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1.
Chemistry ; : e202402687, 2024 Aug 19.
Artículo en Inglés | MEDLINE | ID: mdl-39158121

RESUMEN

Generally, an esterase lipase enzyme can hydrolyze specific substrates called esters in an aqueous solution. Herein, we investigate how a G-quadruplex self-assembly affects the hydrolysis equilibrium in reverse. The biocatalyst, lipase, activates the individual building-blocks through fuel consumption, causing them to undergo a higher degree of self-organization into nanofibers within spheres. We have synthesized five peptide-lipid-conjugated guanine base functionalized molecules to explore how the equilibrium can be shifted through reverse hydrolysis. Among these, NAC5 self-assembled into a G-quadruplex structure which has been confirmed by various spectroscopic techniques. The wide-angle powder XRD, ThT dye binding assay and circular dichroism study is carried out to support the presence of the G-quadruplex structure. The biocatalytic formation of nanofibers enclosed spheres is analyzed using CLSM, FE-SEM and HR-TEM experiments. Additionally, we assess the biocompatibility of the enzyme fueled dissipative self-assembled fibers enclosed spheres, as they have potential applications as a biomaterial in protocells. MTT assay is performed to check the cytotoxicity of G-quadruplex hydrogel, using HEK 293 and McCoy cell lines for viability assessment. Finally, the utility of the novel NAC5 hydrogel as a wound repairing biomaterial is demonstrated by cell migration experiment in a scratch assay.

2.
Inorg Chem ; 63(19): 8567-8579, 2024 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-38668850

RESUMEN

Nowadays, environmentally friendly, low-cost-effective, and sustainable electrocatalysts used widely for hydrogen and oxygen evolution reactions have come into the limelight as a new research topic for scientists. This study highlights the preparation of two unique and symmetrical dinuclear Cu (II) and Mn (III) bifunctional catalysts by a facile simple slow evaporation and diffusion route. [C32H24Cu2F4N4O4] (1) and [C32H24Mn2F4N4O4] (2) both have monoclinic (C2/c (15)) crystal systems, with oxidation states +2 and +3, respectively. Prominent SPR peaks at 372 and 412 nm indicate an M-L charge transfer transition in both complexes. The synthesized electrocatalysts display exceptional catalytic activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Complex 1 exhibits enhanced hydrogen generation in 0.5 M H2SO4 with a small overpotential of 216 mV at -10 mA cm-2 along with a significantly lower Tafel value of 97 mV/dec compared to Complex 2. Moreover, Complex 1 is highly active for the OER in 1 M KOH with a small Tafel slope of 103 mV/dec and a low overpotential of 340 mV to acquire 10 mA cm-2 current density, compared to Complex 2. Complex 1 and Complex 2 remain stable up to 20 h in acidic electrolyte and up to 36 h and 20 h in the basic electrolyte, respectively.

3.
Langmuir ; 39(18): 6466-6475, 2023 05 09.
Artículo en Inglés | MEDLINE | ID: mdl-37106320

RESUMEN

Nowadays, inherent antibacterial hydrogels have gained significant attention due to their utilization against infectious bacteria. Herein, we focus on the development of an injectable, self-healable, dynamic, and G-quadruplex hydrogel with inherent antibacterial activity. The dynamic self-assembled hydrogel is constructed upon multicomponent reactions (MCR) among guanosine, 2-formylphenylboronic acid, and amino acid/peptides in the presence of potassium ions. The role of amino acid/peptides in the formation of the G-quadruplex hydrogel is studied in detail. The G-quadruplex structure is formed via the π-π stacking of G-quartets. The formation of G-quadruplex is investigated by thioflavin T binding assay, CD spectroscopy, and PXRD. The formation of the dynamic imino-boronate bond in the hydrogels is well characterized by temperature-dependent 11B NMR (VT-NMR) and FT-IR spectroscopy. Furthermore, HR-TEM images and rheological experiments reveal the fibrillar networks and viscoelastic property of the hydrogels. The presence of the dynamic imino-boronate ester bonds makes the hydrogel injectable and self-healable in nature. These dynamic G-quadruplex hydrogels show potential antibacterial activity against a series of Gram-positive and Gram-negative bacteria. The hydrogels have been used for the entrapment and sustained release of an anticancer drug doxorubicin over 48 h at different pHs (4.8, 7.4, and 8.5) and temperature without the influence of any external stimuli. Such injectable and self-healable hydrogels could be used in various applications in the field of biomedical science.


