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1.
Environ Sci Technol ; 58(4): 2144-2152, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38234209

RESUMO

The electrocatalytic nitrate reduction reaction (NO3RR) has recently emerged as a promising technique for readily converting aqueous nitrate (NO3-) pollutants into valuable ammonia (NH3). It is vital to thoroughly understand the mechanism of the reaction to rationally design and construct advanced electrocatalytic systems that can effectively and selectively drive the NO3RR. There are several natural enzymes that incorporate molybdenum (Mo) and that can activate NO3-. Based on this, a cadmium (Cd) single-atom anchored Mo2TiC2Tx electrocatalyst (referred to as CdSA-Mo2TiC2Tx) through the NO3RR to generate NH3 was rationally designed and demonstrated. In an H-type electrolysis cell and at a current density of 42.5 mA cm-2, the electrocatalyst had a Faradaic efficiency of >95% and an impressive NH3 yield rate of 48.5 mg h-1 cm-2. Moreover, the conversion of NO3- to NH3 on the CdSA-Mo2TiC2Tx surface was further revealed by operando attenuated total reflection Fourier-transform infrared spectroscopy and an electrochemical differential mass spectrometer. The electrocatalyst significantly outperformed Mo2TiC2Tx as well as reported state-of-the-art catalysts. Density functional theory calculations revealed that CdSA-Mo2TiC2Tx decreased the ability of the d-p orbital to hybridize with NH3* intermediates, thereby decreasing the activation energy of the potential-determining step. This work not only highlights the application prospects of heavy metal single-atom catalysts in the NO3RR but also provides examples of bio-inspired electrocatalysts for the synthesis of NH3.


Assuntos
Amônia , Nitratos , Cádmio , Molibdênio , Eletrodos
2.
Molecules ; 29(8)2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38675616

RESUMO

This paper explores and revisits in detail the formation and characterization of sugar-based aminonitriles, whose ultimate origin can be traced to the interaction of biomolecules with cyanide. Although the synthesis and spectroscopic data of 2-amino-aldononitriles were reported long ago, there are both contradictory and confusing results among the published data. We have now addressed this concern through an exhaustive structural elucidation of acylated 2-amino- and 2-alkyl(aryl)amino-2-deoxyaldonitriles using mass spectrometry and FT-IR, FT-Raman, and NMR spectroscopies. Several structures could be unambiguously determined through single-crystal X-ray diffraction, which allowed us to correct other misassignments. Moreover, this study unveils how steric and electronic effects influence the acylation outcome of the amino, (alkyl, aryl)amino, or acetamido group at C-2. The chirality at the latter, which was assigned tentatively through optical rotation correlation, and hence the preferential threo stereochemistry generated during the cyanohydrin synthesis of 2-amino-2-deoxy aldononitriles have now been established with confidence.

3.
Molecules ; 29(17)2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39274978

RESUMO

A curious and noticeable structural feature in Schiff bases from 2-aminoaldoses is the fact that imino tautomers arranged equatorially in the most stable ring conformation exhibit a counterintuitive reverse anomeric effect (RAE) in the mutarotational equilibrium, i.e., the most stable and abundant anomer is the equatorial one (ß). As shown by our very recent research, this effect arises from the total or partial inhibition of the exo-anomeric effect due to the presence of an intramolecular hydrogen bond between the anomeric hydroxyl and the iminic nitrogen in the axial anomer (α). When the Schiff base adopts either an enamine structure or the imino group is protonated, the exo-anomeric effect is restored, and the axial α-anomer becomes the most stable species. Although the intramolecular H-bonding should appropriately be interpreted as a genuine stereoelectronic effect, the magnitude of the RAE could be affected by other structural parameters. Herein and through a comprehensive analysis of benzylidene, cinnamylidene, naphthalene, phenanthrene, and anthracene aldehydes, we show the robustness of the RAE effect, which is similar in extent to simple aldehydes screened so far, irrespective of the size and/or hydrophobicity of the substituent at the nitrogen atom.

