Synthesis,characterization and evaluation of antioxidant and anticancer activities of novel benzisoxazole-substituted-allyl derivatives

A novel series of various 2-allylbenzo[d]isoxazol-3(2H)-ones were synthesized using benzo[d]isoxazol-3(2H)-one treated with different allyl bromides/chlorides in the presence of water-mediated cesium carbonate as a new catalyst 3(a-h). The structures of the newly synthesized Benzisoxazole-substituted-allyl derivatives were characterized by spectroscopic methods and mass spectrometry. These synthesized compounds were evaluated for their in vitro antioxidant and anticancer activity. Compounds 3b, d, f, h were identified as the best hit against HT-29 Human colon cancer cells. Similarly, compounds like 3b, d, f, h showed significant antioxidant activity compared to the standard drug butylated hydroxy toluene (BHT).      

Synthesis and Structural Characterization of Metal Compounds Incorporating the Ortho-Quinone Manganese Tricarbonyl Complex as an Organometalloligand

Three π-quinonoid compounds incorporating the organometalloligand ortho-quinone manganese tricarbonyl ([(C₆H₄O₂)Mn(CO)₃]^?, o-QMTC) have been synthesized and characterized by IR and X-ray crystallography: [Pd(o-QMTC)(PPh₃)₂]BF₄·CH₂Cl₂ (1), (o-QMTC)Rh(1,5-cyclooctadiene) (2), and Cu(o-QMTC)₂ (3). The formally anionic o-QMTC ligand features Mn-arene bonding that is best described as η⁴-bound. Nevertheless, o-QMTC interplanar angular data and ν_co data suggest significant contribution from η⁵ and η⁶ forms. In each of the compounds, the o-QMTC organometalloligand(s) contribute to a square planar geometry about the Pd(II), Rh(I), or Cu(II) metal center.     

Adsorption of Congo Red dye by native amine and carboxyl modified biomass of <Emphasis Type="Italic">Funalia trogii</Emphasis>: Isotherms,kinetics and thermodynamics mechanisms

Native, iminodiacetic acid and triethylenetetraamine modified biomasses of Funalia trogii were used for removal of Congo Red dye (CRD) from aqueous medium. The native and modified fungal biomasses were characterized using ATR-FTIR, Zeta potential, contact angle studies and analytical methods. FTIR studies of the native and chemically modified adsorbent preparations show that amine, carboxyl and hydroxyl groups are involved in the adsorption of the model dye (i.e., Congo Red). The maximum adsorption of the CRD on the native, carboxyl and amine groups modified fungal biomasses was obtained at pH 5.0. The amount of adsorbed dye on the adsorbent samples increased as the initial concentration of CRD in the solution increased to 200mg/L. The adsorption capacities of native, carboxyl groups and amine modified fungal preparations were 90.4, 153.6 and 193.7mg/g dry adsorbents, respectively. The data was fitted well with the Langmuir isotherm model, and followed the pseudo-second-order equations. Thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) were also calculated. The results showed that triethylenetetraamine (TETA) modified biomass of F. trogii presented an excellent dye removal performance and can be used in various environmental applications such as various micro-pollutants removal from aqueous medium.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Adsorptive performance of calcined <Emphasis Type="Italic">Cardita bicolor</Emphasis> for attenuating Hg(II) and As(III) from synthetic and real wastewaters

The first application of calcined Cardita bicolor oyster shell (CCBS) for Hg(II) and As(III) adsorption from synthetic and real wastewaters was tested. The main elements in CCBS structure were carbon, oxygen, magnesium, phosphor, and calcium. Effects of different parameters like initial pH, contact time, temperature, and CCBS dosage were assessed. The results showed that the maximum recovery of Hg(II) and As(III) adsorption was determined as C₀=10 mg/L, t=80 min, T=25 °C, CCBS dosage=5 g/L, and pH=6 (for mercury ion) and 7 (for arsenic ion). In these conditions, 95.72% Hg(II) and 96.88% As(III) were removed from aqueous solution. The correlation coefficient (R²) values for both adsorbates were obtained >0.98 and >0.96 for Langmuir and Freundlich isotherm models, respectively. Pseudo-second-order kinetic model was more capable to describe kinetic behavior of adsorption process of both metal ions in comparison with pseudo-first-order model. The half life (t_1/2) value for Hg(II) and As(III) with initial concentration of 10 mg/L was 4.032 and 4.957 min, respectively. Moreover, thermodynamic parameters of enthalpy (ΔH ^o ), entropy (ΔS ^o ), and Gibbs free energy (ΔG ^o ) were investigated. Two real wastewaters obtained from a leather factory and a landfill leachate were successfully treated using CCBS. The results confirmed that adsorption process of metals ions was exothermic and spontaneous.     

