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1.
Environ Pollut ; 347: 123705, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38442825

RESUMO

The ongoing challenge of water pollution by contaminants of emerging concern calls for more effective wastewater treatment to prevent harmful side effects to the environment and human health. To this end, this study explored for the first time the implementation of single-crystal boron-doped diamond (BDD) anodes in electrochemical wastewater treatment, which stand out from the conventional polycrystalline BDD morphologies widely reported in the literature. The single-crystal BDD presented a pure diamond (sp3) content, whereas the three other investigated polycrystalline BDD electrodes displayed various properties in terms of boron doping, sp3/sp2 content, microstructure, and roughness. The effects of other process conditions, such as applied current density and anolyte concentration, were simultaneously investigated using carbamazepine (CBZ) as a representative target pollutant. The Taguchi method was applied to elucidate the optimal operating conditions that maximised either (i) the CBZ degradation rate constant (enhanced through hydroxyl radicals (•OH)) or (ii) the proportion of sulfate radicals (SO4•-) with respect to •OH. The results showed that the single-crystal BDD significantly promoted •OH formation but also that the interactions between boron doping, current density and anolyte concentration determined the underlying degradation mechanisms. Therefore, this study demonstrated that characterising the BDD material and understanding its interactions with other process operating conditions prior to degradation experiments is a crucial step to attain the optimisation of any wastewater treatment application.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Humanos , Boro/química , Oxirredução , Diamante/química , Poluentes Químicos da Água/química , Eletrodos , Purificação da Água/métodos
2.
Environ Pollut ; 346: 123688, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38431247

RESUMO

One challenge of the citrus industry is the treatment and disposal of its effluents due to their high toxicity, substantial organic load, and consequent resistance to conventional biotechnological processes. This study introduces a novel approach, using electrochemical oxidation with a boron-doped diamond anode to efficiently remove organic compounds from biodegraded pulp wash (treated using the fungus Pleurotus sajor-caju.) The findings reveal that employing a current density of 20 mA cm-2 achieves notable results, including a 44.1% reduction in color, a 70.0% decrease in chemical oxygen demand, an 88.0% reduction in turbidity, and an impressive 99.7% removal of total organic carbon (TOC) after 6 h of electrolysis. The energy consumption was estimated at 2.93 kWh g-1 of removed TOC. This sequential biological-electrochemical procedure not only significantly reduced the mortality rate (85%) of Danio rerio embryos but also reduced the incidence of morphologically altered parameters. Regarding acute toxicity (LC50) of the residue, the process demonstrated a mortality reduction of 6.97% for D. rerio and a 40.88% lethality decrease for Lactuca sativa seeds. The substantial reduction in toxicity and organic load observed in this study highlights the potential applicability of combined biological and electrochemical treatments for real agroindustrial residues or their effluents.


Assuntos
Diamante , Poluentes Químicos da Água , Diamante/química , Poluentes Químicos da Água/análise , Eletrólise/métodos , Compostos Orgânicos , Eletrodos , Oxirredução
3.
Chemosphere ; 355: 141763, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38522672

RESUMO

The fluoroquinolones ciprofloxacin, danofloxacin, enoxacin, levofloxacin and lomefloxacin, occur in water bodies worldwide and therefore pose a threat to the aquatic environment. Advanced purification procedures, such as electrochemical oxidation, may act as a remedy since they contribute to eliminating contaminants and prevent micropollutants from entering open water bodies. By electrochemical treatment in a micro-flow reactor equipped with a boron-doped diamond (BDD) electrode, the fluoroquinolones were efficiently degraded. A total of 15 new products were identified using high-performance high-resolution chromatography coupled with high-resolution multifragmentation mass spectrometry. The ecotoxicity of the emerging transformation products was estimated through in silico quantitative structure activity relationship analysis. Almost all transformation products were predicted less ecotoxic than the initial compounds. The fluoroquinolone degradation followed three major mechanisms depending on the voltage during the electrochemical oxidation. At approximately 1 V, the reactions started with the elimination of molecular hydrogen from the piperazine moiety. At approx. 1.25 V, methyl and methylene groups were eliminated. At 1.5 V, hydroxyl radicals, generated at the BDD electrode, led to substitution at the piperazine ring. This novel finding of the three reactions depending on voltage contributes to the mechanistic understanding of electrochemical oxidation as potential remedy against fluoroquinolones in the aquatic environment.


