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1.
Macromol Rapid Commun ; 43(19): e2200317, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35798327

RESUMEN

Here, redox active aliphatic luminescent polymers (ALPs) are synthesized via polymerization of N,N-dimethyl-2-propenamide (DMPA) and 2-methyl-2-propenoic acid (MPA). The structures and properties of the optimum ALP3, ALP3-aggregate and Cu(I)-ALP3, ratiometric pH sensing, redox activity, aggregation enhanced emission (AEE), Stokes shift, and oxygen-donor selective coordination-reduction of Cu(II) to Cu(I) are explored via spectroscopic, microscopic, density functional theory-reduced density gradient (DFT-RDG), fluorescence quenching, adsorption isotherm-thermodynamics, and electrochemical methods. The intense blue and green fluorescence of ALP3 emerges at pH = 7.0 and 9.0, respectively, due to alteration of fluorophores from -C(═O)N(CH3 )2 / -C(═O)OH to -C(O- )═N+ (CH3 )2 / -C(═O)O- , inferred from binding energies at 401.32 eV (-C(O- )═N+ (CH3 )2 ) and 533.08 eV (-C(═O)O- ), significant red shifting in absorption and emission spectra, and peak at 2154 cm-1 . The n-π* communications in ALP3-aggregate, hydrogen bondings within 2.34-2.93 Å (intramolecular) in ALP3 and within 1.66-2.89 Å (intermolecular) in ALP3-aggregate, respectively, contribute significantly in fluorescence, confirmed from NMR titration, ratiometric pH sensing, AEE, excitation dependent emission, and Stokes shift and DFT-RDG analyses. For ALP3, Stokes shift, excellent limit of detection, adsorption capacity, and redox potentials are 13561 cm-1 /1.68 eV, 0.137 ppb, 122.93 mg g-1 , and 0.33/-1.04 V at pH 7.0, respectively.


Asunto(s)
Oxígeno , Polímeros , Hidrógeno , Concentración de Iones de Hidrógeno , Oxidación-Reducción , Oxígeno/química , Polímeros/química
2.
Macromol Rapid Commun ; 42(2): e2000522, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33210389

RESUMEN

This work reports the design and synthesis of two nonaromatic biocompatible macromolecular luminogens, i.e., 2-(dimethylamino)ethyl methacrylate-co-2-(dimethylamino)ethyl 3-(N-(methylol)acrylamido)-2-methylpropanoate-co-N-(methylol)acrylamide/DMAEMA-co-DMAENMAMP-co-NMA (P1) and methacrylic acid-co-3-(N-(methylol)acrylamido)-2-methylpropanoic acid-co-N-(methylol)acrylamide/MEA-co-NMAMPA-co-NMA (P2), prepared through in situ anchored acrylamido-ester/DMAENMAMP and acrylamido-acid/NMAMPA third comonomers, respectively, in a facile polymerization of two non-luminous monomers in water medium to circumvent the drawbacks related to aggregation-caused quenching of aromatic luminogens. The structures of P1/P2, in situ anchored comonomers, fluorophores, N-branching associated n-π* interactions, and hydrogen bonding assisted aggregation-enhanced emissions are comprehended by nuclear magnetic resonance, Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible, thermogravimetric analysis (TGA), dynamic light scattering (DLS), transmission electron microscopy (TEM), fluorescence lifetime, and fluorescence imaging. P1 and P2 are appropriate for sensitive detections/exclusions of Fe(III)/Cu(II) and cell-imaging. The intrinsic fluorescence, on-off sensing, selective coordinations of Fe(III) and Cu(II) with fluorophores, emission quenching mechanisms, and removals of Fe(III) and Cu(II) are investigated by DFT/NTO analyses of P1/P2 and Fe(III)-P1 and Cu(II)-P2 complexes, XPS, and isotherms and kinetics parameters. The excellent biocompatibilities, comparable limit of detections, i.e., 1.70 × 10-7 and 1.59 × 10-7 [m], and higher adsorption capacities, i.e., 77.25 and 154.13 mg g-1 , at low ppm; 303 K; and pH = 7 compel P1/P2 to be acceptable for multipurpose applications.


