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1.
Small Methods ; : e2400185, 2024 Apr 15.
Article in English | MEDLINE | ID: mdl-38616739

ABSTRACT

Developing the films of N-containing unsubstituted poly(p-phenylene) (PPP) films for diverse applications is significant and highly desirable because the replacement of sp2 C atoms with sp2 N atoms will bring novel properties to the as-prepared polymers. In this research, an electrochemical-dehalogenation polymerization strategy is employed to construct two N-containing PPP films under constant potentials, where 2,5-diiodopyridine (DIPy) and 2,5-dibromopyrazine (DBPz) are used as starting agents. The corresponding polymers are named CityU-23 (for polypyridine) and CityU-24 (for polypyrazine). Moreover, it is found that both polymers can form films in situ on different conductive substrates (i.e., silicon, gold, ITO, and nickel), satisfying potential device fabrication. Furthermore, the as-obtained thin films of CityU-23 and CityU-24 exhibit good performance of alkaline hydrogen evolution reaction with the overpotential of 212.8 and 180.7 mV and the Tafel slope of 157.0 and 122.4 mV dec-1, respectively.

2.
PNAS Nexus ; 3(2): pgae040, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38328784

ABSTRACT

Aromatic amines (AAs), ubiquitous in industrial applications, pose significant environmental hazards due to their resistance to conventional wastewater treatments. Peracetic acid (PAA)-based advanced oxidation processes (AOPs) have been proposed as effective strategies for addressing persistent AA contaminants. While the organic radicals generated in these systems are believed to be selective and highly oxidative, acetate residue complicates the evaluation of AA removal efficiency. In this work, we explored transformation pathways of AAs in a representative Co(II)-catalyzed PAA system, revealing five side reactions (i.e. nitrosation, nitration, coupling, dimerization, and acetylation) that yield 17 predominantly stable and toxic by-products. The dominant reactive species was demonstrated as Co-OOC(O)CH3, which hardly facilitated ring-opening reactions. Our findings highlight the potential risks associated with PAA-based AOPs for AA degradation and provide insights into selecting suitable catalytic systems aimed at efficient and by-product-free degradation of pollutants containing aromatic -NH2.

3.
Chem Sci ; 14(47): 13601-13628, 2023 Dec 06.
Article in English | MEDLINE | ID: mdl-38075665

ABSTRACT

Due to their excellent stability, ease of modification, high specific surface area, and tunable redox potentials, covalent organic frameworks (COFs) as potential electrodes in supercapacitors (SCs) have raised much research interest because these materials can enable the achievement of high electric double-layer supercapacitance and high pseudocapacitance. Here, the design strategies and SC applications of COF-based electrode materials are summarized. The detailed principles are introduced first, followed by discussions on strategies with diverse examples. The updated advances in design and applications are also discussed. Finally, in the outlook section, we provide some guidelines on the rational design of COF-based electrode materials for high-performance SCs, which we hope will inspire novel concepts for COF-based supercapacitors.

4.
Environ Sci Technol ; 57(48): 20206-20218, 2023 Dec 05.
Article in English | MEDLINE | ID: mdl-37965750

ABSTRACT

In the realm of wastewater treatment, the power of ferrate (Fe(VI)) and peracetic acid (PAA) as oxidants stands out. But their combined might is where the enhancement truly lies. Their collaborative effect intensifies, but the underlying mechanics, especially across varying pH levels and pollutant types, still lurks in obscurity. Our study delved into the sophisticated oxidation interplay among Fe(VI)-PAA, Fe(VI)-H2O2, and standalone Fe(VI) systems. Notably, at a pH of 9.0, boasting a kinetic constant of ∼0.127 M-1·s-1, the Fe(VI)-PAA system annihilated the pollutant sulfamethoxazole, outpacing its counterparts by a staggering 48.73-fold when compared to the Fe(VI)-H2O2 system and 105.58-fold when using Fe(VI) individually. The behavior of active species─such as the dynamic •OH radicals and high-valent iron species (Fe(IV)/Fe(V))─shifted with pH variations, leading to distinct degradation pathways. Our detailed exploration pinpoints the behaviors of certain species across pH levels from 3.0 to 9.0. In more acidic environments, the •OH species proved indispensable for the system's reactivity. Conversely, as the pH inclined, degradation was increasingly steered by high-valent iron species. This intensive probe demystifies Fe(VI) interactions, deepening our understanding of the capabilities of the Fe(VI)-centered system and guiding us toward cleaner water solutions. Importantly, pH value, often underappreciated, holds the reins in organic wastewater decontamination. Embracing this key player is vital as we strategize for more expansive systems in upcoming ventures.