Asunto(s)
Antibacterianos , Hidrogeles , Antibacterianos/farmacología , Hidrogeles/química , Espectroscopía Infrarroja por Transformada de Fourier , Bacterias Gramnegativas , Bacterias Grampositivas , Péptidos , Aminoácidos
4.
Langmuir ; 39(27): 9439-9452, 2023 Jul 11.
Artículo en Inglés | MEDLINE | ID: mdl-37377166

RESUMEN

The use of visible light to propel chemical reactions is an exciting area of study that is crucial in the current socioeconomic environment. However, various photocatalysts have been developed to harness visible light, which consume high energy during synthesis. Thus, synthesizing photocatalysts at gel-liquid interfaces in ambient conditions is of scientific importance. Herein, we report an environmentally benign sodium alginate gel being used as a biopolymer template to synthesize copper sulfide (CuS) nanostructures at the gel-liquid interface. The driving force for the synthesis of CuS nanostructures is varied by changing the pH of the reaction medium (i.e., pH 7.4, 10, and 13) to tailor the morphology of CuS nanostructures. The CuS nanoflakes obtained at pH 7.4 transform into nanocubes when the pH is raised to 10, and the nanostructures deform at the pH of 13. Fourier transform infrared spectroscopy (FTIR) confirms all the characteristic stretching of sodium alginate, whereas the CuS nanostructures are crystallized in a hexagonal crystal system, as revealed by the powder X-ray diffraction analysis. The high-resolution X-ray photoelectron spectroscopy (XPS) spectra show the +2 and -2 oxidation states of copper (Cu) and sulfur (S) ions, respectively. The CuS nanoflakes physisorbed a higher concentration of greenhouse CO2 gas. Owing to a lower band gap of CuS nanoflakes synthesized at a pH of 7.4, compared to other CuS nanostructures prepared at pH 10 and 13, CuS photocatalytically degrades 95% of crystal violet and 98% of methylene blue aqueous dye solutions in 60 and 90 min, respectively, under blue light illumination. Additionally, sodium alginate-copper sulfide (SA-CuS) nanostructures synthesized at a pH of 7.4 demonstrate excellent performance in photoredox reactions to convert ferricyanide to ferrocyanide. The current research opens the door to developing new photocatalytic pathways for a wide range of photochemical reactions involving nanoparticle-impregnated alginate composites prepared on gel interfaces.

5.
Langmuir ; 37(37): 10883-10889, 2021 09 21.
Artículo en Inglés | MEDLINE | ID: mdl-34498463

RESUMEN

In living organisms, tyrosinase selectively produces l-DOPA from l-tyrosine. Here, a bicomponent hydrogel is used as a template for tyrosinase-catalyzed selective generation of l-DOPA from tyrosine. An amphiphilic molecule 1,5-diaminonaphthalene (DAN) coassembles with 1,3,5-benzenetricarboxylic acid (BTC) to form a self-supporting hydrogel. After alteration of complementary acids, DAN does not coassemble to form a hydrogel. The coassembly mechanism is investigated using spectroscopic techniques. The transmission electron microscopy and scanning electron microscopy images reveal the morphology details. The l-DOPA is kept from being oxidized when the hydrogel is used as a template. The enzymatically synthesized l-DOPA can also be separated from the mixture by easy tuning of the bicomponent coassembly.


Asunto(s)
Hidrogeles , Monofenol Monooxigenasa , Levodopa , Monofenol Monooxigenasa/metabolismo , Oxidación-Reducción , Tirosina
6.
Langmuir ; 36(6): 1574-1584, 2020 02 18.
Artículo en Inglés | MEDLINE | ID: mdl-31984750