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.     

A Facile Access to New Polymethylmethacrylate-Anchored Ferrocene Substituted Nickel(II) Unsymmetrical Schiff Base Complexes: Synthesis and Characterization

This paper discloses two new side-chain metallopolymers containing an unsymmetrical organometallic Schiff base complex of Ni(II) linked to a polymethylmethacrylate (PMMA) matrix. The neutral ferrocene substituted Schiff base complex 1, Ni{CpFe(η⁵-C₅H₄)-C(O)CH=C(CH₃)N–o-C₆H₄N=CH-(2-O,5-OH-C₆H₃)} where (Cp = η⁵-C₅H₅), was synthesized via template reaction by condensation of the tridentate half-unit metalloligand Fc-C(O)CH=C(CH₃)-N(H)-o-C₆H₄NH₂ (Fc = ferrocenyl = CpFe(η⁵-C₅H₄)) with 2,5-dihydroxybenzaldehyde in the presence of nickel(II) acetate tetrahydrate. The binuclear Schiff base complex of Ni(II) containing an aromatic free hydroxyl group was reacted under basic conditions with PMMA to afford, upon trans-esterification reaction, metallopolymers 2 (complex 1 monomeric unit/PMMA = 1/5) and 3 (complex 1 monomeric unit/PMMA = 1/3). Elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopies, and cyclic voltammetry were utilized to characterize the newly synthetized compounds. Surface morphology of the metallopolymer film of 2 was studied using atomic force microscopy.     

Structure and Spectral Properties of Pyrazine Ligand Assisted Self-Assembly of a Coordination Polymer Containing Copper-Cyanide Building Blocks

The metal–organic framework $ ^{3}_{\infty } \left[ {{\text{Cu}}_{3} \left( {\text{CN}} \right)_{3} \cdot \left( {\text{pyz}} \right)_{ 2} } \right] $ ∞ 3 [ Cu 3 ( CN ) 3 · ( pyz ) 2 ] , 1, (pyz pyrazine) was prepared in water/acetonitrile solvent at ambient temperature from the adducts K₃[Cu(CN)₄], pyrazine and Me₂SnCl₂. The structure of 1 consists of four-coordinate Cu(1) sites exhibiting a distorted tetrahedral geometry and the linear two-coordinate Cu(2) sites. Notably distorted cages, [Cu₈(CN)₄(pyz)₄], [Cu₈(CN)₆(pyz)₂] and [Cu₆(CN)₂(pyz)₄], can be considered as the basic building blocks of the structure of 1. Box-like structures create inextricably interpenetrated equivalent 3D-frameworks. The structure and spectroscopic properties of 1 were also investigated by thermal analysis and IR, mass, UV/Vis and fluorescence spectra.     

Mechanism of electrodeposition of copper from cupric pyrophosphate solutions

Cathodic polarization curves were measured for copper in cupric pyrophosphate solutions of different concentrations and temperatures. A rotating disc electrode was used to eliminate concentration polarization. For all solutions, two potential regions are distinguishable in the polarization curve; one is less negative than a critical potential E_b around ?0.75 V vs sce (Region I) and the other more negative than E_b (Region II). A weak adsorption of pyrophosphate ions and hence some inhibition of the electrodeposition of copper is expected for Region I but there is no adsorption in Region II. The exchange current density i_o for the copper deposition was obtained by extrapolating the Tafel relation observed in Region II to the rest potential corresponding to the equilibrium potential. The following reaction mechanisms are proposed to explain the dependence of i_o on the concentration of Cu(P₂O₇)^6?₂ and P₂O^4?₇ ions.

