Micellization of Some Bile Salts in Binary Aqueous Solvent Mixtures

The micellization behavior of bile salts—sodium cholate and sodium deoxycholate was studied in aqueous methanol, ethanol and ethylene glycol mixtures (10–20 % v/v) over a temperature range (300–320 K) by surface tension and conductivity methods. Critical micelle concentration, extent of counter ion binding (α), interfacial property (A _min, ζ_max, π-CMC, $ \Updelta G_{\text{ad}}^{ \circ } $ ) and thermodynamic parameters ( $ \Updelta G_{\text{m}}^{ \circ } $ , $ \Updelta H_{\text{m}}^{ \circ } $ , $ \Updelta S_{\text{m}}^{ \circ } $ ) for the micellization process are reported and discussed.     

Structure and Biological Behaviors of Some Metallo Cationic Surfactants

In this study, different cationic surfactants were prepared by esterification with bromoacetic acid of different fatty alcohols, i.e., dodecyl, tetradecyl and hexadecyl species. The products were then reacted with diphenyl amine, and the resulting tertiary amines were quaternized with benzyl chloride to produce a series of quaternary ammonium salts. The metallocationic surfactants were prepared by complexing the cationic surfactants with nickel and copper chlorides. Surface tension of these surfactants were investigated at different temperatures. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ _max), minimum surface area (A _min), efficiency (PC₂₀) and effectiveness (π _CMC) were studied. The thermodynamic parameters such as the free energy of micellization ( $\Updelta G_{\text{mic}}^{^\circ }$ ) and adsorption ( $\Updelta G_{\text{ads}}^{^\circ }$ ), enthalpy ( $\Updelta H_{\text{m}}^{^\circ }$ ), ( $\Updelta H_{\text{ads}}^{^\circ }$ ) and entropy ( $\Updelta S_{\text{m}}^{^\circ }$ ), ( $\Updelta S_{\text{ads}}^{^\circ }$ ) were calculated. FTIR spectra and ¹H-NMR spectra were obtained to confirm the compound structures and purity. In addition, the antimicrobial activities were determined via the inhibition zone diameter of the prepared compounds, which were measured against six strains of a representative group of microorganisms. The results indicate that these metallocationic surfactants exhibit good surface properties and good biological activity on a broad spectrum of microorganisms.     

Thermodynamic Properties of Sulfobetaine-Type Surfactants

Sulfobetaine-type surfactants containing a hydroxy group were synthesized by the reaction of long chain monoalkyl dimethyl tertiary amine with 3-chloro-2-hydroxypropanesulfonic acid sodium salt. The structures were characterized by ¹H NMR and ESI-MS. Their critical micelle concentrations (CMC) in aqueous solution were determined by the plate method in the temperature rang from 298.15 to 328.15 K. The thermodynamic parameters of micellization ( $\Delta G_{\text{mic}}^{\theta}$ , $\Delta H_{\text{mic}}^{\theta}$ and $\Delta S_{\text{mic}}^{\theta}$ ) and surface adsorption ( $\Delta G_{\text{ad}}^{\theta}$ , $\Delta H_{\text{ad}}^{\theta}$ and $\Delta S_{\text{ad}}^{\theta}$ ) were calculated from CMC data. The results showed that the micellization and surface adsorption of these surfactants in aqueous solution was a spontaneous and entropy-driven process. The micellization and surface adsorption became easier when the alkyl chain length increased from 12 carbon atoms to 14. The enthalpy–entropy compensation of micellization and adsorption was investigated. The compensation temperature were found to be (311 ± 2) K for both micellization and adsorption. The $\Delta H_{\text{mic}}^{*}$ and $\Delta H_{\text{ad}}^{*}$ decreased, but the $\Delta S_{\text{mic}}^{*}$ and $\Delta S_{\text{ad}}^{*}$ increased with increasing the hydrophobic chain length from 12 to 14.     