Subject(s)
Water Pollutants, Chemical , Water Purification , Peracetic Acid , Hydrogen Peroxide , Water Pollutants, Chemical/analysis , Iron , Oxidation-Reduction , Sulfonamides , Sulfanilamide , Hydrogen-Ion Concentration , Anti-Bacterial Agents
5.
ACS Nano ; 17(23): 23903-23912, 2023 Dec 12.
Article in English | MEDLINE | ID: mdl-38014811

ABSTRACT

Persistent covalent-organic framework (COF) radicals hold important applications in magnetics and spintronics; however, their facile synthesis remains a daunting challenge. Here, three p-phenylenediacetonitrile-based COFs (named CityU-4, CityU-5, and CityU-6) were synthesized. Upon heat treatment (250 °C for CityU-4 and CityU-5 or 220 °C for CityU-6), these frameworks were brought into their persistent radical forms (no obvious changes after at least one year), together with several observable factors, including color changes, red-shifted absorption, the appearance of electron spin resonance (ESR) signals, and detectable magnetic susceptibility. The theoretical simulation suggests that after heat treatment, lower total energy and nonzero spin density are two main factors to guarantee persistent COFs radicals and polarized spin distributions. This work provides an efficient method for the preparation of persistent COF radicals with promising potentials.

6.
Proc Natl Acad Sci U S A ; 120(30): e2305706120, 2023 Jul 25.
Article in English | MEDLINE | ID: mdl-37459516

ABSTRACT

Singlet oxygen (1O2) plays a pivotal role in numerous catalytic oxidation processes utilized in water purification and chemical synthesis. The spin-trapping method based on electron paramagnetic resonance (EPR) analysis is commonly employed for 1O2 detection. However, it is often limited to time-independent acquisition. Recent studies have raised questions about the reliability of the 1O2 trapper, 2,2,6,6-tetramethylpiperidine (TEMP), in various systems. In this study, we introduce a comprehensive, kinetic examination to monitor the spin-trapping process in EPR analysis. The EPR intensity of the trapping product was used as a quantitative measurement to evaluate the concentration of 1O2 in aqueous systems. This in situ kinetic study was successfully applied to a classical photocatalytic system with exceptional accuracy. Furthermore, we demonstrated the feasibility of our approach in more intricate 1O2-driven catalytic oxidation processes for water decontamination and elucidated the molecular mechanism of direct TEMP oxidation. This method can avoid the false-positive results associated with the conventional 2D 1O2 detection techniques, and provide insights into the reaction mechanisms in 1O2-dominated catalytic oxidation processes. This work underscores the necessity of kinetic studies for spin-trapping EPR analysis, presenting an avenue for a comprehensive exploration of the mechanisms governing catalytic oxidation processes.

7.
Proc Natl Acad Sci U S A ; 120(6): e2215305120, 2023 Feb 07.
Article in English | MEDLINE | ID: mdl-36730199

ABSTRACT

Photosynthesis of hydrogen peroxide (H2O2) by selective oxygen reduction is a green and cost-effective alternative to the energy-intensive anthraquinone process. Although inexpensive polymeric graphitic carbon nitride (g-C3N4) exhibits the ability to produce H2O2, its disordered and amorphous structure leads to a high recombination rate of photogenerated carriers and hinders charge transfer between layers. Herein, we predict that stacked polymeric g-C3N4 with ion intercalation (K+ and I-) can improve carrier separation and transfer by multiscale computational simulations. The electronic structures of g-C3N4 were tailored and modified by intercalating K+ and I- into the layer-by-layer structures. Guided by the computational predictions, we achieved efficient solar-driven H2O2 production by employing this facile and ion-intercalated crystalline g-C3N4. An H2O2 production rate of 13.1 mM g-1 h-1 and an apparent quantum yield of 23.6% at 400 nm were obtained. The synergistic effects of crystallinity regulation and dual interstitial doping engineering triggered the formation of new light absorption centers, the establishment of rapid charge diffusion channels, and the enhancement of two-electron oxygen reduction characteristics. This work sheds light on the dual tuning of crystallinity and electronic structure and broadens the design principles of organic-conjugated polymer photocatalysts for environmental remediation and energy conservation.