Assuntos
Ciprofloxacina , Poluentes Químicos da Água , Ciprofloxacina/química , Levofloxacino/análise , Enoxacino/análise , Diamante/química , Fluoroquinolonas/análise , Piperazina , Oxirredução , Eletrodos , Água , Poluentes Químicos da Água/análise
4.
Biosensors (Basel) ; 14(2)2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38391994

RESUMO

Amperometry is arguably the most widely used technique for studying the exocytosis of biological amines. However, the scarcity of human tissues, particularly in the context of neurological diseases, poses a challenge for exocytosis research. Human platelets, which accumulate 90% of blood serotonin, release it through exocytosis. Nevertheless, single-cell amperometry with encapsulated carbon fibers is impractical due to the small size of platelets and the limited number of secretory granules on each platelet. The recent technological improvements in amperometric multi-electrode array (MEA) devices allow simultaneous recordings from several high-performance electrodes. In this paper, we present a comparison of three MEA boron-doped diamond (BDD) devices for studying serotonin exocytosis in human platelets: (i) the BDD-on-glass MEA, (ii) the BDD-on-silicon MEA, and (iii) the BDD on amorphous quartz MEA (BDD-on-quartz MEA). Transparent electrodes offer several advantages for observing living cells, and in the case of platelets, they control activation/aggregation. BDD-on-quartz offers the advantage over previous materials of combining excellent electrochemical properties with transparency for microscopic observation. These devices are opening exciting perspectives for clinical applications.


Assuntos
Serotonina , Humanos , Boro/química , Diamante/química , Eletrodos , Exocitose , Quartzo
5.
Proc Jpn Acad Ser B Phys Biol Sci ; 100(3): 149-164, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38311394

RESUMO

Since the large-volume press with a double-stage multianvil system was created by the late Professor Naoto Kawai, this apparatus (Kawai-type multianvil apparatus or KMA) has been developed for higher-pressure generation, in situ X-ray and neutron observations, deformation experiments, measurements of physical properties, synthesis of high-pressure phases, etc., utilizing its large sample volume and capacity in stable and homogeneous high temperature generation compared to those of competitive diamond anvil cells. These advancements in KMA technology have been made primarily by Japanese scientists and engineers, which yielded a wealth of new experimental data on phase transitions, melting relations, and physical characteristics of minerals and rocks, leading to significant constraints on the structures, chemical compositions, and dynamics of the deep Earth. KMA technology has also been used for synthesis of novel functional materials such as nano-polycrystalline diamond and transparent nano-ceramics, opening a new research field of ultrahigh-pressure materials science.


Assuntos
Diamante , Tecnologia , Diamante/química , Fenômenos Físicos
6.
Anal Sci ; 40(5): 853-861, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38246930

RESUMO

To minimize background interference in electrochemical enzymatic biosensors employing electron mediators, it is essential for the electrochemical oxidation of electroactive interfering species (ISs), such as ascorbic acid (AA), to proceed slowly, and for the redox reactions between electron mediators and ISs to occur at a low rate. In this study, we introduce a novel combination of a working electrode and an electron mediator that effectively mitigates interference effects. Compared to commonly used electrodes such as Au, glassy carbon, and indium tin oxide (ITO), boron-doped diamond (BDD) electrodes demonstrate significantly lower anodic current (i.e., lower background levels) in the presence of AA. Additionally, menadione (MD) exhibits notably slower reactivity with AA compared to other electron mediators such as Ru(NH3)63+, 4-amino-1-naphthol, and 1,4-naphthoquinone, primarily due to the lower formal potential of MD compared to AA. This synergistic combination of BDD electrode and MD is effectively applied in three biosensors: (i) glucose detection using electrochemical-enzymatic (EN) redox cycling, (ii) glucose detection using electrochemical-enzymatic-enzymatic (ENN) redox cycling, and (iii) lactate detection using ENN redox cycling. Our developed approach significantly outperforms the combination of ITO electrode and MD in minimizing IS interference. Glucose in artificial serum can be detected with detection limits of ~ 20 µM and ~ 3 µM in EN and ENN redox cycling, respectively. Furthermore, lactate in human serum can be detected with a detection limit of ~ 30 µM. This study demonstrates sensitive glucose and lactate detection with minimal interference, eliminating the need for (bio)chemical agents to remove interfering species.