RESUMEN

Injectable, self-healable, and biocompatible dynamic hydrogels prepared from the molecular self-assembly and reversible covalent bond formation of low-molecular-weight hydrogelators are increasing in the field of drug delivery. Herein, we report the formation of G-quadruplex hydrogels via the multicomponent self-assembly and reversible bond formation between guanosine (G) and 1-naphthaleneboronic acid in the presence of the monovalent cation K+. The cation-templated stacking interaction of G4 quartets and the formation of dynamic cyclic boronate esters are responsible for the construction of dynamic G-quadruplex assembly. The in situ-synthesized dynamic cyclic boronate esters are well characterized by 11B nuclear magnetic resonance and Fourier transform infrared spectroscopy methods. The formation and morphology of the G-quadruplex hydrogel are well supported by several spectroscopic and microscopic techniques. The injectability and self-healing ability of the G-quadruplex hydrogel are also investigated. The in vivo cytotoxicity of the G-quadruplex hydrogel is extensively evaluated over different cell lines (HeLa, MCF-7, and HEK293) to observe the biostability and broad-spectrum biocompatibility of the hydrogel. Further, this injectable, biocompatible G-quadruplex hydrogel has been used for encapsulation and sustained release of two important vitamins (B2 and B12) over 40 h at physiological pH (7.46) and temperature (37 °C) without the influence of any external stimuli.


Asunto(s)
Ésteres , Hidrogeles , Preparaciones de Acción Retardada , Células HEK293 , Humanos , Hidrogeles/toxicidad , Vitaminas
7.
Soft Matter ; 16(44): 10065-10095, 2020 Nov 18.
Artículo en Inglés | MEDLINE | ID: mdl-33073836

RESUMEN

In this review, we have focused on the design and development of low molecular weight self-assembling peptide-based materials for various applications including cell proliferation, tissue engineering, antibacterial, antifungal, anti-inflammatory, anticancer, wound healing, drug delivery, bioimaging and 3D bioprinting. The first part of the review describes about stimuli and various noncovalent interactions, which are the key components of various self-assembly processes for the construction of organized structures. Subsequently, the chemical functionalization of the peptides has been discussed, which is required for the designing of self-assembling peptide-based soft materials. Various low molecular weight self-assembling peptides have been discussed to explain the important structural features for the construction of defined functional nanostructures. Finally, we have discussed various examples of low molecular weight self-assembling peptide-based materials for cell culture, antimicrobial, anti-inflammatory, anticancer, wound healing, drug delivery, bioimaging and 3D bioprinting applications.


Asunto(s)
Bioimpresión , Preparaciones Farmacéuticas , Antibacterianos/farmacología , Antiinflamatorios , Técnicas de Cultivo de Célula , Peso Molecular , Péptidos , Cicatrización de Heridas
8.
Inorg Chem ; 59(11): 7469-7478, 2020 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-32396344

RESUMEN

Rational engineering of novel nanohybrid materials for sustainable and efficient energy conversion has gained extensive research interest. Cross-linked nanosheets of organic-inorganic nanohybrids (BSeF/Ni(OH)2) were fabricated by one-step reductive electrosynthesis and subsequently applied for electrocatalytic water electrolysis. The organic-inorganic nanohybrids consist of benzo[2,1,3]selenadiazole-5-carbonyl phenylalanine (BSeF) cross-linked with nickel ions (Ni-BSeF) and nickel hydroxides (Ni(OH)2), which provide abundant active sites and feasible charge transfer at the electrocatalytic interface. The resulting electrodeposited nanohybrid BSeF/Ni(OH)2 exhibits bifunctional electrocatalytic performance with 240 and 401 mV of overpotential at +100 and -100 mA cm-2 for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. The BSeF/Ni(OH)2 offers a longer electrocatalytic activity of 20 h for OER and HER at applied high current densities of +400 and -200 mA cm-2. Coupled with the high OER and HER activity, the two-electrode-based system of BSeF/Ni(OH)2 shows a low cell potential of 1.54 V at 10 mA cm-2. The electrocatalytic performance of Ni-BSeF and Ni(OH)2-based organic-inorganic nanohybrids provides an efficient way to develop a nanohybrid-based catalytic system for energy conversion.