Asunto(s)
Compuestos Férricos , Adsorción , Sustancias Macromoleculares , Espectroscopía de Fotoelectrones , Polimerizacion
3.
Langmuir ; 36(22): 6178-6187, 2020 06 09.
Artículo en Inglés | MEDLINE | ID: mdl-32418427

RESUMEN

Biocompatible, nonconventional, multifunctional, purely aliphatic, light-emitting terpolymers, i.e., acrylonitrile-co-3-(N-isopropylacrylamido)propanenitrile-co-N-isopropylacrylamide (AN-co-NIPAMPN-co-NIPA, 1) and acrylonitrile-co-3-(N-hydroxymethylacrylamido)propanenitrile-co-N-hydroxymethylacrylamide (AN-co-NHMAMPN-co-NHMA, 2), were designed and synthesized via N-H-functionalized C-C + N-C-coupled in situ protrusions/grafting of fluorophore monomers, i.e., NIPAMPN and NHMAMPN, by solution polymerization of two highly hydrophobic nonemissive monomers in water. These scalable and reusable 1 and 2 were suitable for high-performance three-in-one applications, such as Fe(III) sensors, imaging of Madin-Darby canine kidney (MDCK) and human lung cancer (A549) cells, and security inks. The structures of 1 and 2, N-C-coupled in situ attachments/grafting of third fluorophore monomers, grafting events, and aggregation-enhanced emissions (AEEs), were analyzed by 1H and 13C NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, thermogravimetric (TG) analysis, high-resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), fluorescence imaging, and fluorescence lifetime. The geometries, electronic structures, and absorption/emission properties of 1 and 2 at optimized compositions were examined by density functional theory (DFT), time-dependent DFT (TDDFT), and natural transition orbital (NTO) analyses. The limits of detection were 3.20 × 10-7 and 1.37 × 10-7 M for 1 and 2, respectively. The excellent biocompatibility of 1 and 2 was confirmed by >95% retention of MDCK and A549 cell morphologies.

4.
ACS Omega ; 5(7): 3333-3345, 2020 Feb 25.
Artículo en Inglés | MEDLINE | ID: mdl-32118148

RESUMEN

The intrinsically fluorescent highly hydrophilic multifunctional aliphatic terpolymer, maleic acid (MA)-co-2-(N-(hydroxymethyl)acrylamido)succinic acid (NHASA)-co-N-(hydroxymethyl)acrylamide (NHMA), that is, 1, was designed and synthesized via C-C/N-C-coupled in situ allocation of a fluorophore monomer, that is, NHASA, composed of amido and carboxylic acid functionalities in the polymerization of two nonemissive MA and NHMA. The scalable and reusable intrinsically fluorescent biocompatible 1 was suitable for sensing and high-performance adsorptive exclusion of Fe(III), along with the imaging of Madin-Darby canine kidney cells. The structure of 1, in situ fluorophore monomer, aggregation-induced enhanced emission, cell-imaging ability, and superadsorption mechanism were studied via microstructural analyses using 1H/13C NMR, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, atomic absorption spectroscopy, ultraviolet-visible spectroscopy, thermogravimetric analysis, dynamic light scattering, high-resolution transmission electron microscopy, solid-state fluorescence, fluorescence lifetime, and fluorescence imaging, along with measuring kinetics, isotherms, and thermodynamic parameters. The location, electronic structures, and geometries of the fluorophore and absorption and emission properties of 1 were investigated using density functional theory and natural transition orbital analyses. The limit of detection and the maximum adsorption capacity were 2.45 × 10-7 M and 542.81 mg g-1, respectively.