Assuntos
Boro , Diamante , Técnicas Eletroquímicas , Eletrodos , Glucose , Ácido Láctico , Vitamina K 3 , Diamante/química , Vitamina K 3/química , Boro/química , Glucose/análise , Glucose/química , Ácido Láctico/análise , Ácido Láctico/química , Técnicas Biossensoriais , Elétrons , Humanos , Oxirredução
7.
ACS Appl Mater Interfaces ; 16(4): 4361-4374, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38232177

RESUMO

This study demonstrates the control of neuronal survival and development using nitrogen-doped ultrananocrystalline diamond (N-UNCD). We highlight the role of N-UNCD in regulating neuronal activity via near-infrared illumination, demonstrating the generation of stable photocurrents that enhance neuronal survival and neurite outgrowth and foster a more active, synchronized neuronal network. Whole transcriptome RNA sequencing reveals that diamond substrates improve cellular-substrate interaction by upregulating extracellular matrix and gap junction-related genes. Our findings underscore the potential of conductive diamond as a robust and biocompatible platform for noninvasive and effective neural tissue engineering.


Assuntos
Diamante , Engenharia Tecidual , Diamante/farmacologia , Diamante/química , Condutividade Elétrica , Neurônios/fisiologia , Sobrevivência Celular
8.
Med Phys ; 51(2): 1450-1459, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37742343

RESUMO

BACKGROUND: The possible emergence of the FLASH effect-the sparing of normal tissue while maintaining tumor control-after irradiations at dose-rates exceeding several tens of Gy per second, has recently spurred a surge of studies attempting to characterize and rationalize the phenomenon. Investigating and reporting the dose and instantaneous dose-rate of ultra-high dose-rate (UHDR) particle radiotherapy beams is crucial for understanding and assessing the FLASH effect, towards pre-clinical application and quality assurance programs. PURPOSE: The purpose of the present work is to investigate a novel diamond-based detector system for dose and instantaneous dose-rate measurements in UHDR particle beams. METHODS: Two types of diamond detectors, a microDiamond (PTW 60019) and a diamond detector prototype specifically designed for operation in UHDR beams (flashDiamond), and two different readout electronic chains, were investigated for absorbed dose and instantaneous dose-rate measurements. The detectors were irradiated with a helium beam of 145.7 MeV/u under conventional and UHDR delivery. Dose-rate delivery records by the monitoring ionization chamber and diamond detectors were studied for single spot irradiations. Dose linearity at 5 cm depth and in-depth dose response from 2 to 16 cm were investigated for both measurement chains and both detectors in a water tank. Measurements with cylindrical and plane-parallel ionization chambers as well as Monte-Carlo simulations were performed for comparisons. RESULTS: Diamond detectors allowed for recording the temporal structure of the beam, in good agreement with the one obtained by the monitoring ionization chamber. A better time resolution of the order of few µs was observed as compared to the approximately 50 µs of the monitoring ionization chamber. Both diamonds detectors show an excellent linearity response in both delivery modalities. Dose values derived by integrating the measured instantaneous dose-rates are in very good agreement with the ones obtained by the standard electrometer readings. Bragg peak curves confirmed the consistency of the charge measurements by the two systems. CONCLUSIONS: The proposed novel dosimetric system allows for a detailed investigation of the temporal evolution of UHDR beams. As a result, reliable and accurate determinations of dose and instantaneous dose-rate are possible, both required for a comprehensive characterization of UHDR beams and relevant for FLASH effect assessment in clinical treatments.