9.
Chemphyschem ; 20(17): 2221-2229, 2019 09 03.
Artículo en Inglés | MEDLINE | ID: mdl-31243871

RESUMEN

We have designed and synthesized the benzoselenadiazole (BDS) based donor-acceptor-donor (D-A-D) π-conjugated compound 4,7-di((E)styryl)benzo[2,1,3]selenadiazole (1). A single-crystal study of 1 shows J-type molecular aggregation in the solid state. The crystal packing of 1 shows head-to-head dimeric intermolecular assembly via Se⋅⋅⋅N interactions while staircase-type interlock molecular packing has occurred via Se⋅⋅⋅π interaction. The staircase-type interlock packing of dimeric molecular arrangement induces sheet-type, herringbone type architecture along crystallographic a axis and ab plane via CH⋅⋅⋅π interactions. Interestingly, the J-type aggregation of 1 in solid state changes to H-type aggregation upon UV-irradiation. Moreover, our spectroscopic findings in solution state reveal H-type of aggregation of 1 in 90 % aqueous THF. We have further demonstrated white light emission in the binary mixture of 1 and 1-pyrenemethanol (2) in 90 % aqueous THF. Our study reveals solvent specific co-assembly of H-aggregated 1 and 2 in 90 % aqueous THF solution, which shows white light emissive properties with the Commission Internationale de l'Eclairage (CIE) chromaticity coordinates (0.32, 0.31). The observed white light emission arises mainly due to the combination of red light from H-aggregated 1, blue light from monomeric 2 and green light from excimers of 2.

10.
Langmuir ; 35(6): 2383-2391, 2019 02 12.
Artículo en Inglés | MEDLINE | ID: mdl-30626180

RESUMEN

Chirality is the intrinsic property of a molecule that can be tuned by the change in chirality of a molecule or by the addition of a chiral component as an external stimulus. An l-leucine-based dipeptide-appended succinic acid-based bolaamphiphile coassembled with d-tartaric acid to form supramolecular right-handed nanostructured hydrogel, whereas l-tartaric acid coassembled to form supramolecular left-handed nanostructured hydrogel. Scanning electron microscopy and transmission electron microscopy experiments revealed the right- and left-handed helical nanofibers that are responsible for the formation of supramolecular nanostructured hydrogels. The synergistic chiral effect of l-leucine in peptide bolaamphiphile and d/l-tartaric acid plays a significant role in bicomponent gelation with helical nanofibers. The first two amino acids attached to both sides of succinic acid moiety act as a tuning button for supramolecular chirality of amino acids/peptides attached with succinic acid-based bolaamphiphiles. The second amino acid plays the role of modulating supramolecular chirality if the first two amino acids act neutrally to the chirality of bolaamphiphiles, which was confirmed by circular dichroism spectroscopy.


Asunto(s)
Dipéptidos/química , Hidrogeles/química , Nanofibras/química , Leucina/química , Estereoisomerismo , Tartratos/química
11.
Org Biomol Chem ; 16(10): 1728-1735, 2018 03 07.
Artículo en Inglés | MEDLINE | ID: mdl-29457824

RESUMEN

Constrained γ-amino acid gababutin (Gbn) based peptides that form different conformations have been synthesized. Striving to rationalize the impact of side chain orientations framing tetrapeptide-based supramolecular organic frameworks and morphological entities, Gbn incorporated hybrid peptides Boc-Gbn-Aib-Aaa-Aib-OMe (where Aaa = Phe(F) for peptide 1, Leu(L) for peptide 2 and Tyr(Y) for peptide 3) were synthesized by changing the amino acid at the third position. The solution state dual folded conformation (C12/C10 H-bonded) is probed by 2D NMR spectroscopy in support of a DMSO-d6 titration and VT NMR experiments. Peptides 1-3 adopt a C12/C10 type H-bonded dual folded conformation in the crystal state. In addition, distinct supramolecular frameworks result from the modification and orientation of the third residue side chain of peptides 1-3. A solvent induced morphological diversity of peptides 1-3 is attained by modifying the side chain backbone of the tetrapeptides, which are investigated by various microscopic (SEM and AFM) studies. Gbn-based peptides 1-3 show significant morphological and supramolecular packing properties, which are fairly different from those of their gabapentin (Gpn) based analogue peptides.


