The aim of the present research work has focused on investigating the effect of cellulose nanofibers (CNFs) and nano clays (montmorillonite (MMT) & organoclay (OMMT)) at 0.75Wt % on the performance of kenaf/epoxy composites. Mechanical (tensile and flexural) and thermal properties of composites in terms of morphology, thermal stability, weight loss, and dynamic mechanical properties were analyzed. The obtained results revealed that the integration of stiff CNFs as filler enhanced the mechanical and thermal properties, storage and loss modulus while a considerable decrease in Tan δ was realized compared to kenaf/epoxy composites. Enhancement in the properties was observed for OMMT and CNFs composites compared to MMT/kenaf/epoxy composites, which is attributed to the uniform filler distribution and interfacial adhesion between CNFs, OMMT, kenaf and epoxy matrix. The obtained results revealed that OMMT and CNFs based kenaf/epoxy composites can be an efficient alternative for construction applications.
TEMPO-oxidize nanocellulose (TONC) suspension has been obtained from total chlorine free (TCF) oil palm empty-fruit-bunches (OPEFB) pulp using 4-acetamido-TEMPO (2,2,6,6-tetramethyl piperidin-1-oxyl) mediated oxidation with sodium hypochlorite and sodium bromide in water at 25 °C and pH 10. TONC suspension with varied content from 0.5 to 6% (w/w) reinforced polyvinyl alcohol (PVA) polymer based nanocomposite films were prepared by the casting method. The structural interaction between the TONC and PVA was characterized by the Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that the 4% (w/w) TONC content reinforced nanocomposite exhibited the highest tensile strength and modulus with an increase of 122% and 291% respectively, compared to PVA while the elongation at break decreased about 42.7%. Thermal stability of PVA based nanocomposite films was improved after incorporation of TONC. Incorporation of TONC in PVA film increases its crystallinity due to strongly linking between the hydroxyl groups of materials however considerable decreases beyond 2 wt% loading are observed. TONC incorporation beyond 2 wt% also reduces the melting temperature peaks and enthalpy of nanocomposite films. FT-IR spectra, NMR and SEM indicate that there is interaction between the TONC and PVA.
Cellulose acetate (CA) and cellulose acetate phthalate (CAP) were used as additives (1 wt%, 3 wt%, and 5 wt%) to prepare polyphenylsulfone (PPSU) hollow fiber membranes. Prepared hollow fiber membranes were characterized by surface morphology using scanning electron microscopy (SEM), surface roughness by atomic force microscopy (AFM), the surface charge of the membrane was analyzed by zeta potential measurement, hydrophilicity by contact angle measurement and the functional groups by fourier transform infrared spectroscopy (FTIR). Fouling resistant nature of the prepared hollow fiber membranes was evaluated by bovine serum albumin (BSA) and molecular weight cutoff was investigated using polyethylene glycol (PEG). By total organic carbon (TOC), the percentage rejection of PEG was found to be 14,489 Da. It was found that the hollow fiber membrane prepared by the addition of 5 wt% of CAP in PPSU confirmed increased arsenic removal from water as compared to hollow fiber membrane prepared by 5 wt% of CA in PPSU. The removal percentages of arsenic with CA-5 and CAP-5 hollow fiber membrane was 34% and 41% with arsenic removal permeability was 44.42 L/m2h bar and 40.11 L/m2h bar respectively. The increased pure water permeability for CA-5 and CAP-5 hollow fiber membrane was 61.47 L/m2h bar and 69.60 L/m2 h bar, respectively.
In the paper by Asiri et al. [Acta Cryst. (2012), E68, o1154], the title and the chemical name of one of the reagents used in the synthesis are corrected.[This corrects the article DOI: 10.1107/S1600536812011579.].
The title compound, 2C14H14N4O·H2O, comprises a neutral mol-ecule containing a central pyrazol-3-one ring flanked by an N-bound phenyl group and a C-bound 5-methyl-1H-pyrazol-3-yl group (at positions adjacent to the carbonyl substituent), its zwitterionic tautomer, whereby the N-bound proton of the central ring is now resident on the pendant ring, and a water mol-ecule of crystallization. Besides systematic variations in geometric parameters, the two independent organic mol-ecules have broadly similar conformations, as seen in the dihedral angle between the five-membered rings [9.72 (9)° for the neutral mol-ecule and 3.32 (9)° for the zwitterionic tautomer] and in the dihedral angles between the central and pendant five-membered rings [28.19 (8) and 20.96 (8)° (neutral mol-ecule); 11.33 (9) and 11.81 (9)°]. In the crystal, pyrazolyl-N-H⋯O(carbon-yl) and pyrazolium-N-H⋯N(pyrazol-yl) hydrogen bonds between the independent organic mol-ecules give rise to non-symmetric nine-membered {⋯HNNH⋯NC3O} and {⋯HNN⋯HNC3O} synthons, which differ in the positions of the N-bound H atoms. These aggregates are connected into a supra-molecular layer in the bc plane by water-O-H⋯N(pyrazolide), water-O-H⋯O(carbon-yl) and pyrazolyl-N-H⋯O(water) hydrogen bonding. The layers are linked into a three-dimensional architecture by methyl-C-H⋯π(phen-yl) inter-actions. The different inter-actions, in particular the weaker contacts, formed by the organic mol-ecules are clearly evident in the calculated Hirshfeld surfaces, and the calculated electrostatic potentials differentiate the tautomers.
