In situ FTIR micro-spectroscopy to investigate polymeric fibers under supercritical carbon dioxide: CO2 sorption and swelling measurements

An original experimental set-up combining a FTIR (Fourier Transformed InfraRed) microscope with a high pressure cell has been built in order to analyze in situ and simultaneously the CO₂ sorption and the polymer swelling of microscopic polymer samples, such as fibers, subjected to supercritical carbon dioxide. Thanks to this experimental set-up, we have determined as a function of the CO₂ pressure (from 2 to 15 MPa) the CO₂ sorption and the polymer swelling at T = 40 °C of four polymer samples, namely PEO (polyethylene oxide), PLLA (poly-l-lactide acid), PET (polyethylene terephtalate) and PP (polypropylene). The quantity of CO₂ sorbed in all the studied polymers increases with pressure. PEO and PLLA display a significant level of CO₂ sorption (20 and 25% respectively, at P = 15 MPa). However, we observe that a lower quantity of CO₂ can be sorbed into PP and PET (7 and 8% respectively, at P = 15 MPa). Comparing their thermodynamic behaviors and their intrinsic properties, we emphasize that a high CO₂ sorption can be reach if on one hand, the polymer is able to form specific interaction with CO₂ in order to thermodynamically favor the presence of CO₂ molecules inside the polymer and on the other, displays high chains mobility in the amorphous region. PLLA and PEO fulfilled these two requirements whereas only one property is fulfilled by PET (specific interaction with CO₂) and PP (high chains mobility). Finally, we have found that for a given CO₂ sorption, the resulting swelling of the polymer depends mainly on its crystallinity.     

Modeling moisture sorption isotherms in roasted green wheat using least square regression and neural-fuzzy techniques

Roasted green wheat at moisture content from 0.052 to 0.25 (decimal d.b.) and temperatures from 25 to 43 °C was used to model moisture sorption isotherms using conventional non-linear least square regression (NLR) and neural-fuzzy (NF) techniques. The results showed that neural-fuzzy techniques provided a better fit than conventional least square regression with: R² = 0.99 and 0.97, RMSE = 0.01 and 0.0038, E% = 1.01 and 5.9 and SSE = 0.0008 and 0.009, for NF and NLR techniques, respectively. Differential enthalpy decreased from 477.9 kJ/kg at 0.052 (decimal d.b. mc) to 44.7 kJ/kg at 0.25 (decimal d.b. mc) and entropy decreased from 1.16 kJ/kg K at 0.052 (decimal d.b. mc) to 0.014 kJ/kg K at 0.25 (decimal d.b. mc). A linear plot between enthalpy and entropy showed that compensation exists. The isokinetic temperature T_β was 376.13 K which was larger than the harmonic mean temperature T_hm = 307.31 K, showing that the water sorption was entropy-driven. The free energy change ΔG was positive (+38.42 kJ/kg) indicating a non-spontaneous water sorption process.     

One new nickel coordination polymer with an unsymmetric 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione: Synthesis,structure and characterization

A new neutral 2D coordination polymer, {[Ni(pot)₂(H₂O)₂] · 6H₂O}_n (1) (Hpot = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione), has been prepared by reacting Ni^II salt with the Hpot ligand under a mixed solvents medium; 1 possesses large rectangular channels to trap water molecules. It has been characterized by IR and gas sorption property as well as TG analysis.     

A novel cobalt(II) acylpyrazolonate complex with intermolecular hydrogen bond: Synthesis,structure and properties

A new cobalt complex, [Co(L)₂·(H₂O)₂](HL = 4-hexanoyl-3-methyl-1-phenyl-1H -pyrazol-5(4H)-one), was synthesized by us. The complex was characterized by single crystal X-ray diffraction, IR, UV, fluorescence spectra and thermogravimetric analysis. The results of characterization showed that the crystal is monoclinic system with crystal parameters: a = 15.2439(12) Å, b = 7.4101(6) Å, c = 15.7381(18) Å, and Z = 2, S = 1.074. It was found that the Co²⁺ is located in the inversion center of the complex. The Co(II) had an ideal octahedral coordination environment with four oxygen atoms of HL ligands in the equatorial plane and two water molecules in axial positions. The complex exhibits yellow emission as the result of the fluorescence from the intraligand emission excited state.     

Reversible water inclusion in a porous magnetic material synthesized from copper(II) incorporated metal-organic framework showing alternate ferro- and antiferromagnetic interactions

X-ray structural analysis shows that {[Cu₂(CTA) (H₂O)] · 5 H₂O}_n constitutes infinite one-dimensional parallel chains along the c-axis with water columns running down the crystallographic a-axis. The inclusion of water molecules is reversible and is confirmed by X-ray powder diffraction studies. The magnetic data (2–300 K) reveal that there are alternate ferro- (J = 0.29 cm⁻¹) and antiferromagnetic (J = −2.5 cm⁻¹) interactions.     

