Novel three-dimensional microfluidic device for process intensification

Microchannel heat exchangers and chemical reactors have extensive applications in process industries, especially in electronics cooling, air conditioning, and chemical industries. Microchannel devices provide enhanced heat and mass transfer characteristics by controlled flow conditions and high surface-to-volume ratios. The different designs of microchannels are based on planar structures from various fabrication technologies. In the present study a novel three-dimensional micro-structured device, the micro coiled flow inverter (MCFI) with 0.38–0.8 mm internal diameter, has been numerically investigated as a micro heat exchanger. In comparison micro helical coil (MHC) and straight tube of same heat transfer area (d_t = 0.5 mm, A = 3.9 × 10⁻⁴ m²) has been studied, too. The Reynolds and Prandtl numbers are varied from 25 to 1200 and 0.74 to150, respectively. The MCFI offers a four-fold heat transfer enhancement as compared to straight tube of same heat transfer area at N_Re = 1200 and N_Pr = 7. Furthermore, the heat transfer coefficient in MCFI augments by 38.5% as compared to MHC, with slight increase (5–16%) in friction factor. New design correlations are developed for Nusselt number and friction factor in MCFI. The MCFI device offers 1.15–1.7-folds higher thermal merit as compared to micro straight tube.     

Theoretical investigation of mechanical and thermal properties of MPO4 (M = Al,Ga)

Minimum lattice thermal conductivities and mechanical properties of polymorphous MPO₄ (M = Al, Ga) are investigated by first principles calculations. The theoretical minimum thermal conductivities are found to be 1.02 W (m K)^?1 for α-AlPO₄, 1.20 W (m K)^?1 for β-AlPO₄, 0.87 W (m K)^?1 for α-GaPO₄ and 0.88 W (m K)^?1 for β-GaPO₄. The lower thermal conductivities in comparison to YSZ can be attributed to the lattice phonon scattering due to the framework of heterogeneous bonds. In addition, the low shear-to-bulk modulus ratio for both β-AlPO₄ (0.38) and β-GaPO₄ (0.30) is observed. Our results suggest their applications as light-weight thermal insulator and damage-tolerant/machinable ceramics.     

Controlled radical copolymerization of β-pinene and n-butyl acrylate

The feasibility of the radical copolymerization of β-pinene and n-butyl acrylate (n-BA) was clarified for the first time. β-pinene was found to undergo degradative chain transfer during the copolymerization. This degradative chain transfer became less competitive with the copolymerization by the addition of EtAlCl₂, and the copolymer yield, β-pinene incorporation and molecular weight of the copolymer increased remarkably compared with the case in the absence of EtAlCl₂. The monomer reactivity ratios evaluated by the nonlinear least-squares method were r_β-pinene ∼ 0 and r_n-BA ∼ 2.2 in the absence of EtAlCl₂, r_β-pinene ∼ 0 and r_n-BA ∼ 0.86 in the presence of EtAlCl₂ in bulk at 70 ˚C. Furthermore, the possible controlled copolymerization of β-pinene and n-butyl acrylate was then attempted via the reversible addition-fragmentation transfer (RAFT) technique. The copolymerization (f_β-pinene = 0.20) using 2-cyanopropyl-2-yl dithiobenzoate as the RAFT agent displayed the typical features of a controlled system, such as the first-order kinetics and the linear increase in molecular weight with the overall conversion. The livingness of the copolymer chains was further proved by using them as the macroinitiator for the chain extension with styrene by RAFT process.     

A new polymorph telluridoindate [In(en)3][In5Te9(en)2] with photocatalytic properties

A new polymorph telluridoindate [In(en)₃][In₅Te₉(en)₂] (denoted as β-type, en = ethylenediamine) has been solvothermally synthesized and characterized. The crystal data for the β-type are listed as follows: monoclinic, space group Cc (No. 9), a = 11.642(2), b = 20.421(4), c = 17.577(4) Å, β = 92.20(3)°, V = 4175.7(14) Å³, Z = 4. The β-type contains organic-decorated [In₄Te₉(en)]^6 − supertetrahedral cluster and [InTe₃(en)]^3 − tetrahedron, which are interconnected to form an organic-decorated 2-D telluridoindate layer of [In₅Te₉(en)₂^3 −]_n with 9-membered rings. Two relevant conformers of telluridoindates are compared with each other. The β-type indicates absorption edge at 2.23 eV and exhibits photocatalytic activity for degradation of methyl orange (MO).     