4.
Microb Cell Fact ; 22(1): 192, 2023 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-37735405

RESUMO

Microbial degradation of synthetic dyes is considered a promising green dye detoxification, cost-effective and eco-friendly approach. A detailed study on the decolorization and degradation of malachite green dye (MG) using a newly isolated Pseudomonas plecoglossicide MG2 was carried out. Optimization of MG biodegradation by the tested organism was investigated by using a UV-Vis spectrophotometer and the resultant degraded products were analyzed by liquid chromatography-mass spectrometry and FTIR. Also, the cytotoxicity of MG degraded products was studied on a human normal retina cell line. The optimum conditions for the significant maximum decolorization of MG dye (90-93%) by the tested organism were pH 6-7, inoculum size 4-6%, and incubation temperature 30-35 °C, under static and aerobic conditions. The performance of Pseudomonas plecoglossicide MG2 grown culture in the bioreactors using simulated wastewater was assessed. MG degradation (99% at 100 and 150 mg MG/l at an optimal pH) and COD removal (95.95%) by using Pseudomonas plecoglossicide MG2 culture were the best in the tested culture bioreactor in comparison with that in activated sludge or tested culture-activated sludge bioreactors.The FTIR spectrum of the biodegraded MG displayed significant spectral changes, especially in the fingerprint region 1500-500 as well as disappearance of some peaks and appearance of new peaks. Twelve degradation intermediates were identified by LC-MS. They were desmalachite green, didesmalachite green, tetradesmalachite green, 4-(diphenylmethyl)aniline, malachite green carbinol, bis[4-(dimethylamino)phenyl]methanone, [4-(dimethylamino)phenyl][4-(methyl-amino)phenyl]methanone, bis[4-(methylamino)phenyl]methanone, (4-amino- phenyl)[4-(methylamino)phenyl]methanone, bis(4-amino phenyl)methanone, (4-amino phenyl)methanone, and 4-(dimathylamino)benzaldehyde. According to LC-MS and FTIR data, two pathways for MG degradation by using Pseudomonas plecoglossicide MG2 were proposed. MG showed cytotoxicity to human normal retina cell line with LC50 of 28.9 µg/ml and LC90 at 79.7 µg/ml. On the other hand, MG bio-degraded products showed no toxicity to the tested cell line. Finally, this study proved that Pseudomonas plecoglossicide MG2 could be used as an efficient, renewable, eco-friendly, sustainable and cost-effective biotechnology tool for the treatment of dye wastewater effluent.


Assuntos
Esgotos , Águas Residuárias , Humanos , Corantes , Reatores Biológicos , Pseudomonas
5.
Chem Biodivers ; 20(7): e202300450, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37300428

RESUMO

Two novel copper (II) complexes [Cu(TFP)(Gly)Cl] ⋅ 2H2 O complex (1) and [Cu(TFP)(His)Cl] ⋅ 2H2 O complex (2) are synthesized, where TFP stands for trifluropromazine, Gly. represents glycine, and His. is histidine. Chemical composition, IR, mass spectra, and magnetic susceptibility tests are performed. Complex binding with macromolecules was investigated using UV-vis, viscosity, gel electrophoresis, and fluorescence quenching. Fluorescence spectroscopy revealed that each complex could replace ethidium bromide (EB). These complexes exhibit grooved, non-covalent, and electrostatic interactions with CT-DNA. Spectroscopy analysis of the BSA interaction showed that complexes bind to protein (Kb values for (1) is 5.89×103  M-1 and for (2) is 9.08×103  M-1 ) more strongly than CT-DNA (Kb values for (1) is 5.43×103  M-1 and for (2) is 7.17×103  M-1 ). Molecular docking analysis and spectral absorption measurements showed high agreement. Antimicrobial, antioxidant, and anti-inflammatory properties were tested in vitro. The druggability of complex (2) should be tested in vivo as it is more biologically active.


Assuntos
Complexos de Coordenação , Histidina , Histidina/química , Cobre/química , Triflupromazina , Complexos de Coordenação/química , Simulação de Acoplamento Molecular , Glicina/farmacologia , Glicina/química , DNA/química
6.
Molecules ; 28(7)2023 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-37049990

RESUMO

The C3H3NO family of isomers is relevant in astrochemistry, even though its members are still elusive in the interstellar medium. To identify the best candidate for astronomical detection within this family, we developed a new computational protocol based on the minimum-energy principle. This approach aims to identify the most stable isomer of the family and consists of three steps. The first step is an extensive investigation that characterizes the vast number of compounds having the C3H3NO chemical formula, employing density functional theory for this purpose. The second step is an energy refinement, which is used to select isomers and relies on coupled cluster theory. The last step is a structural improvement with a final energy refinement that provides improved energies and a large set of accurate spectroscopic parameters for all isomers lying within 30 kJ mol-1 above the most stable one. According to this protocol, vinylisocyanate is the most stable isomer, followed by oxazole, which is about 5 kJ mol-1 higher in energy. The other stable species are pyruvonitrile, cyanoacetaldehyde, and cyanovinylalcohol. For all of these species, new computed rotational and vibrational spectroscopic data are reported, which complement those already available in the literature or fill current gaps.