Assuntos
Diamante , Hélio , Diamante/química , Hélio/uso terapêutico , Radiometria , Método de Monte Carlo
9.
Chemosphere ; 349: 140834, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38042421

RESUMO

Beauty salons (BS) are places that deal with a wide range of cosmetics with potentially hazardous chemicals, and their effluent should be properly treated before going to the sewage system, once it represents characteristics of industrial wastewater. This work provides an extensive characterization of a BS effluent and its respective electrochemical treatment by comparing NaCl, Na2SO4, and Na2S2O8 as supporting electrolytes with a boron-doped diamond (BDD) as anode, applying 10 or 30 mA cm-2 of current density (j). The inclusion of UVC irradiation was also performed but the improvements achieved in removing the organic matter were null or lower. The analysis of chemical oxygen demand (COD) removal, energy consumption, and total current efficiency (TCE) was required to prove the efficacy of the processes and the comparative study of the performance of different technologies. Precipitate analysis was also done due to the high turbidity of the raw effluent and the appearance of a precipitate before and during the electrolysis, mainly with Na2S2O8. The precipitate confirmed the presence of silicates and small amounts of heavy metals. The results clearly showed that 6 h of treatment with Na2SO4 achieved 58% of COD removal with an energy consumption of about 0.52 kWh m-3, being the best electrolyte option for treating BS effluent by applying 10 mA cm-2. Under these experimental conditions, the final wastewater can be directly discharged into the sewage system with a lower amount of visible precipitate, and with 73% less turbidity. The treatment here proposed can be used as an alternative to decision-makers and governments once it can be a step further in the implementation of better and advanced politics of water sanitation.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Oxirredução , Esgotos , Sulfatos/análise , Poluentes Químicos da Água/análise , Eletrólitos , Diamante/química , Eletrodos
10.
J Prosthet Dent ; 131(1): 164.e1-164.e11, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37945513

RESUMO

STATEMENT OF PROBLEM: High translucency zirconia (HTZ) has gained popularity as an esthetic computer-aided design and computer-aided manufacturing (CAD-CAM) material for monolithic restorations. A detailed comparison between different common surface and heat treatments with a non-treated HTZ control to explain the behavior of the material under stress is lacking. PURPOSE: The purpose of this in vitro study was to evaluate the effect of different surface and heat treatments on the surface roughness parameters (SRPs), topography, crystallography, and phase composition of HTZ used for monolithic restorations. MATERIAL AND METHODS: Ninety Ø11.9×1.18-mm HTZ disks (Prettau Anterior) were milled, sintered, and distributed into 9 groups (n=10); 8 experimental (coarse diamond grinding GC, fine diamond grinding GF, fine diamond grinding and 3-step polishing kit GF+P1, fine diamond grinding and 3-step polishing kit and diamond paste GF+P1+DP, fine diamond grinding and 2-step polishing kit GF+P2, fine diamond grinding and GF+Gl, fine diamond grinding and 3-step polishing and glazing GF+P1+Gl, airborne-particle abrasion with 50-µm alumina), and a control group (C, as-sintered). SRPs (AveSa, AveSv, AveSz) and 3-dimensional (3D) images were obtained using a noncontact 3D-optic-profilometer. The crystal structure was determined with scanning electron microscopy. Phase composition was analyzed by X-ray diffraction (XRD). Surface roughness parameters data were statistically analyzed by 1-way ANOVA and the Tukey HSD test (α=.05). RESULTS: The applied surface and heat treatment resulted in significantly different SRP mean values (P<.001) with different topographies. GC had the highest AveSa, AveSv, and AveSz mean values (0.95, 8.8, 17.4 µm, respectively) with significant microcracks. GF had significantly lower SRP with finer microcracks. GF+P1 had a significantly smoother surface, but GF+P2 resulted in SRP comparable with the GF group. GF+P1+DP had the smoothest homogenous surface (mean Sa: 0.08 µm). GF+P1 and GF+GL were equally effective, while GF+P1+GL was not superior. Airborne-particle abrasion produced a low Sa mean value (0.11 µm) with relatively high Sv and Sz mean values (5.9, 9.2 µm, respectively) and microcracks. A monoclinic phase was detected in all groups. All experimental groups had broadened XRD-peaks with lower intensity, suggesting the presence of the rhombohedral phase. CONCLUSIONS: The different surface and heat treatments altered the HTZ crystals and their surface roughness with distinct topographies. Cubic crystal changes take place under stress as shown by the scanning electron microscope and the XRD diffraction pattern and may transform to the rhombohedral phase.