Thermodynamics of Micellization of Sulfobetaine Surfactants in Aqueous Solution

The thermodynamics of micellization of the sulfobetaine (SB) amphoteric surfactants, that is N-alkyl-N,N-dimethyl-3-ammonio-1-propanesulfonate and N-alkyl-N,N-dimethyl-3-ammonio-1-butanesulfonate (the carbon atom number of the alkyl chain is 12, 14 and 16 respectively) in aqueous solution, have been studied by surface tension measurements with the temperature range from 298.15 to 318.15?K. The critical micelle concentrations (CMC) of SB n-3 and SB n-4 surfactants were determined from the drop-volume methods at different temperatures. The obtained results indicated that the values of critical micelle concentration strongly depended on the surfactants species and temperatures. Thermodynamic parameters ( $ \Updelta G_{\text{mic}}^{ \circ } $ , $ \Updelta H_{\text{mic}}^{ \circ } $ and $ \Updelta S_{\text{mic}}^{ \circ } $ ) of the micelle formation were determined. The micellization was found to be enthalpy-driven at lower temperatures, while this process was entropy-driven at higher temperatures. The enthalpy?Centropy compensation were also investigated. The compensation temperature T _c and $ \Updelta H_{\text{mic}}^{*} $ decreased, while $ \Updelta S_{\text{mic}}^{*} $ increased with the increase in the hydrophobic chain length.     

Hansen solubility parameters of cellulose acetate butyrate–poly(caprolactone) diol blend by inverse gas chromatography

The specific retention volumes, $ V_{\text{g}}^{0} $ , for adsorption of 21 solute probes on the solid surface of cellulose acetate butyrate (CAB)–poly(caprolactone) diol (PCLD) blend determined in the temperature range by inverse gas chromatography were used to evaluate Hansen solubility parameters (HSP). The effect of plasticizer, PCLD, on the HSP of CAB was investigated. The three components of HSP namely dispersive $ \delta_{2}^{\text{d}} $ , polar $ \delta_{2}^{\text{p}} $ , and hydrogen bonding $ \delta_{2}^{\text{h}} $ of the blend surface were compared with the CAB surface. The $ \delta_{2}^{\text{h}} $ of CAB was increased due to the addition of PCLD, while the change in the dispersive and polar components was found to be insignificant. The three HSP were decreasing linearly with increase of temperature for the blend as well as for pure CAB. The variation of HSP with weight fraction of CAB shown that the $ \delta_{2}^{\text{p}} $ was positively deviating from linearity whereas $ \delta_{2}^{\text{d}} $ and $ \delta_{2}^{\text{h}} $ were negatively deviating from linearity.     

Surface and Biological Activity of Some Prepared Iminium Surfactants Based on Schiff Bases

A series of novel iminium surfactants were prepared through quaternization of different prepared fatty Schiff bases with benzyl chloride. The chemical structures were confirmed using FTIR, ¹H-NMR and mass spectroscopy. The surface properties and biological activity of these surfactants were investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ_max) and minimum surface area (A _min), Efficiency (PC₂₀) and Effectiveness (π_CMC) as well as the free energy of micellization ( $ \Updelta G_{\text{mic}}^{\text{o}} $ ) and adsorption ( $ \Updelta G_{\text{ads}}^{\text{o}} $ ) were calculated. It was found that the prepared compounds have good surface and biological activity.     

Polymerization of cyclohexene oxide by methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts

Methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts having non-nucleophilic anions such as $ {\text{SbF}}^{ - }_{6} $ , $ {\text{PF}}^{ - }_{6} $ and $ {\text{AsF}}^{ - }_{6} $ were newly prepared and found to be very active initiators for the polymerization of cyclohexene oxide at room temperature, in dichloromethane without any external stimulation. The effects of counter ion structure, salt and monomer concentration on the polymerization yield and molecular weight, and the mechanism of initiation are presented.     

Salt Effect on Mixed Micelle and Interfacial Properties of Conventional Cationic Surfactants and the Ionic Liquid Surfactant 1-Tetradecyl-3-methylimidazolium Bromide ([C14mim]Br)

The surface properties and mixed micellization behavior of binary combinations of an ionic liquid surfactant, namely, 1-tetradecyl-3-methylimidazolium bromide ([C₁₄mim]Br) with common cationic surfactants viz. tetradecyltrimethylammonium bromide and tetradecylpyridinium bromide in the presence of sodium bromide (NaBr) were investigated by surface tension and conductivity measurements. The critical micelle concentration (CMC) and interfacial parameters, such as the maximum surface excess (Γ_max), minimum area per molecule (A_min) and surface pressure at the CMC (π_CMC) were determined from the surface tension data. The CMC and Γ_max values were found to decrease with increasing salt concentrations. The $ \Updelta G_{\text{ad}}^{ \circ } $ and $ \Updelta G_{\text{m}}^{ \circ } $ values are negative indicating the spontaneity of micelle formation.     