A Novel Substrate Addition Method in the 11β-Hydroxylation of Steroids by Curvularia Lunata

The substrate dissolution in steroids biotransformation is of great importance as it is the bottle-neck for improving the biotransformation ability. In this paper, the effect of organic solvent, surfactant Tween 80, ultrasonic wave and β-cyclodextrins inclusion on the dissolution of substrate RSA during steroids 11β-hydroxylation by Curvularia lunata was studied. Substrate RSA was dissolved in surfactant Tween 80 and then fed to the broth, which notably increased the solubility of substrate in aqueous state, thus improving the hydrocortisone conversion rate. Ultrasonic treatment of substrate or cells both had an obvious effect on the biotransformation. The solubility enhancement of RSA by inclusion complexion with β-cyclodextrins was also evaluated, and the optimum molar ratio of RSA to β-cyclodextrins was 1 : 1. Furthermore the interaction between RSA and β-cyclodextrins in this inclusion complex was assessed by differential scanning calorimetry (DSC) and infrared (IR) spectra. Based on the results of these factors, a novel substrate RSA addition method was performed as follows: β-cyclodextrin was added to RSA blended with 1.2% Tween80 (β-cyclodextrins/RSA 1 : 1, molar ratio), followed by a 20 min sterilization, and then the suspension was fed to the broth. In this way, the hydrocortisone conversion rate was increased by 13.0% than that of the conventional ethanol circumfluence addition method with the RSA addition concentration of 1.0 g L⁻¹.     

PMMA-supported hybrid materials doped with highly near-infrared (NIR) luminescent neutral trikis-β-diketonate Yb3 + complex

Based on self-assembly of a trifluorinated and acylpyrazole-modified β-diketonate ligand HL ((Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidene)-1H-pyrazol-5(4H)-one), LnCl₃⋅ 6H₂O (Ln = La, Yb or Gd) and 2,2′-bpy (2,2′-bipyridine), three trikis-β-diketonate complexes [Ln(L)₃(2,2′-bpy)] (Ln = La, 1; Ln = Yb, 2 or Ln = Gd, 3) were obtained, respectively. Further through physical doping, the series of PMMA-supported hybrid materials PMMA@[Ln(L)₃(2,2′-bpy)] with high thermal stability and good film-forming property are obtained. Especially for PMMA@2, the doping also causes the improved NIR luminescent property (Φ_em = 0.97%) in comparison to the individual Yb^3 +-β-diketonate complex 2 (Φ_em = 0.81%) even up to a concentration of 200:1.     

Enhancement of immobilized enzyme activity by pretreatment of β-glucosidase with cellobiose and glucose

In this study, β-glucosidase from Aspergillus niger was pretreated with cellobiose and glucose to prevent loss of enzyme activity, and pretreated β-glucosidase was immobilized on silica gel as a carrier by covalent binding. To enhance the activity of immobilized β-glucosidase, the effects of substrate concentration and reaction conditions, including temperature, time, and agitation speed, were investigated. The optimal concentrations of cellobiose and glucose, temperature, time, and agitation speed were determined to be 0.02 M, 40 °C, 20 min, and 130 rpm, respectively. The activity of immobilized β-glucosidase after pretreatment was increased to about 176% of that of non-pretreated β-glucosidase. In addition, the optimal pH and temperature of the non-pretreated and pretreated immobilized β-glucosidases were both pH 5.5 and 65 °C, respectively. Moreover, the immobilized β-glucosidases were used repeatedly 20 times, and the enzyme activities were maintained at levels higher than 80% of their initial activities.     