8.
Adv Mater ; 34(31): e2202891, 2022 Aug.
Article in English | MEDLINE | ID: mdl-35679161

ABSTRACT

Single-atom catalysts have emerged as an efficient oxidant activator for eliminating organic pollutants in Fenton-like systems. However, the complex preparation, single active site, lack of understanding of the fundamental mechanism, and harsh pH conditions currently limit their practical applications. In this work, single-atom iron anchored nitrogen-rich g-C3 N4 nanotubes (FeCNs) are designed and synthesized by a facile approach, and eco-friendly peracetic acid (PAA) is selected as the oxidant for Fenton-like reactions. The constructed heterogenous system achieves an enhanced degradation of various organic contaminants over a wide pH range of 3.0-9.0, exhibiting an ultrahigh and stable catalytic activity, outperforming equivalent quantities of pristine g-C3 N4 by 75 times. The 18 O isotope-labeling technique, probe method, and theoretical calculations demonstrate that the efficient catalytic activity relies on the high-valency iron-oxo species coupled with organic radicals generated by PAA. An increase in electron transport from the contaminant to the formed "metastable PAA/FeCN catalyst surface complex" is detected. A double driving mechanism for the tubular g-C3 N4 regulated by a single Fe site and PAA activation is proposed. This work opens an avenue for developing novel catalysts with the coexistence of multiple active units and providing opportunities for significantly improving catalytic efficiency.

9.
Sci Total Environ ; 807(Pt 3): 151009, 2022 Feb 10.
Article in English | MEDLINE | ID: mdl-34662622

ABSTRACT

Saline wastewater poses a challenge during bio-treatment process due to salinity affecting the physiological activity of microorganisms and inhibiting their growth and metabolism. Thus, screening and engineering the salt-tolerant strains with stronger performances are urgent. Shewanella aquimarina XMS-1, a salt-tolerant dissimilated metal reducing bacteria (DMRB), was isolated from seawater environment. Its ability for reducing pollutants and generating electricity was enhanced by overexpression of riboflavin synthesis pathway encoding genes from S. oneidensis MR-1 under salt stress. Furthermore, upon contact with graphene oxide (GO), the engineered strain XMS-1/pYYDT-rib with enhanced flavins synthesis could reduce GO and self-assemble to form a three-dimensional (3D) biohybrid system named XMS-1/flavins/rGO. This 3D biohybrid system significantly enhanced the EET efficiency of S. aquimarina XMS-1. Our findings provide a feasible strategy for treatment of salt-containing industrial wastewater contaminated by metal and organic pollutants.


Subject(s)
Environmental Pollutants , Shewanella , Electricity , Shewanella/genetics
10.
Environ Sci Technol ; 55(17): 11997-12008, 2021 09 07.
Article in English | MEDLINE | ID: mdl-34378391

ABSTRACT

Dissimilatory metal-reducing bacteria (DMRB) with extracellular electron transfer (EET) capability show great potential in bioremediating the subsurface environments contaminated by uranium through bioreduction and precipitation of hexavalent uranium [U(VI)]. However, the low EET efficiency of DMRB remains a bottleneck for their applications. Herein, we develop an engineered CRISPR platform to drive the extracellular electron pumping of Shewanella oneidensis, a representative DMRB species widely present in aquatic environments. The CRISPR platform allows for highly efficient and multiplex genome editing and rapid platform elimination post-editing in S. oneidensis. Enabled by such a platform, a genomic promoter engineering strategy (GPS) for genome-widely engineering the EET-encoding gene network was established. The production of electron conductive Mtr complex, synthesis of electron shuttle flavin, and generation of NADH as intracellular electron carrier are globally optimized and promoted, leading to a significantly enhanced EET ability. Applied to U(VI) bioreduction, the edited strains achieve up to 3.62-fold higher reduction capacity over the control. Our work endows DMRB with an enhanced ability to remediate the radionuclides-contaminated environments and provides a gene editing approach to handle the growing environmental challenges of radionuclide contaminations.