Counter-ion Effect on Micellization of Ionic Surfactants: A Comprehensive Understanding with Two Representatives, Sodium Dodecyl Sulfate (SDS) and Dodecyltrimethylammonium Bromide (DTAB)

Various micelle parameters viz., critical micelle concentration (CMC), counter-ion binding (β), aggregation number (N), hydrodynamic radius (R _h), micelle zeta potential (ζ) and energetic parameters, free energy of micellization ( $ \Updelta G_{\text{m}}^{0} $ ), enthalpy of micellization ( $ \Updelta H_{\text{m}}^{0} $ ) and entropy of micelle formation ( $ \Updelta S_{\text{m}}^{0} $ ) were determined for sodium dodecylsulfate, and dodecyltrimethylammonium bromide in the presence of NaCl for the former and NaBr for the latter. Conductometry and calorimetry methods were used for the measurements of CMC and energetic parameters. The fluorimetric (static quenching) method was employed to determine N and dynamic light scattering to estimate R _h and ζ. The conductometrically determined β was verified from the CMC values by calorimetry using the Corrin–Harkins equation. The results found for the two surfactants of identical tails but different head groups have been presented and discussed. A detailed report on the salt effect using salts containing counter-ions the same as those in the surfactant is found only limitedly in the literature.     

Magnetic cobalt-zinc ferrite/PVAc nanocomposite: synthesis and characterization

Metal oxide nanoparticles are the subject of current interest because of their unusual optical, electronic, and magnetic properties. In this work, cobalt zinc ferrite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ ) nanoparticles have been synthesized successfully through redox chemical reaction in aqueous solution. The synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles have been used for the preparation of homogenous polyvinyl acetate-based nanocomposite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ ) via in situ emulsion polymerization method. Structural, morphological and magnetic properties of the products were determined and characterized in detail by X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The XRD patterns of the $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ confirmed that the formed nanoparticles are single crystalline. According to TEM micrographs, the synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles had nano-needle morphology with an average particle size of 20 nm. The calculated coefficient of variation (CV) of nanoparticles diameters obtained by TEM micrographs was 16.77. The $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles were dispersed almost uniformly in the polymer matrix as was proved by SEM technique. The magnetic parameters of the samples, such as saturation magnetization (M _s) and coercivity (H _c) were measured, as well. Magnetization measurements indicated that the saturation magnetization of synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ nanocomposites was markedly less than that of $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ magnetic nanoparticles. However, the nanocompoites exhibited super-paramagnetic behavior at room temperature under an applied magnetic field.     

Surface characterization of cellulose acetate propionate by inverse gas chromatography

The purpose of this paper is to study the surface energetics of the polymer excipient cellulose acetate propionate (CAP) in the solid form. The net retention volumes, V _N, for n-alkanes and polar solutes have been measured in the temperature range 353.15–403.15 K by inverse gas chromatography. The dispersive surface free energy, $ \gamma_{\text{S}}^{\text{d}} $ , and Lewis acid–base parameters $ K_{\text{a}} $ and $ K_{\text{b}} $ , have been determined using V _N values. The $ \gamma_{\text{S}}^{\text{d}} $ values are decreased linearly with increase of temperature. The $ \gamma_{\text{S}}^{\text{d}} $ value at 353.15 K is 24.50 ± 1.54 mJ/m², and the temperature gradient was found to be ?0.287 mJ/m²/K¹. The $ K_{\text{a}} $ and $ K_{\text{b}} $ values are 0.410 ± 0.021 and 1.708 ± 0.388, respectively, which suggest that the CAP solid surface contain relatively more basic sites. The K _a and K _b values of CAP are compared with the similar values obtained on the cellulose acetate butyrate solid surface.     