Nitrosyl cis-dichlorodiammine ruthenium complex with bridging H3O2− ligand

The ruthenium complex with bridging H₃O₂⁻ ligand was obtained and the crystal structure was determined. The compound cis-[{RuNO(NH₃)₂Cl₂}₂(μ₂-H₃O₂)]Cl crystallizes in the monoclinic space group P2₁/n with cell parameters a = 15.0651(5), b = 6.3624(2), c = 15.3813(6) Å, β = 94.9690(10)°, Z = 4 and R = 0.0185. The hydroxide hydrate anion is coordinated to the ruthenium atoms of the identical cis-{RuNO(NH₃)₂Cl₂} fragments. The protonation of the starting cis-[RuNO(NH₃)₂(NO₂)₂OH] complex leads to the required coordinated aqua/hydroxide ratio if the specific amount of hydrochloric acid is used. The DFT calculations confirm the formation of the dimer structure in the gas phase. However, the presence of water molecules dramatically reduces the dimerization efficiency.     

The structure of hydrated complexes of o-hydroxybenzoic acid in water-modified supercritical carbon dioxide: The Car-Parrinello molecular dynamics simulation

The study of the o-hydroxybenzoic acid (o-HBA)–water molecular structures formed in supercritical carbon dioxide (T = 318 K, ρ = 0.7 g/cm³) by Car-Parrinello molecular dynamics method has been performed. Atom–atom radial distribution functions, coordination numbers, average hydrogen bond (HB) numbers, and vibrational densities of states have been calculated from molecular trajectories saved during simulation procedure. It has been shown that, despite of the high co-solvent polarity, the hydroxyl group of the o-HBA preferably forms an intramolecular HB, whereas o-HBA–water hydrogen bonding involves only acid carboxyl group. The formed o-HBA–(H₂O)₂ complex and remaining water molecules compose a labile hydrogen-bonded cluster. The average HB number per water molecule is equal to 1.93, 26.4% out of the total amount of HBs formed by water molecules being water–o-HBA HBs, and the rest being water–water HBs. Evolution of hydrogen-bonded clusters has been analyzed, using instantaneous structures saved during the simulation. It was shown that water–water HBs are less stable than water–o-HBA ones.     

Preparation in supercritical CO2 of porous poly(methyl methacrylate)–poly(l-lactic acid) (PMMA–PLA) scaffolds incorporating ibuprofen

Partially biodegradable porous scaffolds incorporating bioactive molecules prepared by clean techniques posses an enormous interest in tissue engineering applications. Poly(methyl methacrylate)–poly(l-lactic acid) (PMMA–PLA) blends were submitted to CO₂ supercritical conditions (P = 160–260 bar, T = 60 °C) after certain time and then rapidly depressurized to obtain porous structures that have been related with the supercritical parameters and to the polymer blend composition. In some cases ibuprofen was also incorporated to the formulations previously to the CO₂ treatment and studied the appropriate conditions for avoiding its extraction in SCCO₂. Scaffolds purity, thermal transitions, swelling and degradation behaviour, and the ibuprofen release were also studied to determine the appropriate scaffolds with a desired porosity for cell seeding. Cell culture was performed on the selected porous scaffolds using human fibroblast examined by scanning electron microscopy (SEM).     

Water retention properties of porous geopolymers for use in cooling applications

A series of geopolymers were prepared with varying ratios of sodium silicate, metakaolinite, NaOH and H₂O and their porous properties, water retention and mechanical properties were determined, to develop materials for counteracting heat island effects. Samples were prepared with the molar ratios SiO₂:Al₂O₃:Na₂O:H₂O of 3.66:1:x:y, where x = 0.92–1.08 and y = 14.2–19.5. The porous and mechanical properties of the geopolymers showed a good correlation with the H₂O/Al₂O₃ ratio (y); an increase in y produced an increase in the pore volume (from 0.26 to 0.46 ml/g), the pore size (from 15 to 390 nm) and the water absorption (from 27.2 to 51.1%). The same increase in y decreased the bulk density (from 1.29 to 0.99 g/cm³), the bending strength (from 14.2 to <5 MPa) and the water retention. Thus, the H₂O/Al₂O₃ ratio is the most important factor for controlling the porous properties of these materials, since geopolymers with higher H₂O/Al₂O₃ ratios are more porous and have higher water absorption rates, making them suitable as materials for surface cooling by water evaporation. Geopolymers with lower H₂O/Al₂O₃ ratios are more suitable for water retention applications, and have the advantage of higher mechanical strength.     