7.
Molecules ; 28(18)2023 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-37764377

RESUMO

Na2MoO4 and Na2WO4 are isostructural semiconductors, belonging to the spinel class. They have interesting properties and find applications in numerous sectors. These properties can be tuned by controlling the composition of their solid solutions. Here, different methods to obtain these compounds are presented, both wet and solid-state synthesis. The obtained results show a possible dependence of the material properties on the chosen synthesis method. The pure compounds and their mixtures were characterized by Raman spectroscopy, scanning electron microscopy, and X-ray diffraction.

8.
Molecules ; 28(12)2023 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-37375153

RESUMO

The non-classical bacterial peroxidase from Escherichia coli, YhjA, is proposed to deal with peroxidative stress in the periplasm when the bacterium is exposed to anoxic environments, defending it from hydrogen peroxide and allowing it to thrive under those conditions. This enzyme has a predicted transmembrane helix and is proposed to receive electrons from the quinol pool in an electron transfer pathway involving two hemes (NT and E) to accomplish the reduction of hydrogen peroxide in the periplasm at the third heme (P). Compared with classical bacterial peroxidases, these enzymes have an additional N-terminal domain binding the NT heme. In the absence of a structure of this protein, several residues (M82, M125 and H134) were mutated to identify the axial ligand of the NT heme. Spectroscopic data demonstrate differences only between the YhjA and YhjA M125A variant. In the YhjA M125A variant, the NT heme is high-spin with a lower reduction potential than in the wild-type. Thermostability was studied by circular dichroism, demonstrating that YhjA M125A is thermodynamically more unstable than YhjA, with a lower TM (43 °C vs. 50 °C). These data also corroborate the structural model of this enzyme. The axial ligand of the NT heme was validated to be M125, and mutation of this residue was proven to affect the spectroscopic, kinetic, and thermodynamic properties of YhjA.


Assuntos
Escherichia coli , Peroxidase , Peroxidase/metabolismo , Escherichia coli/genética , Escherichia coli/metabolismo , Peróxido de Hidrogênio/metabolismo , Heme/química , Ligantes , Peroxidases/química , Oxirredução
9.
Int J Mol Sci ; 23(23)2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-36499417

RESUMO

Objects touched by patients and healthcare workers in hospitals may harbor pathogens, including multi-drug resistant (MDR) staphylococci, enterococci (VRE), Escherichia coli, Acinetobacter, and Pseudomonas species. Medical devices contaminated by these pathogens may also act as a source of severe and difficult-to-treat human infections, thus becoming a critical public health concern requiring urgent resolutions. To this end, we recently reported the bactericidal effects of a cationic copolymer (CP1). Here, aiming at developing a bactericidal formulation possibly to be used either for surfaces disinfection or to treat skin infections, CP1 was formulated as a hydrogel (CP1_1.1-Hgel). Importantly, even if not cross-linked, CP1 formed the gel upon simple dispersion in water, without requiring gelling agents or other additives which could be skin-incompatible or interfere with CP1 bactericidal effects in possible future topical applications. CP1_1.1-Hgel was characterized by attenuated-total-reflectance Fourier transform infrared (ATR-FTIR) and UV-Vis spectroscopy, as well as optic and scanning electron microscopy (OM and SEM) to investigate its chemical structure and morphology. Its stability was assessed by monitoring its inversion properties over time at room temperature, while its mechanical characteristics were assessed by rheological experiments. Dose-dependent cytotoxicity studies performed on human fibroblasts for 24 h with gel samples obtained by diluting CP_1.1-Hgel at properly selected concentrations established that the 3D network formation did not significantly affect the cytotoxic profile of CP1. Also, microbiologic investigations carried out on two-fold serial dilutions of CP1-gel confirmed the minimum inhibitory concentrations (MICs) previously reported for the not formulated CP1.Selectivity indices values up to 12 were estimated by the values of LD50 and MICs determined here on gel samples.