Active Sites of a NiSO4/γ-Al2O3 Catalyst for the Oligomerization of Isobutene

Structural characterization, the mechanism of catalytic activity generation and the nature of active sites of a NiSO₄/γ-Al₂O₃ catalyst for isobutene oligomerization were studied by temperature programmed reduction (TPR), X-ray diffraction (XRD), diffuse reflectance infrared fourier transformed (DRIFTS) and X-ray photoelectron spectroscopy (XPS) techniques. The TPR measurements together with the XRD data indicated that calcination of the catalyst at 500 °C did not form either nickel oxide or nickel aluminate. The presence of only one type of surface nickel species formed by the incorporation of nickel ions into the surface vacant sites of γ-alumina lattice was indicated by XPS with Ar⁺ ions sputtering and TPR measurements. XPS analysis of the calcined catalyst suggested that the oxidation state of nickel ions in the calcined catalyst was (+2) and after calcination the nickel ions were coordinated to relatively more basic ligands. The surface acid centers of the catalyst were found to be only Lewis type. SO₄ ^2? ions were found to be present as a chelating bidentate ligand and enhanced the acidity of metal ( $ {\text{Al}}^{3 + } $ and/or $ {\text{Ni}}^{2 + } $ ) Lewis acid centers. The results suggested that the combined effects of the presence of the bidentate SO₄ ^2? ligand and dehydroxylation generate coordinatively unsaturated $ {\text{Ni}}^{2 + } $ that interact with isobutene during the oligomerization reaction. The formation of lower-valent nickel ions ( $ {\text{Ni}}^{x + } ,x\; \le\; 1 $ ) was demonstrated by in situ DRIFTS using CO as a probe molecule and by XPS measurements. Formation of a binuclear bridging carbonyl complex, $ [{\text{Ni}}({\text{CO}})^{ + } ]_{2} $ suggested that some lower-valent nickel species were formed via in situ reduction by isobutene. Analysis of Ni 2p photolines indicated the appearance of a new lower-valent nickel species ( $ {\text{Ni}}^{x + } ,x \;\le\; 1 $ ) during the course of isobutene oligomerization. Hence it is plausible that lower-valent nickel species might act as the active center for the oligomerization reaction, while the SO₄ ^2? ions enhance the acidity of the Lewis acid sites on the surface and assist in the adsorption of reactant molecules on the surface.     

Synthesis and Properties of X-Type Alkyl Sulfonate Gemini Surfactants Derived from Cyanuric Chloride

A series of X-type alkyl sulfonate Gemini surfactants (XC_n, n?=?6, 8, 10) was synthesized by a simple method. The chemical structures of the prepared compounds were confirmed by ¹H NMR, ¹³C NMR, ESI?CMS and Elementary analysis. The surface activity and thermodynamic properties of micellization of the X-type alkyl sulfonate Gemini surfactants were compared with sodium dodecylsulfate by means of surface tension. The properties of XC_n are superior to those of SDS such as the ??_CMC and CMC of XC₁₀ are 26.3?mN/m and 0.2?mmol/L respectively. The adsorption isotherms for XC_n were established by fitting the pre-CMC surface tension data with a quadratic function. The thermodynamic parameters of micellization ( $ \Updelta G_{m}^{ \circ } $ , $ \Updelta H_{m}^{ \circ } $ , $ \Updelta S_{m}^{ \circ } $ ) derived from electrical conductivity indicate that the micellization of XC_n is entropy-driven.     

Inverse gas chromatography characterization of polyaniline complexes: application to volatile organic compounds sensing

Surface thermodynamic characteristics of two polyaniline complexes with inorganic and organic acids were investigated using inverse gas chromatography technique. Thirteen solutes were injected into two separate chromatographic columns packed with polyaniline (PANI) complexes as stationary phases without any chromatographic support. The retention volumes of these solutes were measured to show their strong retention with both PANI complexes, particularly the xylene isomers: ortho, meta and para. The free energy of adsorption, $\Updelta G_{a}$ Δ G a , consisting of dispersive term $\Updelta G_{a}^{d}$ Δ G a d and the acid–base interaction term, $\Updelta G_{a}^{s}$ Δ G a s was also determined showing that it is mainly based on its dispersive contribution. The dispersive surface energy of hydrochloric acid polyaniline complex is ranging from 70.39 mJ/m² at 130 °C to 65.75 mJ/m² at 150 °C while the surface energy of dodecylbenzenesulfonic acid polyaniline complex has shown slight upper difference ranging from 70.90 to 66.23 mJ/m² in the same temperature’s interval, thus reflecting a behavior comparable to that of high surface energy materials. Furthermore, the obtained PANI complexes powders were characterized using fourier transform infrared spectrometry, Raman spectroscopy, UV–visible, XRF and SEM techniques. The measured retention volumes were combined with linear solvation energy relationship (LSER), called Abraham law, to determine physicochemical parameters describing dispersive, polar and acid–base properties, the surface of both polyaniline was found out exhibiting a basic nature.     