One-dimensional supramolecular assembly of an Mn12 single molecule magnet by ligand interactions

A new Mn₁₂ complex was synthesized using ligand substitution reaction of Mn₁₂–OAc with 4-(thiophen-3-yl)benzoic acid and complex’s structural and magnetic properties were analysed. [Mn₁₂O₁₂(O₂CC₆H₄C₄H₃S)₁₆(H₂O)₃]·14CH₂Cl₂ (1) crystallized in the P2₁/c space group. Intermolecular π–π interactions between phenyl and thiophene rings of two adjacent Mn₁₂ molecules result in one-dimensional supramolecular assembly of 1 in the crystal. On the other hand, steric repulsion between the neighbouring molecules causes unusual ligand arrangement and coordination geometry of Mn(III) ion with five coordination. The ac magnetic study of 1 gives U_eff = 69.98 K and 1/τ₀ = 1.456 × 10⁸ s^?1 and dc reduced magnetization measurement gives S = 10, g = 1.95 and D = ?0.425 cm^?1 showing that outer ligand distortion has little effect on the magnetic properties.     

New prototype for the treatment of falling film liquid effluents by gliding arc discharge part I: Application to the discoloration and degradation of anthraquinonic Acid Green 25

Gliding arc discharge (GAD) reactors are continuously in progress in order to improve the treatment efficiency of recalcitrant compounds. However, up to now, they remain difficult to transfer to industrial applications because of some technical constraints in their design. In this study, a new efficient prototype is proposed for the treatment of gravity falling film shaped of liquid effluents. The liquid flow rate is now continuous as the tank containing the solution to be treated is replaced by an inclined plate along which flows the liquid. The various working parameters are optimized and the new prototype efficiency is tested on discolouration and degradation of the anthraquinonique Acid Green 25. The optimized values obtained are: the liquid flow rate ω = 1 L h⁻¹, the plate tilt angle α = 45° and the channel width Δ = 3 mm. The rates of discolouration and degradation reach 95% and 90% respectively after 12 cycles (180 min) of plasma exposition. The GAD in the presence of humid air generates highly oxidizing radical species such as ^•OH with a standard potential E°[(^•OH/H₂O) = 2.85 V/SHE] and its reducer agent H₂O₂ [E°(H₂O₂/H₂O) = 1.68 V/SHE.     

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.     

Solubility and diffusion coefficient of supercritical-CO2 in polycarbonate and CO2 induced crystallization of polycarbonate

The solubility and diffusion coefficient of supercritical CO₂ in polycarbonate (PC) were measured using a magnetic suspension balance at sorption temperatures that ranged from 75 to 175 °C and at sorption pressures as high as 20 MPa. Above certain threshold pressures, the solubility of CO₂ decreased with time after showing a maximum value at a constant sorption temperature and pressure. This phenomenon indicated the crystallization of PC due to the plasticization effect of dissolved CO₂. A thorough investigation into the dependence of sorption temperature and pressure on the crystallinity of PC showed that the crystallization of PC occurred when the difference between the sorption temperature and the depressed glass transition temperature exceeded 40 °C (T − T_g ≥ 40 °C). Furthermore, the crystallization rate of PC was determined according to Avrami's equation. The crystallization rate increased with the sorption pressure and was at its maximum at a certain temperature under a constant pressure.     

Decomposition of allantoin in the presence of Cu(II) ions resulting in the formation of a coordination polymer containing oxalate species

A novel Cu(II) coordination polymer, [Cu(ox)(DMSO)₂]_n (1) (ox-oxalate dianion, DMSO-dimethyl sulphoxide) has been prepared in the reaction of copper nitrate dihydrate and allantoin (5-ureidohydantoin) in DMSO/water solution. Compound (1) crystallizes in the monoclinic, space group P121/c1 with a = 5.1785(7), b = 13.6311(18), c = 8.5386(12) Å, β = 107.524(12)°, V = 574,76(14) Å³, Z = 4, D_cal = 1779 mg/m³, R₁ = 0.0449. The metal ion coordinates through four oxygen atoms belonging to two bidentate bridging oxalate ligands, and two oxygen atoms from two DMSO ligands forming an elongated octahedron. The crystal structure was confirmed by FT-IR and Uv–vis spectroscopic data.     

A novel 3D twofold interpenetrating microporous metal-organic framework containing 1D water tapes with cyclic pentamer units

The self-assembly of Cu²⁺ ions with malate and 1,3-bis(4-pyridyl)propane (bpp) affords a 3D coordination polymer {[Cu(Hmal)(bpp) · 6H₂O]}_n (1) (malic acid = H₃mal). The metal ions were interconnected by α- and β-carboxylate of malate produce infinite [Cu(C₄H₄O₅)]_n layers, which were further pillared by bridging ligand bpp molecules to form a 3D interpenetrating network. Of further interest, lattice water molecules form 1D infinite water tapes in 1D open cavities.     