Assuntos
Polimento Dentário , Temperatura Alta , Teste de Materiais , Cristalografia , Polimento Dentário/métodos , Propriedades de Superfície , Estética Dentária , Zircônio/química , Microscopia Eletrônica de Varredura , Diamante/química , Cerâmica/química
11.
Med Phys ; 51(1): 533-544, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37656015

RESUMO

BACKGROUND: Ion beam therapy allows for a substantial sparing of normal tissues and higher biological efficacy. Synthetic single crystal diamond is a very good material to produce high-spatial-resolution and highly radiation hard detectors for both dosimetry and microdosimetry in ion beam therapy. PURPOSE: The aim of this work is the design, fabrication and test of an integrated waterproof detector based on synthetic single crystal diamond able to simultaneously perform dosimetric and microdosimetric characterization of clinical ion beams. METHODS: The active elements of the integrated diamond device, that is, dosimeter and microdosimeter, were both realized in a Schottky diode configuration featured by different area, thickness, and shape by means of photolithography technologies for the selective growth of intrinsic and boron-doped CVD diamond. The cross-section of the sensitive volume of the dosimetric element is 4 mm2 and 1 µm-thick, while the microdosimetric one has an active cross-sectional area of 100 × 100 µm2 and a thickness of about 6.2 µm. The dosimetric and microdosimetric performance of the developed device was assessed at different depths in a water phantom at the MedAustron ion beam therapy facility using a monoenergetic uniformly scanned carbon ion beam of 284.7 MeV/u and proton beam of 148.7 MeV. The particle flux in the region of the microdosimeter was 6·107  cm2 /s for both irradiation fields. At each depth, dose and dose distributions in lineal energy were measured simultaneously and the dose mean lineal energy values were then calculated. Monte Carlo simulations were also carried out by using the GATE-Geant4 code to evaluate the relative dose, dose averaged linear energy transfer (LETd ), and microdosimetric spectra at various depths in water for the radiation fields used, by considering the contribution from the secondary particles generated in the ion interaction processes as well. RESULTS: Dosimetric and microdosimetric quantities were measured by the developed prototype with relatively low noise (∼2 keV/µm). A good agreement between the measured and simulated dose profiles was found, with discrepancies in the peak to plateau ratio of about 3% and 4% for proton and carbon ion beams respectively, showing a negligible LET dependence of the dosimetric element of the device. The microdosimetric spectra were validated with Monte Carlo simulations and a good agreement between the spectra shapes and positions was found. Dose mean lineal energy values were found to be in close agreement with those reported in the literature for clinical ion beams, showing a sharp increase along the Bragg curve, being also consistent with the calculated LETd for all depths within the experimental error of 10%. CONCLUSIONS: The experimental indicate that the proposed device can allow enhanced dosimetry in particle therapy centers, where the absorbed dose measurement is implemented by the microdosimetric characterization of the radiation field, thus providing complementary results. In addition, the proposed device allows for the reduction of the experimental uncertainties associated with detector positioning and could facilitate the partial overcoming of some drawbacks related to the low sensitivity of diamond microdosimeters to low LET radiation.


Assuntos
Diamante , Prótons , Diamante/química , Radiometria , Carbono/uso terapêutico , Íons , Método de Monte Carlo , Água
12.
Oper Dent ; 49(1): 91-97, 2024 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-38057997