5.
ACS Biomater Sci Eng ; 6(3): 1397-1407, 2020 03 09.
Artículo en Inglés | MEDLINE | ID: mdl-33455376

RESUMEN

The nonconventional purely aliphatic intrinsically fluorescent multifunctional terpolymers, such as 2-acrylamido-2-methylpropane sulfonic acid-co-2-(3-acrylamidopropylamido)-2-methylpropane sulfonic acid-co-acrylamide (AMPS-co-APMPS-co-AM, 1), acrylic acid-co-3-acrylamidopropanoic acid-co-acrylamide (AA-co-APA-co-AM, 2), and methacrylic acid-co-3-acrylamido-2-methyl propanoic acid-co-acrylamide (MAA-co-AMPA-co-AM, 3), were synthesized via N-H functionalized multi-C-C/N-C coupled in situ attachments of fluorophore monomers, that is, APMPS, APA, and AMPA, in solution polymerization of two non-fluorescent monomers. These terpolymers were suitable for selective Cr(III) sensors, high-performance exclusions of Cr(III), and fluorescence imaging of human osteosarcoma cancer cells. The structures of 1, 2, and 3, in situ attachments of fluorescent amino acid monomers, locations of fluorophores, aggregation-induced enhanced emissions, and the superadsorption mechanism were understood via microstructural analyses. The geometries, electronic structures, and the low-lying singlet-singlet absorption and emission of 1, 2, and 3 were explored using density functional theory (DFT), time-dependent DFT, and natural transition orbital analyses. The ionic and variable interactions of 1, 2, and 3 with Cr(III) were envisaged via analyses of adsorbed microstructures, fitting of kinetics data to a pseudo-second-order model, and the measurements of activation energies. For 1/2/3, limit of detection values and adsorption capacities were 1.88 × 10-7/3.75 × 10-7/1.25 × 10-7 M and 1316.35/1431.40/1372.18 mg g-1, respectively, at pHi = 7.0, 303 K, and 1000 ppm. The better overall properties made 3 to be more suitable in sensing and cell imaging.


Asunto(s)
Colorantes , Polímeros , Adsorción , Humanos , Sustancias Macromoleculares , Polimerizacion
6.
ACS Appl Bio Mater ; 3(4): 1995-2006, 2020 Apr 20.
Artículo en Inglés | MEDLINE | ID: mdl-35025321

RESUMEN

The nonconventional purely aliphatic scalable and reusable fluorescent guar gum (GRGM)-grafted-acrylic acid-co-3-(N-isopropylacrylamido)propanoic acid (NIPAPA)-co-N-isopropylacrylamide (GRGM-grafted-1, i.e., 2), was synthesized via grafting of the optimum amount of GRGM and N-H functionalized in situ protrusion of acrylamido-acid fluorophore-monomer, i.e., NIPAPA, in multi C-C/N-C/O-C coupled solution polymerization of two non-emissive monomers in water. The intrinsically fluorescent noncytotoxic 2 envisaged the excellent potentials in sensing and removal of Pb(II), security ink, logic function, and imaging of both cancer and normal cells. The emission intensities of 2 elevated in concentrated solutions and solid state because of concentration-enhanced emission and aggregation-induced enhanced emission (AIEE) characteristics of 2. Additionally, the emission efficiency of 2 elevated considerably with increasing GRGM contents and temperatures. The structure of 2, in situ attached fluorophore-monomer, AIEE, cell-imaging ability, and the superadsorption mechanism were studied employing 1H/13C NMR, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, atomic absorption spectroscopy, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, dynamic light scattering, high-resolution transmission electron microscopy, fluorescence imaging, and fluorescence lifetime, along with measuring isotherms, kinetics, and thermodynamic parameters. The location, geometries, and electronic-structures of fluorophore, along with absorption and emission properties, of 2 were explored via density functional theory (DFT), time-dependent DFT, and natural transition orbital analyses. In solution, cyan light-emitting 2 envisaged an average 1.22 ns lifetime in CHCl3. The limit of detection and the maximum adsorption capacity were 2.94 × 10-7 M and 1100.25 mg g-1 at pH 7.0, 303 K, and 1000 ppm, respectively.