Subject(s)
Shewanella , Uranium , Clustered Regularly Interspaced Short Palindromic Repeats , Electron Transport , Electrons , Shewanella/genetics
11.
Sci Total Environ ; 780: 146662, 2021 Aug 01.
Article in English | MEDLINE | ID: mdl-34030296

ABSTRACT

Soluble microbial products (SMP), a type of polymers released from microbial metabolism and decay, show great potential for wastewater treatment as bioflocculants; however, biogenic flocculant utilization is currently limited to bacterial SMP. In this study, SMP produced by Phanerochaete chrysosporium BKMF-1767 (SMP-P) was investigated to determine the application potential of fungal SMP. SMP-P exhibited high flocculation activity in kaolin suspension at a dosage range of 0.67-0.84 mg/L with Ca2+ assistance, comparable to that of commercial polyacrylamide. The high molecular weight polysaccharides (2.0 × 106-4.7 × 107 Da) in SMP-P, which enabled flocculation via the bridging mechanism and served as the dominant active constituent, were composed of glucose and arabinose at a molar ratio of 1: 0.03, with (1 â†’ 4, 6)-linked glucose as the main backbone and a small proportion of branched structures. They contained hydroxyl and carboxyl, effective functional groups for the flocculation process, and displayed parallel self-orientation behavior in water. Efficient chemical oxygen demand removal was achieved during municipal wastewater treatment using SMP-P as the bioflocculant. This study demonstrates the feasibility of utilizing fugal SMP as bioflocculants and provides guidance for their practical application.


Subject(s)
Phanerochaete , Water Purification , Biological Oxygen Demand Analysis , Flocculation , Hydrogen-Ion Concentration , Wastewater
12.
ACS Appl Mater Interfaces ; 13(17): 19846-19854, 2021 May 05.
Article in English | MEDLINE | ID: mdl-33886264

ABSTRACT

Incorporating artificial photosensitizers with microorganisms has recently been recognized as an effective way to convert light energy into chemical energy. However, the incorporated biosystem is usually constructed in an extracellular manner and is vulnerable to the external environment. Here, we develop an intracellular hybrid biosystem in a higher organism protozoa Tetrahymena pyriformis, in which the in vivo synthesized CdS nanoparticles trigger photoreduction of nitrobenzene into aniline under visible-light irradiation. Integrating a photosensitizer CdS into T. pyriformis enables the photosensitizer CdS, inherent nitroreductase, and the cytoplasmic reductive substance in T. pyriformis to synergistically engage in the photocatalysis process, generating a greatly enhanced aniline yield with a 40-fold increment. Moreover, building an intracellular hybrid biosystem in mutant T. pyriformis could even grant it new capability of reducing nitrobenzene into aniline under visible-light irradiation. Such an intracellular hybrid biosystem paves a new way to functionalize higher organisms and diversify light energy conversion.


Subject(s)
Light , Tetrahymena pyriformis/metabolism , Aniline Compounds/metabolism , Cadmium Compounds/chemistry , Cadmium Compounds/pharmacology , Catalysis , Metal Nanoparticles/chemistry , Microscopy, Fluorescence/methods , Mutation , Nitrobenzenes/metabolism , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Sulfides/chemistry , Sulfides/pharmacology , Tetrahymena pyriformis/genetics
13.
Water Res ; 191: 116799, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33453457