RESUMO

OBJECTIVE: The aim was to compare intrapulp temperature (IPT) changes when flat-fissure diamond burs and pear-shaped tungsten carbide burs were used to cut tooth structure, amalgam, and composite resin with and without water coolant. METHODS: Thermocouples were inserted into the pulp chamber of extracted intact mandibular molars. The thermocouples were connected to an electronic thermometer that detects temperature every second to an accuracy of 0.1°C. IPT changes were recorded while using a high-speed handpiece during MOD cavity preparations (n=40), composite resin removal (n=40), and amalgam removal (n=40). A two-way ANOVA was used for each procedure to test for the effect of bur (pear-shaped tungsten carbide vs flat-fissured diamond) and water coolant (on vs off), with significant main effects (α=0.05) further analyzed using Tukey's multiple comparison test. RESULTS: During MOD cavity preparation, water coolant reduced changes in IPT (0.03±0.27°C) compared to no water coolant (1.27±0.29°C) when tungsten carbide burs were used (p<0.05) but not when diamond burs were used. During composite resin removal, tungsten carbide burs had less changes in IPT (0.55±0.18°C) compared to diamond burs (1.66±0.50°C) with no water coolant (p<0.05). Water coolant also reduced changes in IPT (0.09±0.14°C) compared to no water coolant (1.66±0.50°C) when diamond burs were used (p<0.01). Water coolant did not significantly affect IPT when tungsten carbide burs were used. During amalgam removal, tungsten carbide burs had lower changes in IPT (0.56±0.15°C) compared to diamond burs (1.88±0.43°C) with no water coolant (p<0.05). Water coolant also significantly reduced changes in IPT (0.71±0.2°C) compared to no water coolant (1.88±0.43°C) when diamond burs were used (p<0.05) but not when tungsten carbide burs were used. CONCLUSIONS: Water coolant reduced IPT changes when drilling tooth structure with tungsten carbide burs, but not when removing amalgam or composite. Conversely, water coolant reduced IPT changes when drilling with flat fissure diamond burs to remove amalgam and composite, but not when removing tooth structure. When amalgam and composite were removed without water coolant, the tungsten carbide burs resulted in lower IPT changes than when flat fissure diamond burs were used in the same way.


Assuntos
Compostos de Tungstênio , Água , Temperatura , Água/química , Equipamentos Odontológicos de Alta Rotação , Resinas Compostas/uso terapêutico , Resinas Compostas/química , Compostos de Tungstênio/química , Diamante/química , Propriedades de Superfície
13.
Chemosphere ; 345: 140396, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37820875

RESUMO

Tetrahydrofurfuryl alcohol (THFA), a widely applied raw materials, intermediate and solvent in the fields of agricultural, industry (especially in nuclear industry), is a potentially hazardous and non-biodegradable pollutant in wastewater. In this study, the electrochemical degradation pathways of THFA by a boron-doped diamond (BDD) anode with different current density (jappl = 20, 40 and 60 mA cm-2) and electrolyte solution (KNO3, KCl and K2SO4) was carefully investigated. The results exhibit that high chemical oxygen demand (COD) removal and mineralization rates were achieved by rapid non-selective oxidation in electrolyte solutions mediated by hydroxyl radicals (∙OH) and active chlorine (sulfate) under constant current electrolysis. In-depth data analysis using the high performance liquid chromatography and liquid chromatography/mass spectroscopy, the underlying removal pathways of THFA in KNO3, KCl and K2SO4 electrolyte solutions are proposed according to the effect of different mineralization mechanisms.


Assuntos
Boro , Poluentes Químicos da Água , Boro/química , Diamante/química , Poluentes Químicos da Água/análise , Sulfatos/química , Eletrodos
14.
Environ Sci Pollut Res Int ; 30(55): 117871-117880, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37875760

RESUMO

In this work, a new coating of boron-doped diamond ultra-nanocrystalline (U-NBDD), tailored to prevent massive formation of perchlorates during disinfection, is evaluated as electrode for the reclaiming of treated secondary wastewater by the electrochemically assisted disinfection process. Results obtained are compared to those obtained by using a standard electrode (STD) that was evaluated as a standard in previous research showing outstanding performance for this application. First tests were carried out to evaluate the chlorine speciation obtained after the electrolysis of synthetic chloride solutions at two different ranges of current densities. Concentrations of hypochlorite obtained using the U-NBDD anode at 25 mA cm-2 were 1.5-fold higher, outperforming STD anode; however, at 300 mA cm-2, an overturn on the behavior of anodes occurs where the amount of hypochlorite produced on STD anode was 1.5-fold higher. Importantly, at low current density the formation of chlorates and perchlorates is null using U-NBDD. Then, the disinfection of the real effluent of the secondary clarifier of a municipal wastewater treatment facility is assessed, where inactivation of Escherichia coli is achieved at low charge applied per volume electrolyzed (0.08 A h L-1) at 25 mA cm-2 using the U-NBDD. These findings demonstrate the appropriateness of the strategy followed in this work to obtain safer electro-disinfection technologies for the reclaiming of treated wastewater.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Diamante/química , Desinfecção/métodos , Ácido Hipocloroso , Percloratos , Eletrólise/métodos , Eletrodos , Oxirredução , Poluentes Químicos da Água/química
15.
Anal Chem ; 95(45): 16600-16608, 2023 11 14.
Artigo em Inglês | MEDLINE | ID: mdl-37883708