Asunto(s)
Oligopéptidos/química , Ácido gamma-Aminobutírico/análogos & derivados , Enlace de Hidrógeno , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Conformación Molecular , Oligopéptidos/síntesis química , Pliegue de Proteína , Estructura Secundaria de Proteína , Ácido gamma-Aminobutírico/síntesis química
12.
Langmuir ; 33(40): 10606-10615, 2017 10 10.
Artículo en Inglés | MEDLINE | ID: mdl-28930631

RESUMEN

The molecular origin behind the concentration-dependent intrinsic blue fluorescence of human serum albumin (HSA) is not known yet. This unusual blue fluorescence is believed to be a characteristic feature of amyloid-like fibrils of protein/peptide and originates due to the delocalization of peptide bond electrons through the extended hydrogen bond networks of cross-ß-sheet structure. Herein, by combining the results of spectroscopy, size exclusion chromatography, native gel electrophoresis, and confocal microscopy, we have shown that the intrinsic blue fluorescence of HSA exclusively originates from oligomeric interfaces devoid of any amyloid-like fibrillar structure. Our study suggests that this low energy fluorescence band is not due to any particular residue/sequence, but rather it is a common feature of self-assembled peptide bonds. The present findings of intrinsic blue fluorescence from oligomeric interfaces pave the way for future applications of this unique visual phenomenon for early stage detection of various protein aggregation related human diseases.


Asunto(s)
Albúmina Sérica Humana/química , Amiloide , Fluorescencia , Humanos , Enlace de Hidrógeno , Péptidos , Estructura Secundaria de Proteína
13.
Org Biomol Chem ; 14(17): 4089-102, 2016 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-27064926

RESUMEN

Regulating the nanostructural morphology of synthetic hybrid peptides through external stimuli is still a great challenge. Here, we report the synthesis of constrained amino acid building block gabapentin (Gpn) based hybrid peptides and their structural and morphological diversity in different conditions. The synthesized three hybrid peptides Boc-Gpn-Aib-Phe-Aib-OMe (P), Boc-Gpn-Aib-Leu-Aib-OMe (P) and Boc-Gpn-Aib-Tyr-Aib-OMe (P) are folded into C12/C10 hydrogen-bonded double turn conformations. The double turn feature is probed and confirmed by conformational analysis of hybrid peptides using 2D-NMR studies and X-ray crystallography. DMSO-d6 solvent titration investigations also support the double turn conformation adopted by our reported peptides in CDCl3 solution. Solvent assisted self-assembled morphological features of peptides P-P and the salt-prompted mineralization studies of peptide P under ambient conditions are studied. All three reported peptides P-P form diverse supramolecular scaffolds in solid states through non-covalent interactions to attain higher order architectures.


Asunto(s)
Aminoácidos/química , Oligopéptidos/síntesis química , Aminas/química , Cristalografía por Rayos X , Ácidos Ciclohexanocarboxílicos/química , Gabapentina , Enlace de Hidrógeno , Modelos Moleculares , Estructura Molecular , Oligopéptidos/química , Tamaño de la Partícula , Propiedades de Superficie , Ácido gamma-Aminobutírico/química
14.
Biomacromolecules ; 16(4): 1157-68, 2015 Apr 13.
Artículo en Inglés | MEDLINE | ID: mdl-25714334

RESUMEN

We report lipase-catalyzed inclusion of p-hydroxy benzylalcohol to peptide bolaamphiphiles. The lipase-catalyzed reactions of peptide bolaamphiphiles with p-hydroxy benzylalcohol generate dynamic combinatorial libraries (DCL) in aqueous medium that mimic the natural dissipative system. The peptide bolaamphiphile 1 (HO-WY-Suc-YW-OH) reacts with p-hydroxy benzylalcohol in the presence of lipase forming an activated diester building block. The activated diester building block self-assembles to produce nanofibrillar thixotropic hydrogel. The subsequent hydrolysis results in the dissipation of energy to form nonassembling bolaamphiphile 1 with collapsed nanofibers. The thixotropic DCL hydrogel matrix is used for 3D cell culture experiments for different periods of time, significantly supporting the cell survival and proliferation of human umbilical cord mesenchymal stem cells.


Asunto(s)
Proliferación Celular/efectos de los fármacos , Furanos/química , Hidrogeles/síntesis química , Lipasa/química , Péptidos/química , Piridonas/química , Secuencia de Aminoácidos , Biocatálisis , Humanos , Hidrogeles/química , Hidrogeles/farmacología , Células Madre Mesenquimatosas/efectos de los fármacos , Datos de Secuencia Molecular , Polimerizacion
15.
Int J Mol Sci ; 16(5): 10797-820, 2015 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-25984603

RESUMEN

Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.