Conocarpus fiber is a lignocellulosic biomass rich in cellulose potentially used for producing nanocrystalline cellulose (NCC), a biomaterial extensively employed in various application fields. In the present work, different hydrolysis times of 10, 20 and 30 min were applied to chemically pre-treated Conocarpus fiber to produce CPNC1, CPNC2, and CPNC3 particles. With acid hydrolysis treatment, the yield of NCC product was successfully retained at 17-19%. Individual, rod-like shapes of NCC particles could be clearly observed under microscopy examination. From chemical composition analysis, a relatively pure cellulose compartment was produced for all NCC samples with substantial removal of lignin and hemicellulose. The physicochemical analysis proved that each nanoparticle sample possessed strong cellulose crystalline structure. For thermal analyses, the heat resistance of NCCs was gradually enhanced with the increased hydrolysis times. Therefore, the extracted NCC product from Conocarpus fiber could be a green nano-filler for developing nanocomposite material in the future.
Diarylidenecyclopentanone compound namely, 2,5-bis[4-choloroacetyl-(thiophen-2-ylmethylene)]cyclopentanone (BCTCP) was firstly synthesized using the normal condition of Friedel-Crafts method by reacting 2,5-bis(thiophen-2-ylmethylene)cyclopentanone (BTCP) with chloroacetyl chloride in the presence of aluminum chloride anhydrous. The structure of this compound was confirmed by elemental and spectral analyses including FT-IR,1H-NMR,13C-NMR and mass spectrometry. The electronic absorption and emission properties of BCTCP were studied in different solvents. BCTCP displays a slight solvatochromic effect of the absorption and emission spectrum, indicating a small change in dipole moment of BCTCP upon excitation. BCTCP displayed photodecomposition in chlorinated solvents upon irradiating with 365 nm light. Ground and excited states electronic geometric optimizations were performed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. A DFT natural bond orbital (NBO) analysis complemented the intramolecular charge transfer (ICT). The simulated maximum absorption and emission wavelengths are in line the observed ones in trend, and were proportionally red-shifted with the increase of the solvent polarity. The stability, hardness and electrophilicity of BCTCP in different solvents were correlated with the polarity of the elected solvents.
A very simple and low-cost procedure has been adopted to synthesize efficient copper (Cu), silver (Ag) and copper-silver (Cu-Ag) mixed nanoparticles on the surface of pure cellulose acetate (CA) and cellulose acetate-copper oxide nanocomposite (CA-CuO). All nanoparticles loaded onto CA and CA-CuO presented excellent catalytic ability, but Cu-Ag nanoparticles loaded onto CA-CuO (Cu0-Ag0/CA-CuO) exhibited outstanding catalytic efficiency to convert 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH4. Additionally, the Cu0-Ag0/CA-CuO can be easily recovered by removing the sheet from the reaction media, and can be recycled several times, maintaining high catalytic ability for four cycles.
A new class of conductive metal-organic framework (MOF), polyaniline- aluminum succinate (PANI@Al-SA) nanocomposite was prepared by oxidative polymerization of aniline monomer using potassium persulfate as an oxidant. Several analytical techniques such as FTIR, FE-SEM, EDX, XRD, XPS and TGA-DTA were utilized to characterize the obtained MOFs nanocomposite. DC electrical conductivity of polymer-MOFs was determined by four probe method. A bare glassy carbon electrode (GCE) was modified by nafion/PANI@Al-SA, and examined for Zn (II) ion detection. Modified electrode showed improved efficiency by 91.9%. The modified electrode (PANI@Al-SA/nafion/GCE) exhibited good catalytic property and highly selectivity towards Zn(II) ion. A linear dynamic range of 2.8-228.6 µM was obtained with detection limit of LOD 0.59 µM and excellent sensitivity of 7.14 µA µM-1 cm-2. The designed procedure for Zn (II) ion detection in real sample exhibited good stability in terms of repeatability, reproducibility and not affected by likely interferents. Therefore, the developed procedure is promising for quantification of Zn(II) ion in real samples.