Apparent activation energies are estimated to be about 11 kcal/mol in both cases.     

Synthesis of snowman-shaped microparticles by monomer swelling and polymerization of crosslinked seed particles

Nonspherical snowman-shaped micro-sized particles were synthesized via monomer swelling and the polymerization of crosslinked seed particles. Monodispersed crosslinked polystyrene microspheres and methylmethacrylate were used as seed particles and the swelling monomer, respectively. Methylmethacrylate (MMA) induced crosslinked polystyrene microparticle swelling; however, compared to polystyrene, MMA is relatively hydrophilic. As a result, phase separation was observed, resulting in monomer-swollen, cross-linked particles protruding from the surface of the seed particles. By changing the monomer-to-particle weight ratio from 4 to 8, the ratio of the size of the head to the body of the snowman-shaped particles was varied from 0.3 to 0.7. The morphologies of the snowman-shaped particles were predicted using Surface Evolver software, and the simulation was applied to show the unique self-organization morphologies of snowman-shaped particles. We synthesized snowman-shaped microparticles by swelling and polymerizing cross-linked PS seed particles with methylmethacrylate. The monomer-swollen, cross-linked particles exhibited protrusions from the surface of the microparticles due to the phase separation of seeds from the particles. The size of the protrusion or head of the snowmanshaped particles was controlled by changing the monomer-to-particle weight ratio during the swelling process. Simulations were applied to estimate the aspect ratio of snowman-shaped particles and their self-assembled morphologies.     

Removal of Copper(II) and Zinc(II) from Aqueous Solutions Using a Lignocellulosic-Based Polymeric Adsorbent Containing Amidoxime Chelating Functional Groups

In this study, the adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto amidoximated polymerized banana stem (APBS) has been investigated. Infrared spectroscopy was used to confirm graft copolymer formation and amidoxime functionalization. The different variables affecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration, and temperature have been investigated. The optimum pH for maximum adsorption was 10.5 (99.99%) for Zn²⁺ and 6.0 (99.0%) for Cu²⁺ at an initial concentration of 10 mg L^?1. Equilibrium was achieved approximately within 3 h. The experimental kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models and are well fitted with pseudo- second-order kinetics. The thermodynamic activation parameters such as ΔG^o, ΔH^o, and ΔS^o were determined to predict the nature of adsorption. The temperature dependence indicates an exothermic process. The experimental isotherm data were well fitted to the Langmuir model with maximum adsorption capacities of 42.32 and 85.89 mg g^?1 for Cu(II) and Zn(II), respectively, at 20°C. The adsorption efficiency was tested using industrial effluents. Repeated adsorption/regeneration cycles show the feasibility of the APBS for the removal of Cu(II) and Zn(II) ions from water and industrial effluents.     

Kinetic and Equilibrium Studies on the Adsorption of Crystal Violet Dye using Kaolin as an Adsorbent

Abstract

Experimental investigations are carried out to adsorb toxic crystal violet dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring

1. particle size distribution using particle size analyzer,

2. BET surface area using BET surface analyzer,

3. structural analysis using X ray diffractometer, and

4. microscopic analysis using scanning electron microscope.

The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH, and temperature are studied for the adsorption of crystal violet in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on the pH of the solution. Free energy of adsorption (ΔG ^o ), enthalpy (ΔH ^o ), and entropy (ΔS ^o ) changes are calculated to know the nature of adsorption. The calculated values of ΔG ^o are ?4.11 and ?4.48 kJ/mol at 295 K and 323 K, respectively, for 20 mg/L of dye concentration, which indicates that the adsorption process is spontaneous. The estimated values of ΔH ^o and ΔS ^o show the negative and positive sign, respectively, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in more random fashion than in solution. The adsorption kinetic has been described by pseudo first order, pseudo second order and intra‐particle diffusion models. It is observed that the rate of dye adsorption follows pseudo second order model for the dye concentration range studied in the present case. Standard adsorption isotherms are used to fit the experimental equilibrium data. It is found that the adsorption of crystal violet on kaolin follows the Langmuir adsorption isotherm.     

