RESUMO
Binding of a novel cationic porphyrin-imidazophenazine conjugate, TMPyP(3+)-ImPzn, to four-stranded poly(G) was investigated in aqueous solutions of neutral pH under near physiological ionic conditions using absorption, polarized fluorescent spectroscopy and fluorescence titration techniques. In absence of the polymer the conjugate folds into stable internal heterodimer with stacking between the porphyrin and phenazine chromophores. Binding of TMPyP(3+)-ImPzn to poly(G) is realized by two competing ways. At low polymer-to-dye ratio (P/D < 6) outside electrostatic binding of the cationic porphyrin moieties of the conjugate to anionic polynucleotide backbone with their self-stacking is predominant. It is accompanied by heterodimer dissociation and distancing of phenazine moieties from the polymer. This binding mode is characterized by strong quenching of the conjugate fluorescence. Increase of P/D results in the disintegration of the porphyrin stacks and redistribution of the bound conjugate molecules along the polymer chain. At P/D > 10 another binding mode becomes dominant, embedding of TMPyP(3+)-ImPzn heterodimers into poly(G) groove as a whole is occurred.
Assuntos
Morfolinas/química , Fenazinas/química , Poli G/química , Polímeros/química , Porfirinas/química , Espectrometria de Fluorescência/métodos , Sítios de Ligação , Dicroísmo Circular , Fluorescência , Morfolinas/metabolismo , Fenazinas/metabolismo , Poli G/metabolismo , Polímeros/metabolismo , Porfirinas/metabolismoRESUMO
A cellulose-g-poly-(acrylamide-co-sulfonic acid) polymeric bio-adsorbent (CASA) was prepared by grafting copolymerization, and used to adsorb Cr(III) from leather wastewater. The SEM, XRD, FTIR, and XPS results showed that CASA contains many spherical particles and functional groups such as NH2, CO, and HSO3. The adsorption experiments revealed that CASA presented excellent adsorption performance for Cr(III) (274.69 mg/g of max adsorption capacity) from high-salinity wastewater, which was much better than other reported adsorbents with different structures. Meanwhile, adsorption equilibrium could be reached within 10 min due to the introduction of abundant sulfonic acid groups on its surface. In addition, the adsorption process followed the Langmuir adsorption isotherm, and the experimental data conformed to the pseudo-second-order kinetics model. Moreover, the main adsorption mechanisms include chelation, electrostatic interactions, and cation exchange, which provide an important theoretical basis for the removal of toxic inorganic pollutants from leather wastewater.
Assuntos
Acrilamida/química , Celulose/química , Cromo/isolamento & purificação , Ácidos Sulfônicos/química , Águas Residuárias/química , Purificação da Água/métodos , Adsorção , Cátions , Cromo/química , Concentração de Íons de Hidrogênio , Cinética , Microscopia Eletroquímica de Varredura/métodos , Poli G/química , Polímeros/química , Salinidade , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Eletricidade Estática , Água/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificaçãoRESUMO
Starch is a natural polysaccharide with reasonable biodegradable properties, which grafted with vinyl monomers through different initiators to be applied in enhanced oil recovery (EOR) techniques. Several authors stated about starch modification through copolymerization and grafting of different monomers, however, these derivatives have some drawbacks related to bacterial biodegradation, ionic and thermal aging under severe reservoir conditions. The present study reported the preparation of grafted acryloylated starch with acrylamide/acrylic acid monomers and vinyltrimethylsilane through initiation copolymerization with the aid of quaternary ammonium-based surfmer. The chemical analysis generated by various spectroscopic analysis comprising IR, NMR, meanwhile particles distribution estimated through DLS. The embedded silica through a polymer matrix photographed by TEM, SEM and EDX elementary analysis, and the thermal effect determined by thermal gravimetric analysis. The rheological analysis estimated relative to shear degradation, ionic strength, and thermal aging at imitated reservoir environment. Flooding runs performed on linear non-consolidated sandstone model at nearly practical field conditions, where the displaced oil by polymer effect was recorded through the volumetric collector. The flooding tests designate that the synthesized starch-g-copolymer is prospering for chemical flooding applications under severe reservoir conditions, and achieve a recovery factor of 46% Sor.
Assuntos
Acrilatos/química , Emulsões/química , Óleos/química , Poli G/química , Polímeros/química , Amido/química , Polimerização , Reologia/métodos , Dióxido de Silício/químicaRESUMO
Thin films of guanosine and uridine ribonucleic acid (RNA) homopolymers (poly rG, poly rU) were grown in high vacuum in several steps on highly oriented pyrolytic graphite (HOPG) using electrospray deposition. Between deposition steps, the sample surface was characterized with X-ray and ultraviolet photoemission spectroscopy (XPS, UPS). The resulting spectra series allowed the determination of the orbital alignment at the HOPG interface, as well as the ionization energies of the homopolymer thin films. Comparison with earlier results on cytidine and adenosine RNA homopolymers (poly rC, poly rA) indicates significant ionization energy and charge injection barrier differences between purines and pyrimidines.