Assuntos
Antibacterianos , Hidrogéis , Humanos , Hidrogéis/farmacologia , Hidrogéis/química , Antibacterianos/farmacologia , Microscopia Eletrônica de Varredura , Fibroblastos , Testes de Sensibilidade Microbiana , Polímeros/farmacologia
10.
Environ Monit Assess ; 194(2): 121, 2022 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-35075528

RESUMO

Municipal wastewater sludge (also known as biosolids) is produced in large quantities from wastewater treatment plants (WWTPs). Traditionally, analyses of biosolids revealed the presence of inorganic (including metals) and organic contaminants which pose health concerns to man and the environment. This study investigated physical-chemical parameters and comparative element concentrations (Ag, Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Ni, P, Pb, S, Se, Zn, V, Na, S, and P) in biosolids and composted wastewater sludge (CWS) from Nacogdoches Wastewater Treatment Plant (NWWTP), Lufkin Wastewater Treatment Plant (LWWTP), and Angelina-Neches Compost Facility (NCF) in East Texas (USA). In addition, concentrations in perlite, a hydroponic material, were determined via Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy/energy dispersive X-ray diffraction (SEM/EDX), inductively coupled plasma-optical emission spectroscopy (ICP-OES), X-ray diffraction (XRD)), and thermogravimetric (TGA) analysis. Via ICP-OES analysis, metal concentrations in biosolid samples were similar. Macroelement amounts followed the order: NWWS ≈ LWWS > NCS > perlite. Notably, concentrations in biosolids, CWS, and perlite are below recommended USEPA and WHO maximum ceiling levels. The pH of biosolid samples was determined between 5.33 and 6.74. The weight loses of 6-19% wt at ~ 300-700 ℃ are attributed to volatile compounds and inorganic metal oxides. From environmental and circular economy perspectives, this study shows biosolids to be safe, and potential recycling can be encouraged for use in soil amendments. This finding could find impetus to design of much better WWTPs which improve removal efficiencies and encourage recycling of biosolids.


Assuntos
Metais Pesados , Purificação da Água , Óxido de Alumínio , Biossólidos , Monitoramento Ambiental , Humanos , Metais Pesados/análise , Esgotos/análise , Dióxido de Silício , Espectroscopia de Infravermelho com Transformada de Fourier , Texas , Águas Residuárias
11.
Mar Drugs ; 19(12)2021 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-34940671

RESUMO

Agar is a sulfated polysaccharide extracted from certain marine red algae, and its gel properties depend on the seaweed source and extraction conditions. In the present study, the seaweed Gracilaria gracilis (Gracilariales, Rhodophyta) from Dakhla (Moroccan Atlantic Coast) was investigated for its agar content, structure, and gel properties. The agar yields of G. gracilis were 20.5% and 15.6% from alkaline pretreatment and native extraction, respectively. Agar with alkaline pretreatment showed a better gelling property supported by higher gel strength (377 g·cm-2), gelling (35.4 °C), and melting (82.1 °C) temperatures with a notable increase in 3,6-anhydro-galactose (11.85%) and decrease in sulphate (0.32%) contents. The sulfate falling subsequent to alkaline pretreatment was verified through FT-IR spectroscopy. The 13C NMR spectroscopy showed that alkaline-pretreated agar has a typical unsubstituted agar pattern. However, native agar had a partially methylated agarose structure. Overall, this study suggested the possibility of the exploitation of G. gracilis to produce a fine-quality agar. Yet, further investigation may need to determine the seasonal variability of this biopolymer according to the life cycle of G. gracilis.


Assuntos
Ágar/química , Gracilaria , Animais , Organismos Aquáticos , Oceano Atlântico , Marrocos
12.
Molecules ; 26(9)2021 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-33946938

RESUMO

This review focuses on the ability of some natural antioxidant molecules (i.e., hydroxycinnamic acids, coumarin-3-carboxylic acid, quercetin, luteolin and curcumin) to form Al(III)- and Fe(III)-complexes with the aim of evaluating the coordination properties from a combined experimental and theoretical point of view. Despite the contributions of previous studies on the chemical properties and biological activity of these metal complexes involving such natural antioxidants, further detailed relationships between the structure and properties are still required. In this context, the investigation on the coordination properties of Al(III) and Fe(III) toward these natural antioxidant molecules might deserve high interest to design water soluble molecule-based metal carriers that can improve the metal's intake and/or its removal in living organisms.