ABSTRACT

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) for wastewater treatment have recently attracted widespread interests. However, the degradation of organic pollutants via traditional radical-dominated pathway is severely limited by the side reactions between radicals and the co-existing inorganic anions, especially under high salinity conditions. Herein, an efficient Fe/O co-doped g-C3N4nanosheet catalyst was synthesized to dominantly activate PMS through a dual non-radical pathway with the singlet oxygen and high-valent iron-oxo species (Fe(V)=O). The rapid degradation of model pollutant bisphenol A (BPA) was achieved by dosing PMS (1 mM), catalyst (0.1 g/L) in a simulated high-salt wastewater (≥200 mM) of the developed Fe/O-doped g-C3N4+PMS system with a reaction rate constant of 1204-fold higher than that in g-C3N4+PMS system. The O and Fe co-dopants could reconfigurate the electronic structure of pristine g-C3N4 to produce more non-radical active species. The formed Fe(V)=O played a main role in the BPA degradation by promoting electron transfer from BPA molecule to the "metastable PMS/catalyst complex", which was verified by electrochemical tests and density functional theory calculations. The auxiliary transient productions of ·OH+SO4·- species were also favorable for the pollutant degradation. Excellent reusability in a wide pH range confirmed the practical application prospects of the Fe/O-doped g-C3N4+PMS system. The successive addition of PMS with a low dosage into the system rich in pollutants was confirmed to favor the PMS utilization. Our work unveils the potential applications of a non-radical dominated process for the decontamination of organic pollutants in saline water.


Subject(s)
Environmental Pollutants , Decontamination , Peroxides , Salinity
14.
Environ Microbiol ; 23(2): 1238-1255, 2021 02.
Article in English | MEDLINE | ID: mdl-33369000

ABSTRACT

The advances in synthetic biology bring exciting new opportunities to reprogram microorganisms with novel functionalities for environmental applications. For real-world applications, a genetic tool that enables genetic engineering in a stably genomic inherited manner is greatly desired. In this work, we design a novel genetic device for rapid and efficient genome engineering based on the intron-encoded homing-endonuclease empowered genome editing (iEditing). The iEditing device enables rapid and efficient genome engineering in Shewanella oneidensis MR-1, the representative strain of the electroactive bacteria group. Moreover, combining with the Red or RecET recombination system, the genome-editing efficiency was greatly improved, up to approximately 100%. Significantly, the iEditing device itself is eliminated simultaneously when genome editing occurs, thereby requiring no follow-up to remove the encoding system. Then, we develop a new extracellular electron transfer (EET) engineering strategy by programming the parallel EET systems to enhance versatile EET. The engineered strains exhibit sufficiently enhanced electron output and pollutant reduction ability. Furthermore, this device has demonstrated its great potential to be extended for genome editing in other important microbes. This work provides a useful and efficient tool for the rapid generation of synthetic microorganisms for various environmental applications.


Subject(s)
Bioelectric Energy Sources/microbiology , Electrons , Genetic Engineering/methods , Genome, Bacterial/genetics , Biodegradation, Environmental , Electron Transport/genetics , Environmental Pollutants/metabolism , Gene Editing/instrumentation , Genetic Engineering/instrumentation , Recombination, Genetic , Shewanella/genetics , Shewanella/metabolism
15.
Proc Natl Acad Sci U S A ; 117(37): 23001-23010, 2020 09 15.
Article in English | MEDLINE | ID: mdl-32855303

ABSTRACT

The unique extracellular electron transfer (EET) ability has positioned electroactive bacteria (EAB) as a major class of cellular chassis for genetic engineering aimed at favorable environmental, energy, and geoscience applications. However, previous efforts to genetically enhance EET ability have often impaired the basal metabolism and cellular growth due to the competition for the limited cellular resource. Here, we design a quorum sensing-based population-state decision (PSD) system for intelligently reprogramming the EET regulation system, which allows the rebalanced allocation of the cellular resource upon the bacterial growth state. We demonstrate that the electron output from Shewanella oneidensis MR-1 could be greatly enhanced by the PSD system via shifting the dominant metabolic flux from initial bacterial growth to subsequent EET enhancement (i.e., after reaching a certain population-state threshold). The strain engineered with this system achieved up to 4.8-fold EET enhancement and exhibited a substantially improved pollutant reduction ability, increasing the reduction efficiencies of methyl orange and hexavalent chromium by 18.8- and 5.5-fold, respectively. Moreover, the PSD system outcompeted the constant expression system in managing EET enhancement, resulting in considerably enhanced electron output and pollutant bioreduction capability. The PSD system provides a powerful tool for intelligently managing extracellular electron transfer and may inspire the development of new-generation smart bioelectrical devices for various applications.