Metal cation removal by P(VC-r-AA) copolymer ultrafiltration membranes

A series of amphiphilic copolymers containing poly(vinyl chloride-r-acrylic acid) (P(VC-r-AA) ) was synthesized and used to prepare membranes via a nonsolvent induced phase separation method. The prepared membranes were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and water contact angle and zeta potential measurements. The copolymer P(VC-r-AA) chains did not dissolved in a coagulation bath, indicating that the AA segments were completely retained within the membrane. Enriching degree of AA segments in surface layer was 2 for copolymer membrane. In addition, the introduction of AA segments made the membrane electronegative and hydrophilic so that the membrane was sensitive to the solution pH. The fouling resistance, adsorption of Cu(II), Cr(III) and Ce(IV) ions and the desorption properties of the membranes were also determined. The copolymer membranes exhibited good antifouling performance with a fouling reversibility of 92%. The membranes also had good adsorption capacities for Cu(II), Cr(III) and Ce(IV) ions. The optimal pH for Cu(II) adsorption was 6 and the copolymer membrane has potential applications for low concentration Cu(II) removal.

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Application of ZnO and TiO<Subscript>2</Subscript> nanoparticles coated onto montmorillonite in the presence of H<Subscript>2</Subscript>O<Subscript>2</Subscript> for efficient removal of cephalexin from aqueous solutions

This study considers the feasibility of uptake of cephalexin, an emerging contaminant, from aqueous solutions by using green local montmorillonite (GLM), montmorillonite coated with ZnO (ZnO/GLM) and montmorillonite coated with TiO₂ (TiO₂/GLM) in the presence of H₂O₂. Batch adsorption experiments were carried out as a function of pH, initial concentration of the cephalexin, adsorbent dosage, contact time, and temperature. Finally, the adsorbents were characterized by XRD, SEM and FTIR analyses. XRD patterns showed dramatic changes in the adsorbents after loading with the nanoparticles, confirming successful placing of the nanoparticles onto GLM. The GLM mineral surface after nanoparticle loading appears to be fully exposed and more porous with irregular shapes in particles diameters of 1-50 microns. FTIR analyses also confirmed dramatic changes in surface functional groups after modification with these nanoparticles. The results showed that the removal efficiency of cephalexin was better at lower pH values. Totally, the removal efficiency increased with increase in adsorbent dosage and contact time and decreased with concentration and temperature increase. The thermodynamics values of ΔG ^o and ΔH ^o revealed that the adsorption process was spontaneous and exothermic. In isotherm study, the maximum adsorption capacities (qm) were obtained to be 7.82, 17.09 and 49.26 mg/g for GLM, ZnO/GLM and TiO₂/GLM, respectively. Temkin constant (B _T ) showed that adsorption of cephalexin from solution was exothermic for all three adsorbents.     

Insight into adsorption mechanism of cationic dye onto agricultural residues-derived hydrochars: Negligible role of <Emphasis Type="Italic">π-π</Emphasis> interaction

Hydrochars derived from golden shower pod (GSH), coconut shell (CCH), and orange peel (OPH) were synthesized and applied to remove methylene green (MG5). The results indicated that the hydrochars possessed low specific surface areas (6.65-14.7m²/g), but abundant oxygen functionalities (1.69-2.12mmol/g). The hydrochars exhibited cellular and spherical morphologies. Adsorption was strongly dependent on the solution pH (2-10) and ionic strength (0-0.5M NaCl). Equilibrium can be quickly established in the kinetic study (60-120 min). The maximum Langmuir adsorption capacities at 30 °C followed the order GSH (59.6mg/g)>CCH (32.7mg/g)>OPH (15.6mg/g)> commercial glucose-prepared hydrochar (12.6mg/g). The dye adsorption efficiency was determined by the concentrations of oxygen-containing functionalities on the hydrochar surface. The adsorption process occurred spontaneously (? ΔG^o) and exothermically (?ΔH^o). Desorption studies confirmed the reversible adsorption process. Oxygenation of the hydrochar surface through a hydrothermal process with acrylic acid contributed to increasing MG5 adsorption and identifying the negligible role of π-π interaction to the adsorption process. The analysis of Fourier transform infrared spectrometry demonstrated that the aromatic C=C peak did not significantly decrease in intensity or shift toward higher/lower wavenumbers after adsorption, which further confirms the insignificant contribution of π-π interaction. Electrostatic attraction played a major role in adsorption mechanisms, while minor contributions were accounted for hydrogen bonding and n-π interactions. The primary adsorption mechanisms of MG5 onto hydrochar were similar to biosorbent, but dissimilar to biochar and activated carbon (i.e., π-π interaction and pore filling).     