Crystal and geometry-optimized structure,Hirshfeld surface analysis and spectroscopic studies of tetrachlorocuprate and nitrate salts of 1-(2-fluorophenyl)piperazine cations, (C10H15FN2)[CuCl4] (I) and (C10H14FN2)[NO3] (II)

Two new organic-inorganic hybrid materials, 1-(2-fluorophenyl)piperazine-1,4-diium tetrachlorocuprate, (C₁₀H₁₅FN₂)[CuCl₄] (I) and 1-(2-fluorophenyl)piperazin-4-ium nitrate, (C₁₀H₁₄FN₂)[NO₃] (II), have been synthesized by an acid/base reaction at room temperature in the presence of 1-(2-fluorophenyl)piperazine as an organic-structure directing agent and their structures were determined by single crystal X-ray diffraction. Compound (I), (C₁₀H₁₅FN₂)[CuCl₄], crystallizes in the monoclinic system and P2₁/c space group with a = 7.5253 (2), b = 20.6070 (7), c = 9.7281 (3) Å, β = 103.6730 (17)°, V = 1465.82 (8) Å³ with Z = 4. Full-matrix least-squares refinement converged at R = 0.037 and wR(F²) = 0.088. Compound (II), (C₁₀H₁₄FN₂)[NO₃], belongs to the monoclinic system, space group P2₁/c with the following parameters: a = 10.8034 (2), b = 7.5775 (1), c = 14.4670 (3) Å, β = 111.761 (2)°, V = 1099.91 (4) ų and Z = 4. The structure was refined to R = 0.044, wR(F²) = 0.136.In the structures of (I) and (II), the anionic and cationic entities are interconnected by means of set of hydrogen bonding contacts forming three-dimensional networks. Intermolecular interactions were investigated by Hirshfeld surfaces and the contacts of the four different chloride atoms were notably compared. The results of the optimized molecular structure are presented and compared with the experimental one. The Molecular Electrostatic Potential (MEP) maps and the HOMO and LUMO energy gap of both compounds were computed. The vibrational absorption bands were identified by infrared spectroscopy. Theory (DFT) calculations of normal mode frequencies are compared with experimental ones.     

Mixing enhancement by pulsating chaotic advection

The purpose of this study is to investigate transverse mixing enhancement by superposition of periodic time dependence, in the form of pulsation, on a twisted pipe flow in which the fluid particles trajectories are spatially chaotic. The pulsation makes the secondary flow structure more complex, resulting in stronger velocity gradients that enhance stretching and folding, the main mechanisms of chaotic mixing. Here, the chaotic configuration is six alternating 90° curved pipes. The imposed pulsating conditions range as follows: steady Reynolds numbers 420 ≤ Re_st ≤ 1000, velocity component ratios 1 ≤ (β = U_max,osc/U_m,st) ≤ 4 and frequency parameters 8.37 < (α = r₀(ω/ν)^0.5) < 24.5. The secondary velocity fields are measured by particle image velocimetry. The axial vorticity and transverse strain rate at the outlet of each curved pipe in pulsatile flow are compared with those of the steady flows. Analysis of these criteria for mixing assessment shows that β ≥ 2 and α ≤ 15 are favourable pulsating conditions for transverse mixing enhancement. Moreover, in some pulsation conditions, the cell centres visit a zone in the flow cross-section that is much larger than in the steady case, implying that pulsation also contributes to mixing homogenization.     

Syntheses,characterizations, and redox behaviors of new self-assembled metal complexes with bridging ligands incorporating chalcogen sites

Three new complexes, [Zn(dbsf)₂(dmf)₂] · 5.5dmf (dbsf = 4,4′-sulfonyldibenzoate) (1β), [Cu(tdsa)(phen)₂] · 1.5EtOH (tdsa = 5,5′-thiodisalicylate, phen = 1,10-phenanthroline) (2), and [Cu(sdp)(phen) · Cu(Hsdp)(phen)(CH₃COO)] · 3EtOH (sdp = 4,4′-sulfonyldiphenolate) (3) were prepared and structurally characterized. Complex 1β shows a one-dimensional coordination framework constructed from bridges between Zn(II) centers with two ligands. Complex 2 is a monomeric complex, which assembles by π–π interactions. Complex 3 shows a unique two-dimensional coordination framework that is constructed from two Cu(II) centers, sdp, and Hsdp. The redox properties of these three complexes were characterized by solid-state cyclic voltammetry. Complexes 1β and 3 show irreversible reduction waves because of the reduction of their sulfone sites. Complex 2 shows an irreversible oxidation wave because of oxidation of the sulfide site.     