Asunto(s)
Fenómenos Químicos , Péptidos/síntesis química , Biocatálisis , Hidrólisis , Luz , Modelos Moleculares , Péptidos/química
16.
Nanoscale ; 16(28): 13613-13626, 2024 Jul 18.
Artículo en Inglés | MEDLINE | ID: mdl-38958597

RESUMEN

Over the past several years, a significant increase in the expanding field of biomaterial sciences has been observed due to the development of biocompatible materials based on peptide derivatives that have intrinsic therapeutic potential. In this report, we synthesized nucleobase functionalized peptide derivatives (NPs). Hydrogelation in the synthesized NPs was induced by increasing their hydrophobicity with an aromatic moiety. The aggregation behavior of the NPs was analyzed by performing molecular dynamics simulations and DOSY NMR experiments. We performed circular dichroism (CD), thioflavin-T binding and PXRD to characterize the supramolecular aggregation in the NP1 hydrogel. The mechanical strength of the NP1 hydrogel was tested by performing rheological experiments. TEM and SEM experiments were performed to investigate the morphology of the NP1 hydrogel. The biocompatibility of the newly synthesized NP1 hydrogel was investigated using McCoy and A549 cell lines. The hemolytic activity of the NP1 hydrogel was examined in human blood cells. The stability of the newly formed NP1 hydrogel was examined using proteinase K and α-chymotrypsin. The NP1 hydrogel was used for in vitro wound healing. Western blotting, qRT-PCR and DCFDA assay were performed to determine the anti-inflammatory activity of the NP1 hydrogel. The synthesized NP1 hydrogel also exhibits antibacterial efficacy.


Asunto(s)
Antiinflamatorios , Hidrogeles , Péptidos , Cicatrización de Heridas , Humanos , Hidrogeles/química , Hidrogeles/farmacología , Cicatrización de Heridas/efectos de los fármacos , Péptidos/química , Péptidos/farmacología , Antiinflamatorios/química , Antiinflamatorios/farmacología , Antibacterianos/farmacología , Antibacterianos/química , Células A549 , Materiales Biocompatibles/química , Materiales Biocompatibles/farmacología , Materiales Biocompatibles/síntesis química , Hemólisis/efectos de los fármacos , Animales , Simulación de Dinámica Molecular , Ratones , Línea Celular
17.
ACS Appl Mater Interfaces ; 16(22): 28307-28318, 2024 Jun 05.
Artículo en Inglés | MEDLINE | ID: mdl-38771803

RESUMEN

Bioinspired, self-assembled hybrid materials show great potential in the field of energy conversion. Here, we have prepared a sonication-induced boladipeptide (HO-YF-AA-FY-OH (PBFY); AA = Adipic acid, F = l-phenylalanine, and Y = l-tyrosine) and an anchored, self-assembled nickel-based coordinated polymeric nanohybrid hydrogel (Ni-PBFY). The morphological studies of hydrogels PBFY and Ni-PBFY exhibit nanofibrillar network structures. XPS analysis has been used to study the self-assembled coordinated polymeric hydrogel Ni-PBFY-3, with the aim of identifying its chemical makeup and electronic state. XANES and EXAFS analyses have been used to examine the local electronic structure and coordination environment of Ni-PBFY-3. The xerogel of Ni-PBFY was used to fabricate the electrodes and is utilized in the OER (oxygen evolution reaction). The native hydrogel (PBFY) contains a gelator boladipeptide of 15.33 mg (20 mmol L-1) in a final volume of 1 mL. The metallo-hydrogel (Ni-PBFY-3) is prepared by combining 15.33 mg (20 mmol L-1) of boladipeptide (PBFY) with 3 mg (13 mmol L-1) of NiCl2·6H2O metal in a final volume of 1 mL. It displays an ultralow Tafel slope of 74 mV dec-1 and a lower overpotential of 164 mV at a 10 mA cm-2 current density in a 1 M KOH electrolyte, compared to other electrocatalysts under the same experimental conditions. Furthermore, the Ni-PBFY-3 electrocatalyst has been witnessed to be highly stable during 100 h of chronopotentiometry performance. To explore the OER mechanism in an alkaline medium, a theoretical calculation was carried out by employing the first-principles-based density functional theory (DFT) method. The computed results obtained by the DFT method further confirm that the Ni-PBFY-3 electrocatalyst has a high intrinsic activity toward the OER, and the value of overpotential obtained from the present experiment agrees well with the computed value of the overpotential. The biomolecule-assisted electrocatalytic results provide a new approach for designing efficient electrocatalysts, which could have significant implications in the field of green energy conversion.