RESUMO

Bacterial sensing based on quantum cascade laser spectroscopy coupled with diamond or gallium arsenide thin-film waveguides is a novel analytical tool for gaining high-resolution infrared spectroscopic information of planktonic and sessile bacteria, as shown in the present study for Escherichia coli. During observation periods of up to 24 h, diamond and gallium arsenide thin-film waveguide laser spectroscopy was compared to information obtained via conventional Fourier transform infrared spectroscopy. The proliferation behavior of E. coli at those surfaces was complementarily investigated using atomic force microscopy and scanning electron microscopy.


Assuntos
Escherichia coli , Lasers , Espectroscopia de Infravermelho com Transformada de Fourier , Diamante/química
16.
ACS Nano ; 17(20): 20034-20042, 2023 10 24.
Artigo em Inglês | MEDLINE | ID: mdl-37791968

RESUMO

The viscoelasticity of the cytoplasm plays a critical role in cell morphology, cell division, and intracellular transport. Viscoelasticity is also interconnected with other biophysical properties, such as temperature, which is known to influence cellular bioenergetics. Probing the connections between intracellular temperature and cytoplasmic viscoelasticity provides an exciting opportunity for the study of biological phenomena, such as metabolism and disease progression. The small length scales and transient nature of changes in these parameters combined with their complex interdependencies pose a challenge for biosensing tools, which are often limited to a single readout modality. Here, we present a dual-mode quantum sensor capable of performing simultaneous nanoscale thermometry and rheometry in dynamic cellular environments. We use nitrogen-vacancy centers in diamond nanocrystals as biocompatible sensors for in vitro measurements. We combine subdiffraction resolution single-particle tracking in a fluidic environment with optically detected magnetic resonance spectroscopy to perform simultaneous sensing of viscoelasticity and temperature. We use our sensor to demonstrate probing of the temperature-dependent viscoelasticity in complex media at the nanoscale. We then investigate the interplay between intracellular forces and the cytoplasmic rheology in live cells. Finally, we identify different rheological regimes and reveal evidence of active trafficking and details of the nanoscale viscoelasticity of the cytoplasm.


Assuntos
Nanopartículas , Termometria , Diamante/química , Nanopartículas/química , Temperatura , Termometria/métodos , Espectroscopia de Ressonância Magnética
17.
Chemosphere ; 342: 140171, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37714487

RESUMO

This study upgrades the sustainability of environmental electrochemical technologies with a novel approach consisting of the in-situ cogeneration and use of two important oxidants, hydrogen peroxide (H2O2) and Caro's acid (H2SO5), manufactured with the same innovative cell. This reactor was equipped with a gas diffusion electrode (GDE) to generate cathodically H2O2, from oxygen reduction reaction, a boron doped diamond (BDD) electrode to obtain H2SO5, via anodic oxidation of dilute sulfuric acid, and a proton exchange membrane to separate the anodic and the cathodic compartment, preventing the scavenging effect of the interaction of oxidants. A special design of the inlet helps this cell to reach simultaneous efficiencies as high as 99% for H2O2 formation and 19.7% for Caro's acid formation, which means that the cogeneration reaches efficiencies over 100% in the uses of electric current to produce oxidants. The two oxidants' streams produced were used with different configurations for the degradation of three volatile organic compounds (benzene, toluene, and xylene) in a batch reactor equipped with a UVC-lamp. Among different alternatives studied, the combination H2SO5/H2O2 under UVC irradiation showed the best results in terms of degradation efficiency, demonstrating important synergisms as compared to the bare technologies.