Novel method for the synthesis of a β-tricalcium phosphate coating on a zirconia implant

A novel method for the synthesis of a thin β-tricalcium phosphate (β-TCP) coating on zirconia implants has been developed. The synthesis procedure involves two steps: (i) rapid wet-chemical deposition of a biomimetic CaP coating and (ii) subsequent post-deposition processing of the biomimetic CaP coating, which includes a heat treatment at 900 °C followed by a short sonication in a water bath. The obtained β-TCP coating showed a uniform and dense morphology with a thickness of ≈500 nm and displayed a roughness in the nanometre range (R_a = 28 nm). The β-TCP coating demonstrated an apatite-mineralization ability in a simulated body fluid and enhanced the adsorption of serum proteins on the zirconia. Moreover, the β-TCP coating adhered firmly to the zirconia substrate, developing a notable scratch resistance (L_c = 97 N) and tensile strength (52 MPa) and showed strong resistance towards mechanical forces present during implantation of the coated zirconia implant into the artificial bone.     

Thermal chemical vapor deposition grown graphene heat spreader for thermal management of hot spots

Graphene of different layer numbers was fabricated using thermal chemical vapor deposition (TCVD), and it was demonstrated as a heat spreader in electronic packaging. Platinum thermal evaluation chips were used to evaluate the thermal performance of the graphene heat spreaders. The temperature of a hot spot driven at a heat flux of up to 430 W cm⁻² was decreased from 121 °C to 108 °C (ΔT ≈ 13 °C) with the insertion of the monolayer graphene heat spreader, compared with the multilayer (n = 6–10) ones’ temperature drop of ∼8 °C. Various parameters affecting the thermal performance of graphene heat spreaders were discussed, e.g. layer numbers of graphene, phonon scattering, thermal boundary resistance. We demonstrate the potentials of using a complementary metal oxide semiconductor compatible TCVD process to utilize graphene as a heat spreader for heat dissipation purposes.     

Single crystal X-ray structure analysis for two thiazolylazo indole dyes

To determine the tautomeric form of the hetarylazo indole dye 3-(5-methylthiazol-2-yldiazenyl)-2-phenyl-1H-indole (1), 1-methyl-3-(thiazol-2-yldiazenyl)-2-phenyl-1H-indole (2) was synthesized as a model compound and both molecules were characterized by single crystal X-ray diffraction. (1) crystallized in the monoclinic system, space group C2/c, a = 31.064(2), b = 7.4051(5), c = 27.7138(18) Å, β = 97.617(1)°, V = 6318.9(7) Å³, Z = 8, while dye 2 crystallized in the monoclinic system, space group P2₁/n, a = 11.4660(11), b = 9.8223(9), c = 14.2049(14) Å, β = 97.418(2)°, V = 1586.4(3) Å³, Z = 4. The asymmetric unit of 1 contains two crystallographically independent molecules, in which geometries and conformations differ slightly, while there is only one molecule in the asymmetric unit for 2. The intermolecular N–H?N hydrogen bonds in (1) link the molecules, via parallel, infinite sheets, along the a axis and stabilize the crystal structure; in 2, there is no classical intermolecular hydrogen bond.     