Subject(s)
Electron Transport/physiology , Shewanella/physiology , Cell Respiration/physiology , Chromium/metabolism , Electrons , Quorum Sensing/physiology , Shewanella/metabolism
16.
Anal Chem ; 92(15): 10606-10612, 2020 08 04.
Article in English | MEDLINE | ID: mdl-32633502

ABSTRACT

Electrochemically active bacteria (EAB) are capable of extracellular electron transfer (EET) to insoluble metal oxides, and thus play a great role in the fields of environment, energy, and geosciences. However, rapid and accurate quantification of the EET ability of EAB is still challenging. In this work, we develop a riboflavin-based fluorescence method for facile, accurate, and in situ measurement of the EET ability of EAB. This method is successfully used to quantify the single-cellular EET ability of Geobacter sulfurreducens DL-1 (60.29 ± 13.02 fA) and Shewanella oneidensis MR-1 (2.11 ± 0.47 fA), the two widely present EAB in the environment. It also enables quantitative identification of EET-related c-type cytochromes in the outer membrane of S. oneidensis MR-1. This method provides a useful tool to rapidly identify EAB in diverse environments and elucidate their electron transfer mechanisms.


Subject(s)
Extracellular Space/metabolism , Geobacter/cytology , Riboflavin/metabolism , Shewanella/cytology , Electron Transport , Fluorescent Dyes/metabolism , Geobacter/metabolism , Shewanella/metabolism
17.
Environ Sci Technol ; 54(6): 3599-3608, 2020 03 17.
Article in English | MEDLINE | ID: mdl-32062962

ABSTRACT

Pursuing efficient approaches to promote the extracellular electron transfer (EET) of extracellular respiratory bacteria is essential to their application in environmental remediation and waste treatment. Here, we report a new strategy of tuning electron flux by clustered regularly interspaced short palindromic repeat (CRISPR)-ddAsCpf1-based rediverting (namely STAR) to enhance the EET capacity of Shewanella oneidensis MR-1, a model extracellular respiratory bacterium widely present in the environment. The developed CRISPR-ddAsCpf1 system enabled approximately 100% gene repression with the green fluorescent protein (GFP) as a reporter. Using a WO3 probe, 10 representative genes encoding for putative competitive electron transfer proteins were screened, among which 7 genes were identified as valid targets for EET enhancement. Repressing the valid genes not only increased the transcription level of the l-lactate metabolism genes but also affected the genes involved in direct and indirect EET. Increased riboflavin production was also observed. The feasibility of this strategy to enhance the bioreduction of methyl orange, an organic pollutant, and chromium, a typical heavy metal, was demonstrated. This work implies a great potential of the STAR strategy with the CIRPSR-ddAsCpf1 system for enhancing bacterial EET to favor more efficient environmental remediation applications.


Subject(s)
Environmental Pollutants , Shewanella , Clustered Regularly Interspaced Short Palindromic Repeats , Electron Transport , Electrons
18.
Sci Total Environ ; 710: 136322, 2020 Mar 25.
Article in English | MEDLINE | ID: mdl-31923680

ABSTRACT

Many strategies have been proposed to treat wastewater containing toxic contaminants, such as nitrobenzene, prior to discharge. Most of these degradation processes, especially biodegradation, undergo a limited step of nitrobenzene reduction into aniline and a subsequent fast step of aniline mineralization. The low efficiency of nitrobenzene reduction and the requirement of an anaerobic atmosphere limit the overall degradation performance. In this communication, eosin Y is reported as a potential homogeneous catalyst for the rapid photoreduction of nitrobenzene under aerobic conditions. As a result, a conversion (~10 min) of nitrobenzene (25 mg/L) into aniline driven by visible light was achieved. The reduction rate constants under aerobic conditions (0.30 min-1) were even slightly higher than those under anaerobic conditions (0.28 min-1), and the lifetime of the catalytic system was extended. Furthermore, the mechanism of nitrobenzene transformation was speculated based on the identification of intermediate products. To provide guidance for the practical application of this pretreatment strategy, the impact of pH value and widely existing heavy metal ions on photoreduction were also demonstrated. The results from this work provide a novel insight into the integrated control of organic pollutants produced in chemical industries.