In this work, poly(MBAAm-co-SBMA) zwitterionic polymer nanoparticles were synthesized in one-step via distillation-precipitation polymerization (DPP) and were characterized. [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) as monomer and N, N'-methylene bis(acrylamide) (MBAAm) as cross-linker are used for the synthesis of nanoparticles. As far as our knowledge, this is the first such report on the synthesis of poly(MBAAm-co-SBMA) nanoparticles via DPP. The newly synthesized nanoparticles were further employed for the surface modification of polysulfone (PSF) hollow fiber membranes for dye removal. The modified hollow fiber membrane exhibited the improved permeability (56 L/ m2 h bar) and dye removal (>98% of Reactive Black 5 and >80.7% of Reactive orange 16) with the high permeation of salts. Therefore, the as-prepared membrane can have potential application in textile and industrial wastewater treatment.
Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.
Lignocellulosic biomass waste is a cheap, eco-friendly, and sustainable raw material for a wide array of applications. In the present study, an easy, fast, and economically feasible route has been proposed for the preparation of different zero-valent metal nanoparticles (ZV-MNPs) based on Cu, Co, Ag, and Ni NPs using empty fruit bunch (EFB) biomass residue as support material. The catalytic efficiency of ZV-MNPs/EFB catalyst was investigated against five model pollutants, such as methyl orange (MO), congo red (CR), methylene blue (MB), acridine orange (AO), and 4-nitrophenol (4-NP) using NaBH4 as a source of hydrogen and electron. Comparative study revealed that among as-prepared ZV-MNPs/EFB catalysts, Cu-NPs immobilized onto EFB (Cu/EFB) exhibited maximum catalytic efficiency towards pollutant abasement. Degradation reactions were highly efficient, and were completed within a short time (4 min) in case of MO, CR, and MB, whilst AO and 4-NP were reduced in less than 15 min. Kinetic investigation revealed that the degradation rate of model pollutants accorded with pseudo-first order model. Furthermore, supported catalysts were easily recovered after the completion of experiment by simply pulling the catalyst from reaction system. Recyclability tests performed on Cu/EFB revealed that more than 97% of the reduction was achieved in case of MO dye for four successive cycles of reuse. The as-prepared heterostructure showed multifunctional properties, such as enhanced uptake of contaminants, high catalytic efficiency, and easy recovery, hence, offers great prospects in wastewater purification.
Polymeric rubber and organic semiconductor H2Pc-CNT-composite-based surface- and sandwich-type shockproof deformable infrared radiation (IR) sensors were fabricated using a rubbing-in technique. CNT and CNT-H2Pc (30:70 wt.%) composite layers were deposited on a polymeric rubber substrate as electrodes and active layers, respectively. Under the effect of IR irradiation (0 to 3700 W/m2), the resistance and the impedance of the surface-type sensors decreased up to 1.49 and 1.36 times, respectively. In the same conditions, the resistance and the impedance of the sandwich-type sensors decreased up to 1.46 and 1.35 times, respectively. The temperature coefficients of resistance (TCR) of the surface- and sandwich-type sensors are 1.2 and 1.1, respectively. The novel ratio of the H2Pc-CNT composite ingredients and comparably high value of the TCR make the devices attractive for bolometric applications meant to measure the intensity of infrared radiation. Moreover, given their easy fabrication and low-cost materials, the fabricated devices have great potential for commercialization.
We report the synthesis and biological evaluation of two new series of 2-amino-6-benzyl-4-phenyl-4,6-dihydrobenzo[c]pyrano[2,3-e][1,2]thiazine-3‑carbonitrile 5,5-dioxides and 2-amino-6-methyl-4-phenyl-4,6-dihydrobenzo[c]pyrano[2,3-e][1,2]thiazine-3‑carbonitrile 5,5-dioxides. The synthetic methodology involves a multistep reaction starting with methyl anthranilate which was coupled with methane sulfonyl chloride. The product of the reaction was subjected to N-benzylation and N-methylation reactions followed by ring closure with sodium hydride resulting in the formation of respective 2,1-benzothiazine 2,2-dioxides. These 2,1-benzothiazine precursors were subjected to multicomponent reaction with malononitrile and substituted benzaldehydes for the synthesis of two new series of pyranobenzothiazines (6a-r and 7a-r). The synthesized compounds were screened as selective inhibitors of monoamine oxidase A and monoamine oxidase B. The in vitro results suggested that compound 6d and 7q are the selective inhibitors of monoamine oxidase A, however, the selective and potent inhibitors of monoamine oxidase B included compounds 6h and 7r. Moreover, some dual inhibitors were noticed like 7l having more inhibitory activity towards both the isozymes. Moreover, the binding modes of the selective and potent inhibitors of monoamine oxidase A and B were investigated by molecular docking analysis. The results suggested that the synthetic derivatives may be potential towards the monoamine oxidase isozymes.