Synthesis,characterization and third-order nonlinear optical properties of novel hyperbranched donor–acceptor polyfluorenes based on 1,3,6,8-tertsubstituted carbazole core

Two novel hyperbranched donor–acceptor polyfluorenes based on 1,3,6,8-tertsubstituted carbazole core (4BrCzP1 and 4BrCzP2) were synthesized and characterized. The third order nonlinear optical properties of the materials were studied using Z-scan technique with femtosecond Ti: sapphire laser with delivering pulses of 140 fs at 800 nm. The nonlinear optical refractive index was 9.29 × 10^?8 esu for 4BrCzP1 and 3.19 × 10^?7 esu for 4BrCzP2, respectively. While the third order nonlinear susceptibility was 1.29 × 10^?9 esu for 4BrCzP1 and 4.33 × 10^?9 esu for 4BrCzP2, respectively. The experimental results indicated that the hyperbranched polyfluorenes was a promising candidate in the application of third order nonlinear optical materials.     

Enrichment of Nigella damascena extract with volatile compounds using supercritical fluid extraction

β-Elemene, germacrene A and damascenine were extracted from lady-in-a-mist (Nigella damascena L.) seeds with supercritical carbon dioxide at 10–30 MPa and 40–60 °C. The influence of supercritical fluid extraction (SFE) conditions on the yield and concentration of volatiles in the extract and the extraction kinetics were studied. The extraction yields and the apparent solubility of volatile compounds increased with increasing density of CO₂. The highest total yield was obtained at 30 MPa and 40 °C but the selectivity for volatiles was low under these conditions. With respect to both yield of volatiles and their concentration in extract, the best results were at 12 MPa and 40 °C, either with one separator or with additional separator maintained at 5 MPa and 25 °C. The yields of β-elemene, germacrene A and damascenine reached 0.72, 3.31 and 3.65 mg g⁻¹ and their concentration in the extract was 2.62, 12.04 and 13.28 wt.%, respectively. Though the yields of germacrene A and damascenine were by about 20% higher using Soxhlet extraction with hexane than using SFE, their concentration in the extract where fatty oil prevailed was only 1.19 and 1.20 wt.%, respectively. Under the conditions of hydrodistillation, partial conversion of germacrene A to β-elemene occurred and its yield was higher than using the other methods but the composition of volatiles in the SFE extracts better corresponds to the original raw material.     

Microwave dielectric properties and crystal structure of the tungstenbronze-type like (Ba1 − αSrα)6(Nd1 − βYβ)8Ti18O54 solid solutions

A study of the dielectric properties, especially the Q × f value, of the tungstenbronze-type like (Ba_1 − αSr_α)_6 − 3xNd_8 + 2xTi₁₈O₅₄ solid solutions in x = 0 system was carried out. These compositions near x = 0 have very low Q × f values. To improve the Q × f value of these materials, we tried two substitutional systems, which are (Ba_1 − αSr_α)₆Nd₈Ti₁₈O₅₄ and Ba₄Sr₂(Nd_1 − βY_β)₈Ti₁₈O₅₄. In the former composition, the Q × f value was increased from 206 to 5880 GHz in the range of 0 ≤ α ≤ 0.5. And we found that Sr ions substituted for Ba ions in A1 sites have good effect on increasing the Q × f value, but Sr ions substituted for Ba ions in A2 sites have poor effect on increasing it. The latter composition also has a small effect on increasing the Q × f value.     

Lattice oxygen of La1−xSrxMO3 (M = Mn,Ni) and LaMnO3−αFβ perovskite oxides for the partial oxidation of methane to synthesis gas

The partial oxidation of methane to synthesis gas by using the lattice oxygen of La_1−xSr_xMO₃ (M = Mn, Ni; x = 0–0.4) and LaMnO_3−αF_β (β/(3 − α) = 0.1) perovskite oxides was explored. Approximately 75% CO selectivity at 16% CH₄ conversion with H₂/CO molar ratio of ca. 2.5 can be achieved at 800 °C. The stability of the perovskite structure and the reactivity/selectivity of lattice oxygen are found to be dependent on (i) B-site element, (ii) degree of substitution of La with Sr, and (iii) fluorination of the perovskite oxide.     