Assuntos
Poli G/química , Poli U/química , RNA/química , Grafite/química , Membranas Artificiais , Poli A/química , Poli C/química , Propriedades de SuperfícieRESUMO
Double-stranded RNA homopolymer poly(rC).poly(rG) has been used as a new pH-sensitive drug carrier. The poly(rC).poly(rG) had proton buffering capacity around pH 6, owing to protonation of cytosine, as determined by acid-base titration. By circular dichroism measurement, the protonation caused conformational change of the RNA. The poly(rC).poly(rG) and doxorubicin (Dox), as an anticancer drug, formed the complexes which released the drugs at endosomal pH. The resulting complex exhibited higher anticancer activity than the Dox alone. These results result suggest that the poly(rC).poly(rG) is a promising biopolymer for a new class of pH-sensitive drug carriers.
Assuntos
Portadores de Fármacos , Poli C/metabolismo , Poli G/metabolismo , Polímeros/química , RNA de Cadeia Dupla/química , RNA de Cadeia Dupla/metabolismo , Antibióticos Antineoplásicos/química , Antibióticos Antineoplásicos/farmacologia , Carcinoma Hepatocelular/tratamento farmacológico , Carcinoma Hepatocelular/metabolismo , Sobrevivência Celular/efeitos dos fármacos , Dicroísmo Circular , Doxorrubicina/química , Doxorrubicina/farmacologia , Humanos , Concentração de Íons de Hidrogênio , Neoplasias Hepáticas/tratamento farmacológico , Neoplasias Hepáticas/metabolismo , Poli C/química , Poli G/química , RNA de Cadeia Dupla/genética , Células Tumorais CultivadasRESUMO
Most theories of the origin of biological organization assume that polymers with lengths in the range of 30-60 monomers are needed to make a genetic system viable. But it has not proved possible to synthesize plausibly prebiotic polymers this long by condensation in aqueous solution, because hydrolysis competes with polymerization. The potential of mineral surfaces to facilitate prebiotic polymerization was pointed out long ago. Here we describe a system that models prebiotic polymerization by the oligomerization of activated monomers--both nucleotides and amino acids. We find that whereas the reactions in solution produce only short oligomers (the longest typically being a 10-mer), the presence of mineral surfaces (montmorillonite for nucleotides, illite and hydroxylapatite for amino acids) induces the formation of oligomers up to 55 monomers long. These are formed by successive 'feedings' with the monomers; polymerization takes place on the mineral surfaces in a manner akin to solid-phase synthesis of biopolymers.
Assuntos
Aminoácidos/química , Biopolímeros , Minerais/química , Oligonucleotídeos/síntese química , Origem da Vida , Serina Endopeptidases , Proteínas de Bactérias/química , Bentonita/química , Carbodi-Imidas , Durapatita/química , Etildimetilaminopropil Carbodi-Imida/química , Evolução Molecular , Ácido Glutâmico/química , Modelos Químicos , Poli A/síntese química , Poli A/química , Poli G/síntese química , Poli G/química , SoluçõesRESUMO
We have previously observed that double-stranded DNA fragments containing a tract of the tandemly repeated sequence poly(CA). poly(TG) can associate in vitro to form stable complexes of low electrophoretic mobility, which are recognized with high specificity by proteins HMG1 and HMG2. The formation of such complexes has since been observed to depend on interactions of DNA with polypropylene surfaces, with the suggestion that the formation of low mobility complexes might be the result of strand dissociation followed by misaligned reassociation of the repetitive sequences. The data presented here show that at high ionic strength the interactions of DNA with polypropylene are sufficiently strong for DNA to remain bound to the polypropylene surface, which suggests that DNA might also be involved in interactions with hydrophobic molecules in vivo. Under such conditions, low-mobility complexes are found only in the material adsorbed to the polypropylene surface, and all DNA fragments are able to form low-mobility structures, whether or not they contain repetitive sequences. Preventing the separation of strands by ligating hairpin loop oligonucleotides at both ends of the fragments does not prevent the formation of low-mobility complexes. Our results suggest two different pathways for the formation of complexes. In the first, dissociation is followed by misaligned reassociation of repetitive sequences, yielding duplexes with single-stranded end regions that associate to form multimeric complexes. In the second, repetitive as well as nonrepetitive DNA molecules bound to polypropylene adopt a conformation with locally unwound regions, which allows interactions between neighboring duplexes adsorbed on the surface, resulting in the formation of low-mobility complexes.
Assuntos
DNA/química , Polipropilenos/química , DNA/ultraestrutura , Escherichia coli/química , Conformação de Ácido Nucleico , Plasmídeos , Poli A/química , Poli C/química , Poli G/química , Poli T/químicaRESUMO
A ribonuclease, with a molecular mass of 30 kDa and a potent inhibitory activity toward HIV-1 reverse transcriptase (IC50=300 nM), was isolated from dried fruiting bodies of the edible wild mushroom Thelephora ganbajun. The ribonuclease exhibited a unique polyhomoribonucleotide specificity, with the highest activity toward poly(U), about 50% and 25% as much activity toward poly(A) and poly(C), respectively, and minimal activity toward poly(G). Unlike other mushroom RNases, the ribonuclease was adsorbed on DEAE-cellulose and Q-Sepharose, and unadsorbed on CM-cellulose. A temperature of 40 degrees C and a pH of 6-7 were required for maximal activity of the enzyme. The enzyme was characterized by an N-terminal sequence without any homology to known proteins.