Herein, we have investigated the interaction of bovine serum albumin (BSA), the most abundant globular protein, with a conventional cationic surfactant, cetyldimethylethylammonium bromide (CDMEAB), through a conductivity technique in the absence/presence of electrolyte solutions at various temperatures (298.15-323.15 K). The interaction of the protein with drugs/surfactants and other additives plays a crucial role in the body. Hence, the main concern of the study is to extract the impact of BSA on surfactant molecules and vice versa. From the specific conductivity versus concentration of surfactant plots, three different noticeable critical micelle concentration (c*) values were obtained for pure CDMEAB and its mixture with protein/protein + salts. The presence of BSA and electrolytes altered the c* values of CDMEAB revealing interactions among the studied constituents where the salt solutions reduced the c* values and created a convenient environment for favorable micellization. The negative magnitudes achieved for standard free energy changes (ΔG 0 m) suggest spontaneity of micellization while the values of ΔH 0 m and ΔS 0 m signified the existence of some electrostatic and hydrophobic interactions. The values of molar heat capacity (ΔC 0 m) were positive as well as small which was an indication of less structural deformation. Molecular Dynamics (MD) simulation for all atoms revealed that the salt ions promoted non-covalent interaction between BSA and CDMEAB, and such interactions were not observed in the absence of the salt. Protein structure remained nearly same in spite of strong interaction with CDMEAB as evident from the overall RMSD (root-mean-square deviation) values of the alpha carbons and backbone of the protein and RMSF (root-mean-square fluctuation) values of the amino acid residues present in BSA. In this work thermodynamic parameters of transfer (such as ΔG 0 m.tr., ΔH 0 m.tr., and ΔC 0 p.m.tr.) were also evaluated and the results are discussed in detail. Besides, contributions of enthalpy and entropy to free energy changes were also analyzed.
This work reports silver nanoparticles (AgNPs) supported on biopolymer carboxymethyl cellulose beads (Ag-CMC) serves as an efficient catalyst in the reduction process of p-nitrophenol (p-NP) and methyl orange (MO). For Ag-CMC synthesis, first CMC beads were prepared by crosslinking the CMC solution in aluminium nitrate solution and then the CMC beads were introduced into AgNO3 solution to adsorb Ag ions. Field emission scanning electron microscopy (FE-SEM) analysis suggests the uniform distribution of Ag nanoparticles on the CMC beads. The X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis revealed the metallic and fcc planes of AgNPs, respectively, in the Ag-CMC catalyst. The Ag-CMC catalyst exhibits remarkable reduction activity for the p-NP and MO dyes with the highest rate constant (kapp) of a chemical reaction is 0.519 and 0.697 min-1, respectively. Comparative reduction studies of Ag-CMC with CMC, Fe-CMC and Co-CMC disclosed that Ag-CMC containing AgNPs is an important factore in reducing the organic pollutants like p-NP and MO dyes. During the recyclability tests, the Ag-CMC also maintained high reduction activity, which suggests that CMC protects the AgNPs from leaching during dye reduction reactions.
Polypyrrole (PPy) and polypyrrole/cerium oxide nanocomposite (PPy/CeO2) were prepared by the chemical oxidative method in an aqueous medium using anhydrous ferric chloride (FeCl3) as an oxidant. The successful formulation of materials was confirmed by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmittance electron microscopy (TEM). A four-in-line probe device was used for studying DC electrical conductivity and ammonia vapor sensing properties of PPy and PPy/CeO2. The significant improvement in both the conductivity and sensing parameters of PPy/CeO2 compared to pristine PPy reveals some synergistic/electronic interaction between PPy and cerium oxide nanoparticles (CeO2 NPs) working at molecular levels. The initial conductivity (i.e., conductivity at room temperature) was found to be 0.152 Scm-1 and 1.295 Scm-1 for PPy and PPy/CeO2, respectively. Also, PPy/CeO2 showed much better conductivity retention than pristine PPy under both the isothermal and cyclic ageing conditions. Ammonia vapor sensing was carried out at different concentration (0.01, 0.03, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 vol %). The sensing response of PPy/CeO2 varied with varying concentrations. At 0.5 vol % ammonia concentration, the % sensing response of PPy and PPy/CeO2 sensor was found to be 39.1% and 93.4%, respectively. The sensing efficiency of the PPy/CeO2 sensor was also evaluated at 0.4. 0.3, 0.2, 0.1, 0.05, 0.03, and 0.01 vol % ammonia concentration in terms of % sensing response, response/recovery time, reversibility, selectivity as well as stability at room temperature.