Influence of pulsed electric field and heat treatment on Emblica officinalis juice inoculated with Zygosaccharomyces bailii

The effects of pulsed electric field (PEF) applying 26 kV cm⁻¹ with 1 μs monopolar pulses (for 500 μs) on inactivation of Zygosaccharomyces bailii and the stability for the key quality characteristics (vitamin C, phenolic content, antioxidant capacity, nonenzymatic index, 5-hydroxymethyl-2-furfural (HMF), °brix, and pH) in Emblica officinalis juice were studied. These results were then compared to those of heat treatment (90 °C for 60 s) up to 40 days on storing at 4 °C. PEF treatment reduced 5.1 log cycles of Z. bailii with decreases in HMF concentration and browning index relative to heat treated juice. Simultaneously, PEF treated juice retained 63% of vitamin C and 88.9% of antioxidant capacity (p < 0.05). However, heat treated juice lowered 4.9 log cycles of Z. bailii and exhibited significant degradation of vitamin C and antioxidant capacity (p < 0.01). After all, both treatments did not induce any major changes in pH and °brix levels of emblica juice. Electron microscopy was used as a tool to find Z. bailii damage induced. Investigation of their morphology showed a leakage of cellular debris owing to the rupture of cell membrane of PEF treated Z. bailii. Thus, PEF treatment on emblica juice may offer an enormous potential for upgrading its quality than the heat processing method.     

Influence of molecular weight of polydimethylsiloxane precursors and crosslinking content on degree of ethanol swelling of crosslinked networks

Using PDMS (polydimethylsiloxane) as a basic polymeric matrix to the preparation of ethanol-permselective pervaporation membranes is a vibrant field of research. In this paper, a detailed study of the effects of the molecular weight of PDMS precursors and the content of the TEOS (tetraethyl orthosilicate) crosslinker on the degree of swelling in ethanol and ethanol contact angle is reported. Five PDMS precursors with molecular weights of 26.6 K, 35.5 K, 50.2 K, 71.7 K, and 110.4 K, and five crosslinking contents (1 wt%, 2 wt%, 5 wt%, 10 wt%, and 15 wt%) were chosen to prepare twenty-five PDMS networks. Considering only the maximum tensile strength of the networks, the optimum molecular weight of the precursor was found to be 35.5 K and the optimum crosslinker content was 5 wt%. The average Young’s modulus of the PDMS network prepared under these conditions reached 0.63 MPa after using toluene to extract the network. Some uncrosslinked precursors always occur in the networks, and have some influence on the molecular weight of the precursors and the crosslinker content that is used. It was found that the content of the uncrosslinked precursors has direct effect on the contact angle of ethanol sessile drops at the surface of the extracted PDMS networks, and higher extraction corresponded to a smaller ethanol contact angle. A combined parameter (S), defined as the quotient of the extraction amount (A_E) and the tensile elastic modulus (E_Y), gives a good linear relationship with the increase in weight of networks swelled in ethanol. This means that the degree of equilibrium swelling of the networks is simultaneously strongly influenced by the tensile modulus and the content of the uncrosslinked precursors.     

Modifier–substrate interactions of various types in the Orito reaction: Reversal of the enantioselection in the hydrogenation of ketopantolactone on Pt modified by β-isocinchonine and O-phenylcinchonidine

The enantioselective hydrogenation of ketopantolactone (KPL) on Pt–alumina catalyst modified by β-isocinchonine (β-ICN) and O-phenylcinchonidine (PhOCD) in toluene, acetic acid and their mixtures under otherwise identical experimental conditions was studied. Reversal of the enantioselection was obtained dependent on the concentration of acetic acid (ee_max = 17% (S) on Pt–PhOCD and 50% (R) on Pt–β-ICN, respectively). The possible role in enantioselection of adducts forming in the reaction mixture and the stability of PhOCD under the conditions of the hydrogenation was investigated by ESI-MS. The results of the nonlinear phenomenon measurements on β-ICN + PhOCD mixtures suggest that the intermediate surface complexes β-ICN–KPL and PhOCD–KPL responsible for the opposite enantioselection include different types of interactions and the enantioselection is directed by the competition between these interactions.