Assuntos
Alumínio/química , Antioxidantes/química , Produtos Biológicos/química , Complexos de Coordenação/química , Compostos Férricos/química , Modelos Moleculares , Modelos Teóricos , Algoritmos , Antioxidantes/farmacologia , Sítios de Ligação , Produtos Biológicos/farmacologia , Quelantes/química , Quelantes/farmacologia , Fenômenos Químicos , Metais/química , Análise Espectral
13.
Molecules ; 26(17)2021 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-34500655

RESUMO

Understanding the structural determinants for metal ion coordination in metalloproteins is a fundamental issue for designing metal binding sites with predetermined geometry and activity. In order to achieve this, we report in this paper the design, synthesis and metal binding properties of METP3, a homodimer made up of a small peptide, which self assembles in the presence of tetrahedrally coordinating metal ions. METP3 was obtained through a redesign approach, starting from the previously developed METP molecule. The undecapeptide sequence of METP, which dimerizes to house a Cys4 tetrahedral binding site, was redesigned in order to accommodate a Cys2His2 site. The binding properties of METP3 were determined toward different metal ions. Successful assembly of METP3 with Co(II), Zn(II) and Cd(II), in the expected 2:1 stoichiometry and tetrahedral geometry was proven by UV-visible spectroscopy. CD measurements on both the free and metal-bound forms revealed that the metal coordination drives the peptide chain to fold into a turned conformation. Finally, NMR data of the Zn(II)-METP3 complex, together with a retrostructural analysis of the Cys-X-X-His motif in metalloproteins, allowed us to define the model structure. All the results establish the suitability of the short METP sequence for accommodating tetrahedral metal binding sites, regardless of the first coordination ligands.


Assuntos
Metaloproteínas/química , Metaloproteínas/metabolismo , Sítios de Ligação , Biologia Computacional , Espectroscopia de Ressonância Magnética
14.
Angew Chem Int Ed Engl ; 60(42): 22672-22677, 2021 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-34423516

RESUMO

Quasi-solid polymer electrolytes (QPE) composed of Li salts, polymer matrix, and solvent, are beneficial for improving the security and energy density of batteries. However, the ionic conduction mechanism, existential form of solvent molecules, and interactions between different components of QPE remain unclear. Here we develop a multispectral characterization strategy combined with first-principles calculations to unravel aforesaid mysteries. The results indicate that the existential state of solvent in QPE is quite different from that in liquid electrolyte. The Li cations in gel polymer electrolyte are fully solvated by partial solvent molecules to form a local high concentration of Li+ , while the other solvent molecules are fastened by polymer matrix in QPE. As a result, the solvation structure and conduction mechanism of Li+ are similar to those in high-concentrated liquid electrolyte. This work provides a new insight into the ionic conduction mechanism of QPE and will promote its application for safe and high-energy batteries.

15.
Protein Expr Purif ; 172: 105633, 2020 08.
Artigo em Inglês | MEDLINE | ID: mdl-32259580

RESUMO

A full-length cDNA sequence of plant type CRY (designated Hae-P-CRY) was cloned from the green alga Haematococcus pluvialis. The cDNA sequence was 3608 base pairs (bp) in length, which contained a 2988-bp open reading frame encoding 995 amino acids with molecular mass of 107.7 kDa and isoelectric point of 6.19. Multiple alignment analysis revealed that the deduced amino acid sequence of Hae-P-CRY shared high identity of 47-66% with corresponding plant type CRYs from other eukaryotes. The catalytic motifs of plant type CRYs were detected in the amino acid sequence of Hae-P-CRY including the typical PHR and CTE domains. Phylogenetic analysis showed that the Hae-P-CRY was grouped together with other plant type CRYs from green algae and higher plants, which distinguished from other distinct groups. The transcriptional level of Hae-P-CRY was strongly decreased after 0-4 h under HL stress. In addition, the Hae-P-CRY gene was heterologously expressed in Escherichia coli BL21 (DE3) and successfully purified. The typical spectroscopic characteristics of plant type CRYs were present in Hae-P-CRY indicated that it may be an active enzyme, which provided valuable clue for further functional investigation in the green alga H. pluvialis. These results lay the foundation for further function and interaction protein identification involved in CRYs mediated signal pathway under HL stress in H. pluvialis.