18.
ACS Appl Bio Mater ; 6(12): 5301-5309, 2023 Dec 18.
Artículo en Inglés | MEDLINE | ID: mdl-37971725

RESUMEN

The development of biomolecule-derived biocompatible scaffolds for drug delivery applications is an emerging research area. Herein, we have synthesized a series of nucleobase guanine (G) functionalized amino acid conjugates having different chain lengths to study their molecular self-assembly in the hydrogel state. The gelation properties have been induced by the correct choice of chain lengths of fatty acids present in nucleobase functionalized molecules. The effect of alkali metal cations, pH, and the concentration of nucleobase functionalized amino acid conjugates in the molecular self-assembly process has been explored. The presence of Hoogsteen hydrogen bonding interaction drives the formation of a G-quadruplex functionalized hydrogel. The DOSY nuclear magnetic resonance is also performed to evaluate the self-assembling behavior of the newly formed nucleobase functionalized hydrogel. The nanofibrillar morphology is responsible for the formation of a hydrogel, which has been confirmed by various microscopic experiments. The mechanical behaviors of the hydrogel were evaluated by rheological experiments. The in vitro biostability of the synthesized nucleobase amino acid conjugate is also investigated in the presence of hydrolytic enzymes proteinase K and chymotrypsin. Finally, the nucleobase functionalized hydrogel has been used as a drug delivery platform for the control and sustained pH-responsive release of vitamins B2 and B12. This synthesized nucleobase functionalized hydrogel also exhibits noncytotoxic behavior, which has been evaluated by their in vitro cell viability experiment using HEK 293 and MCF-7 cell lines.


Asunto(s)
Hidrogeles , Vitaminas , Humanos , Hidrogeles/farmacología , Hidrogeles/química , Preparaciones de Acción Retardada/farmacología , Células HEK293 , Aminoácidos/química
19.
ACS Appl Bio Mater ; 6(2): 640-651, 2023 02 20.
Artículo en Inglés | MEDLINE | ID: mdl-36706228

RESUMEN

The multicomponent reaction-directed self-assembled hydrogels offer the opportunities to fabricate materials with ubiquitous properties which sometimes are not possible to generate from single components. Therefore, multicomponent-derived hydrogels have enormous applications in biomedical fields, and the number of such systems is increasing day by day. Herein, the multicomponent self-assembly techniques have been employed to develop a biomimetic low-molecular-weight G-quadruplex hydrogel under physiological conditions. The bioconjugation of guanosine, 4-formylphenylboronic acid, and cytosine-functionalized nucleopeptide (NP) is important to generate the multicomponent self-assembled dynamic imino-boronate ester-mediated bioconjugated G-quadruplex hydrogels. Using thioflavin T fluorescence assay, powder X-ray diffraction, and circular dichroism spectroscopic techniques, we confirm the existence of a G-quartet-like structure as the key parameter for the formation of nanofibrillar hydrogels. The multicomponent self-assembled G-quadruplex hydrogel possesses excellent inherent antibacterial activity against a broad range of bacterial species. The in vitro cytocompatibility of the synthesized hydrogel was evaluated on MCF-7 and HEK 293T cell lines to study the biocompatibility of the hydrogel. The proposed injectable, biocompatible, and NP-coupled G-quadruplex hydrogel with inherent antibacterial efficiency holds promising importance to prevent localized bacterial infections.


Asunto(s)
Antibacterianos , Hidrogeles , Hidrogeles/farmacología , Hidrogeles/química , Antibacterianos/farmacología , Antibacterianos/química
20.
Chem Commun (Camb) ; 58(54): 7534-7537, 2022 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-35703336

RESUMEN

Self-assembled benzoselenadiazole (BSe)-capped tripeptide based nanofibrillar hydrogels have been developed with inherent anticancer and anti-inflammatory activity.


Asunto(s)
Antiinflamatorios , Hidrogeles , Antiinflamatorios/farmacología , Hidrogeles/farmacología
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