Activity and selectivity of a {\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} catalytic membrane in the partial hydrogenation reactions of acetylene and 1,3-butadiene

A ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane supported on a macroporous $\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ tube was prepared by sol–gel processing and used in the partial hydrogenation of acetylene and 1,3-butadiene. The average pore diameter of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was 3.6 nm. The gases were separated by Knudsen diffusion. The activity and selectivity of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was compared to that of ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ catalysts used in a conventional packed bed reactor. The highest selectivity to the partially hydrogenated products occurred when the reactant was premixed with H₂ and was passed through the membrane wall.     

Surface Adsorption and Aggregation Properties of Novel l-Lysine-Based Gemini Surfactants

Four chiral l-lysine-based gemini surfactants with different spacers were synthesized, namely, disodium (18R,23R)-12,20,21,29-tetraoxo-13,19,22,28-tetraazatetracontane-18,23-dicarboxylate([C₁₂-2-C₁₂]Na₂), disodium (18R,25R)-12,20,23,31-tetraoxo-13,19,24,30-tetraazadotetracontane-18,25-dicarboxylate([C₁₂-4-C₁₂]Na₂), disodium(18R,27R)-12,20,25,33-tetraoxo-13,19,26,32-tetraazatetratetracontane-18,27-dicarboxylate([C₁₂-6-C₁₂]Na₂), disodium(2R,2′R)- 2,2′-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(6-dodecanamidohexanoate) ([C₁₂-T-C₁₂]Na₂). The chemical structures of the prepared compounds were confirmed by ¹H-NMR, ESI–MS and IR spectra. Further, the critical micelle concentration (CMC) of these surfactants in aqueous solutions was determined by surface tension and conductometry methods at 25 °C. Moreover, the adsorption and micellization behaviors of these surfactants were estimated by pC₂₀, the minimum average area per surfactant molecule (A_min), and standard free energy for micellization and adsorption ( \( \Updelta G_{\text{mic}}^{^\circ } \) and \( \Updelta G_{\text{ads}}^{^\circ } \) ). The results show that the four gemini surfactants have low CMC values and significantly low surface tension. Furthermore, the surfactants show strong adsorption at the air–water interface. The CMC and A_min values of the surfactants were found to be in the order of [C₁₂-2-C₁₂]Na₂ < [C₁₂-4-C₁₂]Na₂ < [C₁₂-6-C₁₂]Na₂ < [C₁₂-T-C₁₂]Na₂, which were in agreement with the sequence of \( \Updelta G_{\text{mic}}^{^\circ } \) and \( \Updelta G_{\text{ads}}^{^\circ } \) . The circular dichroism of the surfactants indicated the formation of chiral aggregates above the CMC values.     

Determination of equilibrium silver sulphate concentration in the system Cu-H2SO4-CuSO4-H2O-Ag2SO4-Ag as a function of composition

The value of the ratio \(\gamma _{{\text{Cu}}^{{\text{2 + }}} } /\gamma _{{\text{Ag}}^{\text{ + }} }^2 \) ( \(\gamma _{{\text{Cu}}^{{\text{2 + }}} } ,\gamma _{{\text{Ag}}^{\text{ + }} } \) -are the mean activity coefficients of copper and silver ions, respectively) was calculated from the measured emf of the cell $${\text{Cu(Hg)|H}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{ (}}c_{\text{x}} {\text{)}} - {\text{CuSO}}_{\text{4}} {\text{ (}}c_{\text{y}} {\text{)|Hg}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{, Hg}}$$ and the solubility of Ag₂SO₄ in H₂SO₄ (c _x) and CuSO₄ (c _y) solutions. The concentration of H₂SO₄ in the solution was varied from 0.5 to 2.1 mol dm^?3 that of CuSO₄ from 0.4 mol dm^?3 to saturation. The results were presented as a function: $$\frac{{\gamma _{{\text{Cu}}^{{\text{2 + }}} } }}{{\gamma _{{\text{Ag}}^{\text{ + }} }^2 }} = a_0 + a_1 c_{\text{x}} + a_2 c_{\text{y}} + a_3 c_{\text{x}}^{\text{2}} + a_4 c_{\text{x}} c_{\text{y}} + a_5 c_{\text{y}}^2 .$$ This function allows the estimation of the equilibrium silver ion concentration \(c_{{\text{Ag}}^{\text{ + }} }^{{\text{eq}}} \) in solutions containing both H₂SO₄ and CuSO₄ in the presence of metallic copper. The function is also very useful for the estimation of the \(c_{{\text{Ag}}^{\text{ + }} }^{{\text{eq}}} \) near a working copper electrode.     