The thermoelectric power in Bi2O3

The thermo electric power, ΔE/ΔT, of the cell $$\begin{gathered} O_2 + N_{2, } Pt/Bi_2 O_3 (\delta phase)/Pt, O_2 + N_2 \hfill \\ (T + \Delta T) (T) \hfill \\ \end{gathered}$$ has been measured as a function of oxygen pressure (10^?4 atm ? p(O₂) ? 1 atm) in the temperature range 650–800° C. The experimental result can be described by: $$[ \in ({\rm O}_2 /{\rm O}^{2 - } ) - \in (e, Pt)] = [45.6 \pm 5.6 log p(O_2 ) - 261](\mu VK^{ - 1} )$$ within experimental error, where ε(O₂/O²), the Seebeck coefficient ofδ-Bi₂O₃, stands for \(\mathop {\lim }\limits_{\Delta T \to 0} \Delta E/\Delta T\) The change of ΔE/ΔT with oxygen pressure corresponds to the change of the partial molar entropy of O₂. The heat of transport of O^2? ions is calculated to be 0.13 eV ± 0.01 whereas the activation enthalpy for ionic conduction is 0.30 eV. From this discrepancy it is concluded that the free ion model of Rice and Roth cannot be applied, while the extended lattice gas model of Girvin might explain the results when strong polaron coupling is assumed.     

Kinetic,thermodynamic and equilibrium studies on the removal of copper ions from aqueous solutions by natural and modified clinoptilolites

This paper presents the adsorption of Cu(II) ions from aqueous solution on Na and Fe-modified clinoptilolite. The copper adsorption experiments were performed in a batch system considering an optimum contact time of 24 h. Changes in the surfaces and structure were characterized by SEM data. According to the SEM results, it was anticipated that the removal efficiency of Fe-modified clinoptilolite was the highest compared with the natural and Na-modified clinoptilolites. Adsorption of Cu(II) ions by modified clinoptilolites was investigated as a function of the initial Cu(II) concentration, solution pH, and temperature. According to the results, the maximum adsorbed Cu amount onto Fe-modified was 19.40mg/l at the optimum operating condition with a pH value of 5.5 and temperature of 60 °C. According to the thermodynamic evaluations, positive ΔS and negative ΔG were found for the adsorption process showing that the adsorption reaction is a spontaneous process and more favorable at high temperatures. Sorption data have been interpreted in terms of Langmuir and Freundlich, Temkin and Dubinin-Radushkevich. The adsorption equilibrium was best described by the Langmuir adsorption isotherm. In addition, according to the Sips model, the sorption of Cu(II) ions on the Fe-modified clinoptilolite was found to be heterogeneous. The kinetic study showed that the Fe-modified clinoptilolite followed the pseudo-second order model. The results indicated that the clinoptilolite-rich tuff in its iron oxide form could be efficiently used for the removal of copper from aqueous solutions.     

