Assessment of adsorption properties of inorganic–organic hybrid cyclomatrix type polyphosphazene microspheres for the removal of Pb(II) ions from aqueous solutions

Abstract

Inorganic–organic hybrid cyclomatrix type polyphosphazene microspheres (poly[cyclotriphosphazene-co-(4,4′-diaminodiphenylmethane)]) (HDMS) and poly[cyclotetraphosphazene-co-4,4′-diaminodiphenylmethane)] (ODMS) were prepared to investigate their possible use as alternative adsorbents for the comparative study on Pb(II) ions removal from aqueous solutions. The structures of the microspheres were elucidated by Fourier Transform Infrared (FTIR) spectroscopy and Dynamic Light Scattering (DLS) measurements, and the surface morphologies were also observed by Scanning Electron Microscopy (SEM). The adsorption of Pb(II) ions onto HDMS and ODMS from aqueous solutions was examined by means of pH, temperature, contact time and concentration. Furthermore, adsorption kinetics and isotherm models were applied and the experimental data fitted well with Langmuir isotherm and pseudo-second-order kinetic models. The maximum adsorption capacities of HDMS and ODMS for Pb(II) ions were obtained as 157.8 and 308.0?mg g^?1 at 20?°C and pH 5.5, respectively.     

New Heterocyclic Phosphorus Ylides: Synthesis,Crystal Structure,and Theoretical Calculation of Alkyl Substituted 3-(4-Benzoyl-1,5-diphenyl-2,3-dihydro-1H-pyrazol-3-yl)-3-oxo-2-(triphenylphosphoranylidene) Propanoates

Novel alkyl substituted 3-(4-benzoyl-1,5-diphenyl-2,3-dihydro-1H-pyrazol-3-yl)-3-oxo-2-(triphenylphosphoranylidene) propanoates (3) were synthesized from 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonylchloride (1) and alkyl (triphenylphosphoranylidene) acetates (2a–b). The synthesized compounds were characterized by elemental analysis, spectroscopic studies (3a–b), and single crystal X-ray diffraction (3a). The mechanism of the reaction between (1) and (2a) was studied by AM1, and the geometrical parameters of the studied molecules were also carried out in B3LYP methods with the standard 6–31G (d,p) basis set. NBO analysis were studied for 1 and 2a B3LYP methods with the standard 6–31G (d,p) basis set.     

Crystal structure,spectroscopic properties and density functional theory study of (Z)-1-[(2,4-dimethoxyphenylamino)methylene]naphthalen-2(1H)-one

The Schiff base (Z)-1-[(2,4-dimethoxyphenylamino)methylene]naphthalen-2(1H)-one was synthesized from the reaction of 2-hydroxy-1-naphthaldehyde with 2,4-dimethoxyaniline. The title compound has been characterized by FT-IR, UV-Vis and, X-ray single-crystal techniques. The present X-ray investigation shows that the compound exists in the keto-amine tautomeric form. Molecular geometry and vibrational frequencies of the compound in the ground state have been calculated using the density functional theory (DFT) with 6–311G(d, p) basis set and compared with the experimental data. The calculated results show that the optimized geometry is compatible with the crystal structure and the theoretical vibrational frequencies are in good agreement with the experimental values. Besides, molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO) and non-linear optical (NLO) properties of the compound were investigated using the same theoretical calculations.     

Development of a rapid-scan fiber-integrated terahertz spectrometer

Scientists in terahertz (THz) wave technologies have benefited from the recent developments in ultrafast laser technologies and RF technologies and applied these new gained techniques into characterizing a wide variety of phenomena. Undoubtedly, the most successful of these applications has been in the development of time-domain terahertz spectroscopic and imaging systems which has been utilized in the characterization of dielectrics and semiconductors. This pulsed technique has allowed users to characterize dynamical behavior inside materials under illumination with picosecond resolution. Typically pump/probe or similar dynamical measurements require the use of amplified pulses derived from free-space solid state lasers in the $\upmu $ J–mJ range and since interferometric techniques are typically used in pulsed measurements the measurement time of a THz spectrum can last at least tens of minutes. Better systems can be realized based on fiber laser technologies. Here we discuss the advantages of a THz spectrometer driven by an ultrafast Ytterbium doped fiber laser whose repetition rate can be tuned rapidly allowing for rapid dynamical measurements. The efficient gain medium, robust operation and compact design of the system opens up the possibility of exploring rapid detection of various materials as well as studying dynamical behavior using the high brightness source.     

Chemically Orthogonal Three‐Patch Microparticles

Compared to two‐dimensional substrates, only a few methodologies exist for the spatially controlled decoration of three‐dimensional objects, such as microparticles. Combining electrohydrodynamic co‐jetting with synthetic polymer chemistry, we were able to create two‐ and three‐patch microparticles displaying chemically orthogonal anchor groups on three distinct surface patches of the same particle. This approach takes advantage of a combination of novel chemically orthogonal polylactide‐based polymers and their processing by electrohydrodynamic co‐jetting to yield unprecedented multifunctional microparticles. Several micropatterned particles were fabricated displaying orthogonal click functionalities. Specifically, we demonstrate novel two‐ and three‐patch particles. Multi‐patch particles are highly sought after for their potential to present multiple distinct ligands in a directional manner. This work clearly establishes a viable route towards orthogonal reaction strategies on multivalent micropatterned particles.     