Total concentration of main components in solutions for metal electroplating as a criterion for classifying and choosing resource-saving compositions of solutions

A comparative analysis is performed of the variations in the total concentration of the main components $\left( {\sum\limits_i {c_i } } \right)$ , in the solutions proposed and used in different years for electroplating individual metals (Cr, Cu, Ni, Zn, Sn, Cd, Pb, and Fe). A quantitative concentration criterion is determined for classifying solutions into resource-saving ( $\left( {\sum\limits_i {c_i \leqslant 2.32} } \right)$ mol-equiv/L) and resourceintensive ( $\left( {\sum\limits_i {c_i \geqslant 2.78} } \right)$ mol-equiv/L) compositions. In addition to scientific interest, this material can be useful for developing studies aimed at reducing the negative environmental impact of electroplating shops or sections.     

Formation and characterization of nanoporous structures on surface of LPD-derived GeO2 ceramic film

This work represents an idea of forming nanoporous structures on surface of a LPD (liquid phase deposition)-derived GeO₂ ceramic film by thermal reduction of GeO₂ under hydrogen atmosphere. SEM, XRD and Raman analyses show that well-defined nanopores with size in range of 10–100 nm have been formed on surface of GeO₂ film by annealing at 600 °C for 5–10 min. The pore formation process is furthered by structural defects which serve as active sites for the thermal reduction reaction. Fast phase transformation from hexagonal GeO₂ to tetragonal GeO₂ has occurred within the first 5 min of annealing. Green-yellow (2.32 eV) and violet (2.9 eV) photoluminescences originating from $ {\text{O}} {-} \mathop {\text{Ge}}\limits^{ \bullet \bullet } {-} {\text{O}} $ and ≡Ge–Ge≡ defects are observed in the film samples. The photoluminescence peak intensity decreases with increase of annealing time due to diminution of O/Ge ratio. The film annealed for 5 min exhibits a maximum green-yellow to violet PL peak ratio, which is related to generation of some new $ {\text{O}} {-} \mathop {\text{Ge}}\limits^{ \bullet \bullet } {-} {\text{O}} $ defects at the phase interface.     

[CuL(H2O)2]{[CuL][Fe(CN)6]}2·2H2O (L=3,10-Bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane): A Novel Three-Dimensional Coordination Polymer via H-Bonded Linkages of One-Dimensional Zigzag Chain

A complex with the formula [CuL(H₂O)₂]{[CuL][Fe(CN)₆]}₂·2H₂O, where L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and crystallographically characterized. The structure is composed of a one-dimensional zigzag chain of $\left\{ {[{\text{CuL}}][{\text{Fe(CN)}}_{\text{6}} ]} \right\}_2^{2 - } $ units, and [CuL(H₂O)₂]²⁺ units. The one-dimensional zigzag chain extents through ${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Fe}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Cu}}$ linkages. The adjacent two polymer chains are linked by the ${\text{O}}{\kern 1pt} - {\kern 1pt} {\text{H}}{\kern 1pt} \cdot \cdot \cdot {\kern 1pt} {\text{N}}{\kern 1pt} \equiv {\kern 1pt} {\text{C}}{\kern 1pt} - $ hydrogen bonding between [CuL(H₂O)₂]²⁺ and [Fe(CN)₆]^3?, forming a 3D supramolecular structure with inner hydrophilic channels. Magnetic susceptibility measurements show no exchange interaction between the Cu(II) and Fe(III) ions due to the longer ${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{N}}$ (axial) bond length.