Efficient and Reusable Pb(II) Metal–Organic Framework for Knoevenagel Condensation

A microporous lead–organic framework {[Pb₄(µ₈-MTB)₂(H₂O)₄]·5DMF·H₂O}_n (MTB?=?methanetetrabenzoate, DMF?=?N,N′-dimethylformamide) was synthesized and studied as a catalyst in Knoevenagel condensation reactions. The framework is built from tetranuclear [Pb₄(µ₃-COO)(µ₂-COO)₆(COO)(H₂O)₄] clusters and exhibits a 3D structure, with repeated 1D jar-like cavities with sizes about 14.98?×?7.88 and 14.98?×?13.17 Å² and BET specific surface area of 980 m² g^?1. To obtain open framework with unsaturated Pb(II) sites needed for catalysis, the thermal activation of the solvent exchanged sample was performed (DMF was exchanged by EtOH). The activated compound was tested in Knoevenagel condensation of bulky aldehydes and active methylene compounds at different temperatures. Excellent catalytic conversion and selectivity in condensation of small-sized aldehydes with malononitrile was observed, which indicates that the opened Pb(II) sites play a significant role in the heterogeneous catalytic process. Leaching test confirmed the stability of the catalyst in catalytic reactions. Moreover, the compound displayed good recyclability after several reuses without significant decrease in the original catalytic activity.

Graphical Abstract

Novel Pb(II) metal–organic framework was tested in Knoevenagel condensation. The catalyst showed excellent catalytic conversion, selectivity and recyclability. Aldehydes with lower kinetic diameter demonstrated high conversions and yields. Catalyst is less efficient for condensation of larger aromatic aldehydes.

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Synthesis of novel calix[6]-1,4-crown-based netty polymer and its excellent adsorption capabilities for aniline derivatives

By introducing four ester groups on p-tert-butylcalix[6]-1,4-crown-4 and then ammonolysis with ethanolamine, p-tert-butylcalix[6]-1,4-crown-4 amido derivative with four terminal hydroxyl groups (4) was obtained in good yield. Further by reacting compound 4 with 1,1,1-tris(tosylatemethyl)propane (6) in NaH/THF system, the novel netty calix[6]-1,4-crown-based polymer 7 was prepared in ??4+3?? condensation mode. The structure of polymer 7 was confirmed by elemental analysis, IR and ¹H NMR spectra. The loose pores and cross-linked netty architecture were observed for polymer 7 in its SEM images. The M _n of polymer 7 was 39,816 which indicated an average of approximately 23 calixarene units in each polymer molecule. Polymer 7 exhibited outstanding adsorption abilities for series of aniline derivatives (aniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-nitroaniline, m-nitroaniline and p-nitroaniline). The adsorption percentages for these aniline derivatives were above 90?%. The saturation adsorption capacities for aniline and p-nitroaniline were as high as 2.30 and 2.22?mmol/g, respectively. The adsorption abilities of polymer 7 kept stable at pH 6?C10 and it could be re-used after desorption of 10?% HCl. The high adsorption abilities of polymer 7 for aniline derivatives were not just because of ?ШC?? stack action of the phenyl groups and the hydrogen bond action, but also due to the stable conformation of calix[6]arene skeleton and big cavity, which were favorable for adsorption of aniline derivatives.     

Strictly two-dimensional self-avoiding walks: Density crossover scaling

The density crossover scaling of thermodynamic and conformational properties of solutions and melts of self-avoiding and highly flexible polymer chains without chain intersections confined to strictly two dimensions (d = 2) is investigated by means of molecular dynamics and Monte Carlo simulations of a standard coarse grained bead-spring model. We focus on properties related to the contact exponent set by the intrachain subchain size distribution. With R ～ N ^ν being the size of chains of length N and ρ the monomer density, the interaction energy e _int between monomers from different chains and the corresponding number n _int of interchain contacts per monomer are found to scale as with ν = 3/4 and θ₂ = 19/12 for dilute solutions and ν = 1/d and θ₂ = 3/4 for N? g(ρ) ≈ 1/ρ². Irrespective of ρ, long chains thus become compact packings of blobs of contour length with d _p = d ? θ₂ = 5/4 being the fractal line dimension. Due to the generalized Porod scattering of the compact chains, the Kratky representation of the intramolecular form factor F(q) reveals a non-monotonous behavior approaching with increasing chain length and density a power-law slope $F(q)q^d /\rho \approx 1/(qR)^{\theta _2 } $ in the intermediate regime of the wavevector q. The specific intermolecular contact probability is argued to imply an enhanced compatibility for polymer blends confined to ultrathin films. We comment briefly on finite persistence length effects.