Assuntos
Clorófitas/genética , Clonagem Molecular , Criptocromos , Expressão Gênica , Criptocromos/biossíntese , Criptocromos/química , Criptocromos/genética , Criptocromos/isolamento & purificação , Escherichia coli/genética , Escherichia coli/metabolismo , Proteínas Recombinantes/biossíntese , Proteínas Recombinantes/química , Proteínas Recombinantes/genética , Proteínas Recombinantes/isolamento & purificação
16.
Mikrochim Acta ; 187(3): 186, 2020 02 22.
Artigo em Inglês | MEDLINE | ID: mdl-32088793

RESUMO

A colorimetric nanoprobe was developed for the quantification of tobramycin in exhaled breath condensate (EBC). The nanoprobe consists of silver nanoparticles (Ag NPs) modified with sodium dodecyl sulfate (SDS), which is applied in the presence of sodium metaborate. Characterization of the synthesized SDS-capped Ag NPs by transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDX) showed that the nanoparticles were well synthesized with nearly uniform size and an average diameter of < 30 nm. Interaction of sodium metaborate with the SDS-capped Ag NPs and tobramycin results in aggregation of the nanoparticles and consequently decreases the absorbance intensity, leading to the production of a new absorbance peak and a color change from yellow to purple. The absorbance intensity was recorded at λmax = 400 nm and 522 nm and λ522/λ400 was used as the analytical signal. The experimental parameters were investigated and optimized using a multivariate optimization method (central composite design). The current nanoprobe gives a linear response for tobramycin from 1.0 to 50.0 ng mL-1 with a detection limit of 0.5 ng mL-1. The intra- and inter-day relative standard deviations for five replicated analyses of 10.0 ng mL-1 tobramycin are 2.8% and 4.2%, respectively. Graphical abstractSchematic representation of SDS-capped silver nanoparticles's response to tobramycin in the presence of sodium metaborate.


Assuntos
Testes Respiratórios/métodos , Colorimetria/métodos , Expiração/fisiologia , Nanopartículas Metálicas/química , Tobramicina/química , Humanos
17.
Int J Mol Sci ; 21(18)2020 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-32911811

RESUMO

Archon2 is a fluorescent voltage sensor derived from Archaerhodopsin 3 (Arch) of Halorubrum sodomense using robotic multidimensional directed evolution approach. Here we report absorption and emission spectroscopic studies of Archon2 in Tris buffer at pH 8. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and fluorescence excitation spectra were determined. The thermal stability of Archon2 was studied by long-time attenuation coefficient measurements at room temperature (21 ± 1 °C) and at refrigerator temperature (3 ± 1 °C). The apparent melting temperature was determined by stepwise sample heating up and cooling down (obtained apparent melting temperature: 63 ± 3 °C). In the protein melting process protonated retinal Schiff base (PRSB) with absorption maximum at 586 nm converted to de-protonated retinal Schiff base (RSB) with absorption maximum at 380 nm. Storage of Archon2 at room temperature and refrigerator temperature caused absorption coefficient decrease because of partial protein clustering to aggregates at condensation nuclei and sedimentation. At room temperature an onset of light scattering was observed after two days because of the beginning of protein unfolding. During the period of observation (18 days at 21 °C, 22 days at 3 °C) no change of retinal isomer composition was observed indicating a high potential energy barrier of S0 ground-state isomerization.


Assuntos
Proteínas Arqueais/química , Corantes Fluorescentes/química , Proteínas Arqueais/metabolismo , Fluorescência , Halorubrum/química , Halorubrum/metabolismo , Isomerismo , Fenômenos Físicos , Bases de Schiff/química , Espectrometria de Fluorescência/métodos , Espectrometria por Raios X/métodos , Temperatura , Espectroscopia por Absorção de Raios X/métodos
18.
Molecules ; 25(18)2020 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-32971782

RESUMO

Alginates are widely used as gelling agents in textile print pastes, medical industries, impression material in dentistry, and anticoagulant material in toothpaste. In the present study, the content and spectroscopic characterization (1H NMR and FT-IR) of the sodium alginates were investigated in the eight brown seaweeds Sargassum muticum, Fucus vesiculosus f. volubilis, Carpodesmia tamariscifolia, Bifurcaria bifurcata, Laminaria ochroleuca, Cystoseira humilis, Saccorhiza polyschides, and Fucus guiryi harvested from the NW Atlantic coast of Morocco. The results proved that the most studied algae depicted alginate yields higher than 18% dry weight. The FT-IR analysis showed that the spectra of the extracted alginates exhibited significant similarities to the commercial alginate from Sigma-Aldrich. The 1H NMR spectroscopy indicated that the extracted alginates have a high content of ß-d-mannuronic (M) than α-l-guluronic acid (G) with M/G ratio values ranging from 1.04 to 4.41. The homopolymeric fractions FMM are remarkably high compared to the FGG and heteropolymeric fractions (FGM = FMG) especially for F. guiryi, C humilis, C. tamariscifolia, L. ochroleuca, and S. polyschides. Nevertheless, the heteropolymeric fractions (FGM/FMG) are quite abundant in the alginates of S. muticum, F. vesiculosus f. volubilis, and B. bifurcata accounting for more than 52% of the polymer diads. Based on these results, the investigated algal species (except Fucus guiryi and Bifurcaria bifurcata) could be regarded as potential sources of alginates for industrial uses.


