (n(2)). The counterion and temperature effects on the micelle formation and micellar growth extend our previous work on ammonium and potassium salts n(2) micellar solutions. Lithium, sodium, cesium and diethanol ammonium salts are studied at 0.1 and 0.2 M surfactant concentration in the temperature interval 28-67 degrees C. SANS spectra have been analyzed by a two-shell model for the micellar form factor and a screened Coulombic plus steric repulsion potential for the structure factor in the frame of the mean spherical approximation of a multicomponent system reduced to a generalized one component macroions system (GOCM). At 28 degrees C, for all the salts, the micelles are ellipsoidal with an axial ratio that increases from 1.6 to 4.2 as the counterion volume increases. The micellar core short axis is 13 A and the shell thickness 4.0 A for the alkali micelles, and 14 and 5.1 A for the diethanol ammonium micelles. Therefore, the core short axis mainly depends on the surfactant tail length and the shell thickness on the carboxylate polar head. The bulky diethanol ammonium counterion solely influences the shell thickness. Micellar charge and average aggregation number depend on concentration, temperature and counterion. At 28 degrees C, the fractional ionization decreases vs the counterion volume (or molecular weight) increase at constant concentration for both C = 0.1 M and C = 0.2 M. The increase of the counterion volume leads also to more ellipsoidal shapes. At C = 0.2 M, at 67 degrees C, for sodium and cesium micelles the axial ratio changes significantly, leading to spherical micelles with a core radius of 15 A, lower average aggregation number, and larger fractional ionization.     

Modular intersection cohomology complexes on flag varieties

We present a combinatorial procedure (based on the W-graph of the Coxeter group) which shows that the characters of many intersection cohomology complexes on low rank complex flag varieties with coefficients in an arbitrary field are given by Kazhdan–Lusztig basis elements. Our procedure exploits the existence and uniqueness of parity sheaves. In particular we are able to show that the characters of all intersection cohomology complexes with coefficients in a field on the flag variety of type A _n for n < 7 are given by Kazhdan–Lusztig basis elements. By results of Soergel, this implies a part of Lusztig’s conjecture for SL(n) with n ≤ 7. We also give examples where our techniques fail. In the appendix by Tom Braden examples are given of intersection cohomology complexes on the flag varities for SL(8) and SO(8) which have torsion in their stalks or costalks.     

Inelastic neutron-scattering measurements of incommensurate magnetic excitations on superconducting LiFeAs single crystals

Magnetic correlations in superconducting LiFeAs were studied by elastic and by inelastic neutron-scattering experiments. There is no indication for static magnetic ordering, but inelastic correlations appear at the incommensurate wave vector (0.5±δ,0.5-/+δ,0) with δ~0.07 slightly shifted from the commensurate ordering observed in other FeAs-based compounds. The incommensurate magnetic excitations respond to the opening of the superconducting gap by a transfer of spectral weight.