19.
Phys Chem Chem Phys ; 17(7): 5115-23, 2015 Feb 21.
Article in English | MEDLINE | ID: mdl-25600651

ABSTRACT

We describe the synthesis and characterization of bicontinuous cubic poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer gels prepared within lyotropic cubic poly(oxyethylene)10 nonylphenol ether (NP-10) templates with Ia3[combining macron]d (gyroid, GYR) symmetry. The chemical polymerization of EDOT monomer in the hydrophobic channels of the NP-10 GYR phase was initiated by AgNO3, a mild oxidant that is activated when exposed to ultraviolet (UV) radiation. The morphology and physical properties of the resulting PEDOT gels were examined as a function of temperature and frequency using optical and electron microscopy, small-angle X-ray scattering (SAXS), dynamic mechanical spectroscopy, and electrochemical impedance spectroscopy (EIS). Microscopy and SAXS results showed that the PEDOT gels remained ordered and stable after the UV-initiated chemical polymerization, confirming the successful templated-synthesis of PEDOT in bicontinuous GYR nanostructures. In comparison to unpolymerized 3,4-ethylenedioxythiophene (EDOT) gel phases, the PEDOT structures had a higher storage modulus, presumably due to the formation of semi-rigid PEDOT-rich nanochannels. Additionally, the storage modulus (G') for PEDOT gels decreased only modestly with increasing temperature, from ∼1.2 × 10(5) Pa (10 °C) to ∼7 × 10(4) Pa (40 °C), whereas G' for the NP-10 and EDOT gels decreased dramatically, from ∼5.0 × 10(4) Pa (10 °C) to ∼1.5 × 10(2) Pa (40 °C). EIS revealed that the impedance of the PEDOT gels was smaller than the impedance of EDOT gels at both high frequencies (PEDOT ∼10(2) Ω and EDOT 2-3 × 10(4) Ω at 10(5) Hz) and low frequencies (PEDOT 10(3)-10(5) Ω and EDOT ∼5 × 10(5) Ω at 10(-1) Hz). These results indicated that PEDOT gels were highly ordered, mechanically stable and electrically conductive, and thus should be of interest for applications for which such properties are important, including low impedance and compliant coatings for biomedical electrodes.


Subject(s)
Bridged Bicyclo Compounds, Heterocyclic/chemistry , Gels/chemistry , Polymers/chemistry , Bridged Bicyclo Compounds, Heterocyclic/chemical synthesis , Electric Conductivity , Electrochemical Techniques , Gels/chemical synthesis , Polyethylene Glycols/chemical synthesis , Polyethylene Glycols/chemistry , Polymerization , Polymers/chemical synthesis , Rheology
20.
J Mater Chem B ; 2(1): 129-136, 2014 Jan 07.
Article in English | MEDLINE | ID: mdl-32261306

ABSTRACT

Functional scaffolds that could mimic cells' natural growth state in vitro are crucial for meeting the requirements of complex biological systems. However, the compact macrostructure and poor cell survival macro-environment of biomaterials are still two major challenges limiting their practical applications in bone tissue regeneration. In this study, we fabricated a highly fluffy and porous biomineral hydroxylapatite (HA) encapsulated poly-l-lactic acid (PLLA) composite fibrous scaffold (fluffy-HAFSs) by employing an improved electrospinning technique combined with a bio-mineralization technique. In the scaffold, deep interconnected pores of 65 ± 35 µm formed among these fluffy HA fibers, which permitted the easy entry of cells into the fluffy-HAFSs with no extra help to achieve complicated 3D cell culture methodologies. Human mesenchymal stem cells (hMSCs) were seeded onto the composite fibrous scaffolds and cultured for 14 days in vitro. The morphology and biochemical activities of hMSCs were tested over the culture period. Evidence was provided for the hMSCs entry into the interior of the fluffy-HAFSs and achievement of 3D cell distribution. Furthermore, these hMSCs exhibited higher degrees of growth, osteogenic differentiation and mineralization than those on HA deposited traditional electrospun fibrous meshes (HAFMs). These results indicated that the novel fluffy-HAFSs might be potentially applied as bone repairing and regeneration scaffolds.

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