7.
ACS Omega ; 4(1): 1763-1780, 2019 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-31459433

RESUMEN

Herein, grafting of starch (STR) and in situ strategic inclusion of 2-(3-(acrylamido)propylamido)-2-methylpropane sulfonic acid (APMPS) via solution polymerization of 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) and acrylamide (AM) have resulted in the synthesis of smart STR-grafted-AMPS-co-APMPS-co-AM (i.e., STR-g-TerPol) interpenetrating terpolymer (TerPol) network hydrogels. For fabricating the optimum hydrogel showing excellent physicochemical properties and recyclability, amounts of ingredients and temperature of synthesis have been optimized using multistage response surface methodology. STR-g-TerPol bearing the maximum swelling ability, along with the retention of network integrity, has been employed for individual and/or simultaneous removal(s) of metal ions (i.e., M(III)), such as Bi(III) and Sb(III), and dyes, such as tris(4-(dimethylamino)phenyl)methylium chloride (i.e., crystal violet) and (7-amino-8-phenoxazin-3-ylidene)-diethylazanium dichlorozinc dichloride (i.e., brilliant cresyl blue). The in situ strategic protrusion of APMPS, grafting of STR into the TerPol matrix, variation of crystallinity, thermal stabilities, surface properties, mechanical properties, swellability, adsorption capacities (ACs), and ligand-selective superadsorption have been inferred via analyses of unadsorbed and/or adsorbed STR-g-TerPol using Fourier transform infrared (FTIR), 1H/13C NMR, UV-vis, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray, dynamic light scattering, and rheological analyses and measuring the lower critical solution temperature, % gel content, pH at point of zero charge (pHPZC), and network parameters, such as ρc and M c. The prevalence of covalent, ionic (I), and variegated interactions between STR-g-TerPol and M(III) has been understood through FTIR analyses, fitting of kinetics data to the pseudosecond-order model, and by the measurement of activation energies of adsorption. The formation of H-aggregate type dimers and hypochromic and hypsochromic shifts has been explained via UV-vis analyses during individual and/or simultaneous removal(s) of cationic dyes. Several isotherm models were fitted to the equilibrium experimental data, of which Langmuir and combined Langmuir-Freundlich models have been best fitted for individual Bi(III)/Sb(III) and simultaneous Sb(III) + Bi(III) removals, respectively. Thermodynamically spontaneous chemisorption processes have shown the maximum ACs of 1047.39/282.39 and 932.08/137.85 mg g-1 for Bi(III) and Sb(III), respectively, at 303 K, adsorbent dose = 0.01 g, and initial concentration of M(III) = 1000/30 ppm. The maximum ACs have been changed to 173.09 and 136.02 mg g-1 for Bi(III) and Sb(III), respectively, for binary Sb(III) + Bi(III) removals at 303 K, adsorbent dose = 0.01 g, and initial concentration of Bi(III)/Sb(III) at 30/5 and 5/30 ppm.

8.
Membranes (Basel) ; 9(5)2019 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-31052381

RESUMEN

For the fulfilment of increasing global demand and associated challenges related to the supply of clean-and-safe water, PV has been considered as one of the most attractive and promising areas in desalinating salty-water of varied salinities. In pervaporative desalination, the sustainability, endurance, and structural features of membrane, along with operating parameters, play the dominant roles and impart paramount impact in governing the overall PV efficiency. Indeed, polymeric- and organic-membranes suffer from several drawbacks, including inferior structural stability and durability, whereas the fabrication of purely inorganic membranes is complicated and costly. Therefore, recent development on the high-performance and cost-friendly PV membrane is mostly concentrated on synthesizing composite- and NCP-membranes possessing the advantages of both organic- and inorganic-membranes. This review reflects the insights into the physicochemical properties and fabrication approaches of different classes of PV membranes, especially composite- and NCP-membranes. The mass transport mechanisms interrelated to the specialized structural features have been discussed. Additionally, the performance potential and application prospects of these membranes in a wide spectrum of desalination and wastewater treatment have been elaborated. Finally, the challenges and future perspectives have been identified in developing and scaling up different high-performance membranes suitable for broader commercial applications.

9.
J Hazard Mater ; 369: 746-762, 2019 05 05.
Artículo en Inglés | MEDLINE | ID: mdl-30836295

RESUMEN

Herein, guar gum (GG)-g-(acrylic acid (AA)-co-3-acrylamido propanoic acid (AMPA)-co-acrylamide (AM))-g-cow buffing dust (CBD)/(GGTPCBD), a smart carbohydrate and protein-based doubly-grafted interpenetrating terpolymer hydrogel showing excellent physicochemical properties and recyclability was synthesized by in situ strategic allocation of AMPA during solution polymerization of AA and AM through systematic optimization of the amounts of components and reaction temperature for superadsorption of Hg(II), Pb(II), methyl violet (MV), methylene blue (MB), p-nitrophenol (PNP), and vitamin-C (vit.C). The in situ strategic protrusion of AMPA, grafting of both GG and CBD into AA-co-AMPA-co-AM, and ligand-selective superadsorption was inferred by advanced microstructural analyses of unadsorbed- and/or adsorbed-GGTPCBD using FTIR, 1H/13C NMR, O1s-/N1s-/C1s-/Pb4f7/2,5/2-/Hg4f7/2,5/2-XPS, UV-vis, TGA, DSC, XRD, DLS, SEM, EDX, % gel content, % -COOH, and pHPZC. The prevalence of covalent, ionic, and variegated interactions was rationalized by FTIR, fitting of kinetics data to the pseudosecond order model, and activation energies of adsorption. The BET and Langmuir isotherms fitted the best to MB and Hg(II)/Pb(II)/MV, respectively. Thermodynamically spontaneous chemisorption processes showed the maximum adsorption capacities (ACs) of 976.64, 859.23, 116.80, and 58.52 mg g-1 for Pb(II), Hg(II), MV, and MB, respectively, at 303 K, adsorbent dose = 0.01 g, and initial concentration of metal ions/dyes = 800/30 ppm.