The role of spontaneous waves in the deflagration-to-detonation transition in submillimetre channels

Flame acceleration and transition to detonation in submillimetre two-dimensional planar and three-dimensional square channels were simulated by solving the compressible reactive Navier–Stokes equations. A simplified chemical–diffusive model was used to describe the diffusive transport and chemical reaction of a highly reactive mixture, such as stoichiometric ethylene and oxygen in 2D and 3D channels. The walls of the channels were modelled as no-slip and adiabatic. The initial flame acceleration and precursor shock formation were consistent with earlier results. Viscous dissipation in the boundary layer heats the reactants, which have been compressed by the precursor shock. The strength of the precursor shock and the amount of viscous dissipation increase until the temperature of the boundary layer is high enough to ignite the reactants. This produces a spontaneous wave, which, in most of the cases considered, initiates the detonation. The spontaneous wave first forms where the flame attaches to the wall in the planar channels, and forms at the corner where two walls meet in the square channels. In a separate study, the boundary layer also ignited in a computation for a circular tube containing a mixture hydrogen and oxygen represented by a detailed chemical reaction mechanism. The formation of spontaneous waves to the extent studied appears to be robust, and is relatively insensitive to channel geometry, fuel and oxidiser mixture, and the level of detail in the chemical–diffusive models used.     

Poly(p‐phenylene) with Poly(ethylene glycol) Chains and Amino Groups as a Functional Platform for Controlled Drug Release and Radiotherapy

Conventional cancer treatments such as chemotherapy, radiotherapy, or combination of these two result in side effects, which lower the quality of life of the patients. To overcome problems with these methods, altering the drug properties by conjugating them to carrier polymers has emerged. Such polymeric carriers also hold the potential to make tumor cells more sensitive to radiation therapy. Herein, poly(p‐phenylene) (PPP) polymer with poly(ethylene glycol) (PEG) chains and primary amino groups (PPP‐NH₂‐g‐PEG) is synthesized and conjugated with anticancer drug Doxorubicin (DOX). pH dependent drug release experiments are performed at pH 5.3 and pH 7.4, respectively. Cell viability studies on human cervix adenocarcinoma cells show that lower doses of DOX inhibit cell proliferation when conjugated with nontoxic doses of PPP‐NH₂‐g‐PEG polymer. Additionally, PPP‐NH₂‐g‐PEG/Cys/DOX bioconjugate significantly increases radiosensitive properties of DOX. It is possible to use lower doses of DOX when conjugated to PPP‐NH₂‐g‐PEG in combination with radiotherapy.

     

Dimensionally stable Nafion–polyethylene composite membranes for direct methanol fuel cell applications

Nafion^® impregnated Solupor^®, microporous UHMWPE film, (N-PE), Nafion^®117 (N117) and a membrane prepared using a DE2020 Nafion^® dispersion (DE2020) were characterized with respect to their swelling degree (SD), methanol cross-over, proton conductivity and DMFC performance at various methanol concentrations in order to understand the effect of impregnation of an ion-conductive polymer membrane to the fuel cell performance.     

Vibrational spectroscopy investigation using ab initio and density functional theory analysis on the structure of 5-chloro-10-oxa-3-thia-tricyclo[5.2.1.0(1,5)]dec-8-ene-3,3-dioxide

The IR spectra of 5-chloro-10-oxa-3-thia-tricyclo[5.2.1.0(1,5)]dec-8-ene-3,3-dioxide (COTDO) has been recorded in the region 4000-525cm(-1). The optimized molecular geometry, frequency and intensity of the vibrational bands of COTDO in the ground state has been calculated using the Hartree-Fock and density functional using Becke's three-parameter hybrid method with the Lee, Yang, and Parr correlation functional methods with 6-31G(d,p) and 6-311G(d,p) basis sets. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental IR spectra. The calculated geometrical parameters and harmonic vibrations are predicted in a very good agreement with the experimental data. The theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions (PEDs) using VEDA 4 program. With the help of this modern technique we were able to complete the assignment of the vibrational spectra of the title compound.     

Synthesis of Schiff and Mannich bases of isatin derivatives with 4-amino-4,5-dihydro-1H-1,2,4-triazole-5-ones

Ethyl imidate hydrochlorides 1 were prepared by passing HCl gas through solutions of substituted benzyl cyanides and absolute ethanol. Ethoxycarbonylhydrazones 2 were synthesized from the reaction of compounds 1 with ethyl carbazate. Treatment of 2 with hydrazine hydrate leads to the formation of substituted 4-amino-4,5-dihydro-1H-1,2,4-triazole-5-ones 3. Isatin and 5-chloroisatin were added to 3 to form Schiff bases 4 and N-Mannich bases 5 of these compounds were synthesized by reacting with formaldehyde and piperidine. Their chemical structures were confirmed by means of IR, (1)H- and (13)C-NMR data and by elemental analysis.