Assuntos
Oxidantes , Poluentes Químicos da Água , Peróxido de Hidrogênio/química , Oxirredução , Eletrodos , Boro/química , Diamante/química , Poluentes Químicos da Água/química
18.
Water Sci Technol ; 88(5): 1294-1316, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37771228

RESUMO

In this work, the electrochemical degradation of ciprofloxacin (CIP) was studied in a filter-press-type reactor without division in a batch recirculation manner. For this purpose, two boron-doped diamond (BDD) electrodes (as cathode and anode) were employed. Also, the optimal operating conditions were found by response surface methodology (RSM) following a central composite face-centered design with three factors, namely current intensity (i), initial pH (pH0), and initial concentration ([C]0) with two responses, namely remotion efficiency (η) and operating cost. Optimal operating conditions were i = 3 A, pH0 = 8.49, and [C]0 = 33.26 mg L-1 within an electrolysis time of 5 h, leading to a maximum removal efficiency of 93.49% with a minimum operating cost of $0.013 USD L-1. Also, a TOC analysis shows an 80% of mineralization extent with an energy consumption of 5.11 kWh g-1 TOC. Furthermore, the CIP degradation progress was followed by mass spectrometry (LC/MS) and a degradation pathway is proposed.


Assuntos
Ciprofloxacina , Poluentes Químicos da Água , Ciprofloxacina/química , Poluentes Químicos da Água/química , Oxirredução , Eletrólise/métodos , Diamante/química , Eletrodos
19.
Curr Opin Biotechnol ; 83: 102975, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37573624

RESUMO

Single-cell analysis can unravel functional heterogeneity within cell populations otherwise obscured by ensemble measurements. However, noninvasive techniques that probe chemical entities and their dynamics are still lacking. This challenge could be overcome by novel sensors based on nitrogen-vacancy (NV) centers in diamond, which enable nuclear magnetic resonance (NMR) spectroscopy on unprecedented sample volumes. In this perspective, we briefly introduce NV-based quantum sensing and review the progress made in microscale NV-NMR spectroscopy. Last, we discuss approaches to enhance the sensitivity of NV ensemble magnetometers to detect biologically relevant concentrations and provide a roadmap toward their application in single-cell analysis.


Assuntos
Diamante , Nitrogênio , Espectroscopia de Ressonância Magnética/métodos , Diamante/química , Análise de Célula Única
20.
J Environ Manage ; 344: 118718, 2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37541001

RESUMO

Antibiotic-containing wastewater is a typical biochemical refractory organic wastewater and general treatment methods cannot effectively and quickly degrade the antibiotic molecules. In this study, a novel boron-doped diamond (BDD) pulse electrochemical oxidation (PEO) technology was proposed for the efficient removal of levofloxacin (LFXN) from wastewater. The effects of current density (j), initial pH (pH0), frequency (f), electrolyte types and initial concentration (c0(LFXN)) on the degradation of LFXN were systematically investigated. The degradation kinetics under four different processes have also been studied. The possible degradation mechanism of LFXN was proposed by Density functional theory calculation and analysis of degradation intermediates. The results showed that under the optimal parameters, the COD removal efficiency (η(COD)) was 94.4% and the energy consumption (EEC) was 81.43 kWh·m-3 at t = 120 min. The degradation of LFXN at pH = 2.8/c(H2O2) followed pseudo-first-order kinetics. The apparent rate constant was 1.33 × 10-2 min-1, which was much higher than other processes. The degradation rate of LFXN was as follows: pH = 2.8/c(H2O2) > pH = 2.8 > pH = 7/c(H2O2) > pH = 7. Ten aromatic intermediates were formed during the degradation of LFXN, which were further degraded to F-, NH4+, NO3-, CO2 and H2O. This study provides a promising approach for efficiently treating LFXN antibiotic wastewater by pulsed electrochemical oxidation with a BDD electrode without adding H2O2.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Antibacterianos , Levofloxacino/análise , Peróxido de Hidrogênio , Poluentes Químicos da Água/química , Boro/química , Diamante/química , Oxirredução , Eletrodos
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