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.     

Study effect of different parameters on the sulphate sorption onto nano alumina

The aim of this research work is to investigate sorption characteristic of modified nano alumina (n-Al) for the removal of SO₄^2? from aqueous solutions and wastewater. The sorption of SO₄^2? by batch method is carried out. The optimum conditions of sorption were found to be: a sorbent dose of 0.3 g in 100 ml of SO₄^2?, contact time of 35 min, pH = 5. In optimum condition, removal efficiency was 85.6% for the SO₄^2?. Three equations, i.e. Morris–Weber, Lagergren and pseudo second order have been tested to track the kinetics of removal process. The Langmuir, Freundlich and D–R are subjected to sorption data to estimate sorption capacity. It can be concluded that n-Al has potential to remove SO₄^2? ions from aqueous solutions at different concentrations. It was found that the temperature has positive effect on the process and negative ΔG values indicated thermodynamically feasible and spontaneous nature of the sorption. Positive value of ΔS reveals the increased randomness at the solid–solution interface during the fixation of the ion on the active sites of the sorbent. The effect of other anions was studied and it was found the existence of them in the solution has considerable effect on the sulphate removal.     

Synthesis,crystal structure and photophysical properties of a novel Pt(II) complex with multi-functionalized cyclometalating ligand

A novel Pt(II) complex [(L)PtCl] (HL = 4-{p-[N-(4-(9-carbazole))butyl-N-phenyl] aniline}-6-phenyl-2,2′-bipyridine) has been synthesized and verified by ¹H NMR, elemental analysis and X-ray crystallography. The crystal (C₄₄H₃₅N₄ClPt, M_r = 850.30) belongs to monoclinic system, space group P2(1)/c, with a = 21.864(6), b = 9.306(3), c = 17.240(5) Å, β = 96.483(6)°, Z = 4, V = 3485.3(16) ų, D_C = 1.620 g/cm³, μ(Mo-Kα) = 4.141 mm^? 1, F(000) = 1688, R₁ = 0.0591, wR₂ = 0.0976. The coordinate geometry of the Pt atom is a distorted square planar configuration. The complex molecules are stacked by a weak π–π interaction in a head-to-tail fashion along the b axis to form 1D chain and the alternating 1D chains are packed to form the 2D lamellar system. The complex shows an intense metal-to-ligand charge transfer (¹MLCT) (dπ(Pt) → π*(L)) transitions (ε ～ 2 × 10⁴ dm³ mol^? 1 cm^? 1) at 448 nm in the UV–Vis absorption spectrum and a strong phosphorescence at 592 nm in CH₂Cl₂ solution at room temperature. An intramolecular energy transfer process from the carbazole unit to the arylamine-modified [(C^N^N)PtCl] emissive center exists in the complex.     

Hydrothermal synthesis,structure and fluorescent property of a novel cuprous thiocyanate inorganic polymer directed by 1,5-bis(pyridinium) pentane cation

A novel cation-templated 3D cuprous thiocyanate polymer, {(bppt)[Cu₂(NCS)₄]}_n, bppt = 1,5-bis (pyridinium) pentane, was hydrothermally synthesized and structurally characterized. The compound crystallizes in monoclinic system, space group P2(1)/c with cell parameters of a = 10.1571(8) Å, b = 15.9785(13) Å, c = 15.3983(12) Å, V = 2407.4(3) Å³, Z = 4, D_c = 1.622 g cm^?3, F(0 0 0) = 1192, μ = 2.133 mm^?1, R₁ = 0.0551, wR₂ = 0.1246. In the polymeric architecture, Cu₂(NCS)₄ dimer is connected by NCS^? bridging ligand to constitute a infinite 3D framework with the organic cation bppt trapped in it. Photoluminescence investigation reveals that a slightly red shift of 27 nm for the complex takes place comparing with the organic cation.     

Optimized and functionalized paper sludge activated with potassium fluoride for single and binary adsorption of reactive dyes

The yield and adsorption uptake of optimized paper sludge activated carbon (PSAC) prepared using potassium fluoride as alternative chemical activation agent was investigated. The PSAC was functionalized with ethylenediamine (FPSAC) and both adsorbents were used for single and binary adsorption of Reactive orange 16 (RO16) and Reactive blue 19 (RB19). Effect of pH on the adsorption process, equilibrium, kinetics, isotherm and thermodynamic studies were carried out. Optimum PSAC preparation parameters were: activation temperature, X₁ = 810 °C; activation time, X₂ = 105 min; and impregnation ratio, X₃ = 0.95 which gave adsorption uptake of 178 and 158 mg/g for RO16 and RB19, respectively.