10.
ACS Omega ; 3(4): 4163-4180, 2018 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-31458651

RESUMEN

Pectin-g-(sodium acrylate-co-3-(N-isopropylacrylamido) sodium propanoate-co-N-isopropylacrylamide) interpenetrating polymer networks (PANIPNs) were synthesized through systematic multistage optimization of equilibrium swelling ratio by response surface methodology for individual and/or synergistic removal(s) of cationic safranine (SF), anionic methyl orange, and M(II/III), such as Hg(II), Cd(II), and Cr(III). The relative effects of copolymer compositions on ligand-selective adsorption, strong/weak H-bonds, thermal stabilities, crystallinity, surface properties, swelling abilities, cross-link densities, network parameters, hydrophilic-hydrophobic characteristics, and adsorption capacities (ACs) were measured through extensive microstructural analyses of adsorbed and/or unadsorbed PANIPN41 and PANIPN21 bearing sodium acrylate and N-isopropylacrylamide (SA/NIPAm) in 4:1 and 2:1 ratios, respectively, using Fourier transform infrared, 1H and 13C NMR, X-ray photoelectron spectroscopy, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy, along with measuring lower critical solution temperature, % gel content (% GC), % -COOH, and pHPZC. Extensive UV-vis measurements were carried out at varying copolymer compositions, initial pH (pHi), and dyes, interpreted considering monomer-dimer and azonium-ammonium equilibrium of dye, dye-dye complexation, ligand-selective PANIPNs-dye adduct formation, π-π stacking interactions, and orientation effect of dyes. Thermodynamically feasible chemisorption processes showed the maximum ACs of 127.61, 96.78, 103.36, and 99.41 mg g-1 for SF, Hg(II), Cd(II), and Cr(III), respectively, under optimum conditions.

11.
ACS Omega ; 3(9): 10692-10708, 2018 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-31459187

RESUMEN

Herein, gum ghatti (GGTI)-g-[sodium acrylate (SA)-co-3-(N-(4-(4-methyl pentanoate))acrylamido)propanoate (NMPAP)-co-4-(acrylamido)-4-methyl pentanoate (AMP)-co-N-isopropylacrylamide (NIPA)] (i.e., GGTI-g-TetraP), a novel interpenetrating tetrapolymer network-based sustainable hydrogel, possessing extraordinary physicochemical properties and excellent recyclability, has been synthesized via grafting of GGTI and in situ strategic protrusion of NMPAP and AMP during the solution polymerization of SA and NIPA, through systematic multistage optimization of ingredients and temperature, for ligand-selective superadsorption of hazardous metal ions (M(II)), such as Sr(II), Hg(II), and Cu(II). The in situ allocation of NMPAP and AMP via N-H and C-H activations, grafting of GGTI into the SA-co-NMPAP-co-AMP-co-NIPA (TetraP) matrix, the effect of comonomer compositions on ligand-selective adsorption, crystallinity, thermal stabilities, surface properties, swellability, adsorption capacities (ACs), mechanical properties, and the superadsorption mechanism have been apprehended via extensive microstructural analyses of unloaded and/or loaded GGTI-g-TetraP1 and GGTI-g-TetraP2 bearing SA/NIPA in 8:1 and 2:1 ratios, respectively, using Fourier transform infrared (FTIR), 1H/13C/DEPT-135 NMR, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, field emission scanning electron microscopy, rheological analysis, and energy-dispersive X-ray spectrometry, along with measuring % gel content, pH at point of zero charge (pHPZC), and % graft ratio. The thermodynamically spontaneous chemisorption has been inferred from FTIR, XPS, fitting of kinetics data to pseudo-second-order model, and activation energies. The chemisorption data have exhibited excellent fitting to the Langmuir isotherm model. For Sr(II), Hg(II), and Cu(II), ACs were 1940.24/1748.36, 1759.50/1848.03, and 1903.64/1781.63 mg g-1, respectively, at 293 K, 0.02 g of GGTI-g-TetraP1/2, and initial concentration of M(II) = 500-1000 ppm.

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