Assuntos
Alginatos/química , Alginatos/isolamento & purificação , Espectroscopia de Ressonância Magnética , Alga Marinha/química , Espectroscopia de Infravermelho com Transformada de Fourier , Oceano Atlântico , Marrocos
19.
Artigo em Inglês | MEDLINE | ID: mdl-32614255

RESUMO

Recently, Silver nanoparticles (AgNPs) have become widely applied nanomaterial in human contacting areas such as cosmetics, food and medicine due to their antibacterial property. On the other hand, surfactants are essential ingredient of several industrial and consumer formulations. Based on these important applications, the current research was aimed to carry out the synthesis and characterization of Tween 80 capped silver nanoparticles (T80-AgNPs) using gamma radiation reduction method. Characterization of T80-AgNPs was occurred by using UV-Vis, XRD, FTIR and TEM techniques. UV-Visible spectra showed surface plasmon resonance (SPR) peak in the range of 420 nm signifying the synthesis of colloidal AgNPs. TEM confirmed the formation of spherical and uniformly distributed AgNPs with average size of 18 nm. XRD analysis illustrated the formation of pure crystalline AgNPs. The FTIR analysis provides evidence for the stabilization of AgNPs by Tween 80. The synthesized T80-AgNPs were evaluated for antibacterial activity against both Escherichia coli (E. coli) as gram negative (G -ve) bacteria and Staphylococcus aureus (S. aureus) as gram positive (G + ve) bacteria and anti-biofilm activity to P. aeruginosa. The results show that T80-AgNPs exhibits excellent antibacterial and antibiofilm activities.


Assuntos
Antibacterianos/química , Antibacterianos/farmacologia , Raios gama , Nanopartículas Metálicas/química , Polissorbatos/química , Prata/química , Biofilmes/efeitos dos fármacos , Escherichia coli/efeitos dos fármacos , Humanos , Testes de Sensibilidade Microbiana , Pseudomonas aeruginosa/efeitos dos fármacos , Prata/farmacologia , Nitrato de Prata/química , Staphylococcus aureus/efeitos dos fármacos
20.
J Biol Inorg Chem ; 24(7): 1009-1022, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31385067

RESUMO

Three new dinuclear Pd(II) complexes with general formula [{Pd(en)Cl}2(µ-L)](NO3)2 [L is bridging ligand quinoxaline (Pd1), quinazoline (Pd2) and phthalazine (Pd3)] were synthesized and characterized by elemental microanalyses, UV-Vis, IR and NMR (1H and 13C) spectroscopy. The interaction of dinuclear Pd1-Pd3 complexes with calf thymus DNA (CT-DNA) has been monitored by viscosity measurements, UV-Vis and fluorescence emission spectroscopy in aqueous phosphate buffer solution (PBS) at pH 7.40 and 37 °C. In addition, these experimental conditions have been applied to investigate the binding affinities of Pd1-Pd3 complexes to the bovine serum albumin (BSA) by fluorescence emission spectroscopy. In vitro antiproliferative and apoptotic activities of the dinuclear Pd(II) complexes have been tested on colorectal and lung cancer cell lines. All tested Pd(II) complexes had lower cytotoxic effect than cisplatin against colorectal cancer cells, but also had similar or even higher cytotoxicity than cisplatin against lung cancer cells. All complexes induced apoptosis of colorectal and lung cancer cells, while the highest antiproliferative effect exerted Pd2 complex.


Assuntos
DNA/metabolismo , Compostos Heterocíclicos/química , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Paládio/química , Soroalbumina Bovina/metabolismo , Antineoplásicos/química , Antineoplásicos/metabolismo , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Humanos , Ligantes , Modelos Moleculares , Conformação Molecular , Compostos Organometálicos/metabolismo
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