Radio-frequency Atmospheric-pressure Glow Discharge Research Articles

Application of a pm-rf-APGD-type plasma brush for deactivation of antibiotics from liquid solutions leads to impaired development of drug resistance by bacterial pathogens

The presence of antibiotics residuals in the natural environment contributes to development and spread of drug resistance determinants among bacteria, often including clinically significant human pathogens. To tackle with this threat, we constructed a plasma brush, generating pulse-modulated radio-frequency atmospheric pressure glow discharge (pm-rf-APGD), named pm-rf-APGD-type plasma brush, intended for degradation of biologically active pharmaceuticals from both single- and five-component solutions of ciprofloxacin (CFX), enrofloxacin (EFX), ofloxacin (OFX), doxycycline (DXC), and trimethoprim (TMP). The mean antibiotics removal efficiency, achieved mainly due to the action of reactive oxygen species (ROS), was 93.3 %. This removal efficiency corresponded to a mean 62.7% decrease in the antibacterial activities. We revealed the transformation products resulting from an oxygen attack and/or internal fragmentation of the treated pharmaceuticals. Based on a laboratory evolution study, bacterial exposure to the pm-rf-APGD-treated drug lead to significantly lower rates of antibiotic resistance development in juxtaposition with a long-term exposure to the sublethal dose of the active molecules. Thus, we anticipate a great potential of high-throughput, continuous flow, eco-friendly pm-rf-APGD-type plasma brush for routine decontamination processes in the future disposal pipelines of pharmaceuticals-containing wastewaters.

Biosafe removal of diclofenac from wastewaters by a continuous-flow mode cold atmospheric pressure plasma system

Diclofenac (DCF) is not only a versatile non-steroidal anti-inflammatory drug, but also an emerging water pollutant. There is an urgent need for innovative technology of wastewater treatment to reduce the impact of DCF on the environment. Thus, we examined the applicability of pulse-modulated radio-frequency atmospheric pressure glow discharge (pm-rf-APGD) for degradation of 1.56–50.0 mg L-1 DCF from both aqueous solutions and synthetic wastewaters. The removal rates varied from 84.0 ± 3.8% to 100.0 ± 0.1% for the aqueous solution and increased together with the decreasing concentration of DCF. For synthetic wastewaters, the DCF removal was enclosed in the range from 21.0 ± 1.0% to 74.8 ± 0.1%. The energy efficiencies varied from 0.0116 to 0.312 g kW-1h-1 for aqueous solutions and from 0.00779 to 0.0087 g kW-1h-1 for synthetic wastewaters, respectively. By application of ultraperformance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS), the pm-rf-APGD-driven DCF degradation pathways were revealed to involve decomposition, nitration, and dehalogenation reactions yielding dichloroaniline, nitro-diclofenac and 8-chlorocarbazole-1-acetic acid, respectively, before achieving the total decomposition of DCF to carbon dioxide, water, chlorides, nitrates and amines. Notable increases in the contents of the radicals, i.e., H2O2 in addition to NO2- and NO3-, were observed in the plasma-treated DCF solutions in contrast to the controls. Finally, no cytotoxic activity of the pm-rf-APGD-treated DCF solutions was demonstrated on model non-malignant human endothelial cells (HUVEC) and human immortalized keratinocytes (HaCaT). We anticipate that the described continuous-flow pm-rf-APGD-based reaction discharge system might be applied for biosafe removal of DCF from the effluents originating from wastewater treatment plants.

Characterization of cold atmospheric plasma-modified dentin collagen.

The aim of this study was to evaluate the crosslinking effect of the radio-frequency atmospheric-pressure glow discharge (RF-APGD) plasma jet treatment on dentin collagen. The dentin collagen was treated by an RF-APGD plasma jet with the gas temperature of 4°C under different treatment times, while the control was a non-treatment group. The dentin collagen was characterized in terms of atomic force microscopy-based nanoindentation, differential scanning calorimeter, Raman analysis and X-ray photoelectron spectroscopy (XPS) measurement. The crosslinking effect of the plasma-treated dentin collagen was found compared to that of the control group. The elastic modulus and denaturation temperature of the dentin collagen after plasma treatment for 30 s were significantly higher than those in the control group (p<0.05). The RF-APGD plasma jet treatment can promote the crosslinking of the dentin collagen, which is of great significance to improve its mechanical and thermal stabilities.

Application of pulse-modulated radio-frequency atmospheric pressure glow discharge for degradation of doxycycline from a flowing liquid solution.

Doxycycline (DOX), an antibiotic commonly used in medicine and veterinary, is frequently detected in natural waterways. Exposition of bacteria to DOX residuals poses a selective pressure leading to a common occurrence of DOX-resistance genetic determinants among microorganisms, including virulent human pathogens. In view of diminishment of the available therapeutic options, we developed a continuous-flow reaction-discharge system generating pulse-modulated radio-frequency atmospheric pressure glow discharge (pm-rf-APGD) intended for DOX removal from liquid solutions. A Design of Experiment and a Response Surface Methodology were implemented in the optimisation procedure. The removal efficiency of DOX equalling 79 ± 4.5% and the resultant degradation products were identified by High-Performance Liquid Chromatography–Diode Array Detection, Liquid Chromatography Quadruple Time of Flight Mass Spectrometry, Ultraperformance Liquid Chromatography–Tandem Mass Spectrometry, total organic carbon, total nitrogen, Attenuated Total Reflectance Furrier Transform–Infrared, and UV/Vis-based methods. The pm-rf-APGD-treated DOX solution due to the generated Reactive Oxygen and Nitrogen Species either lost its antimicrobial properties towards Escherichia coli ATCC25922 or significantly decreased biocidal activities by 37% and 29% in relation to Staphylococcus haemolyticus ATCC29970 and Staphylococcus aureus ATCC25904, respectively. Future implementation of this efficient and eco-friendly antibiotic-degradation technology into wastewater purification systems is predicted.

Electron dissipation after radio-frequency discharge burst at atmospheric pressure

The discharge characteristics and mechanism of pulse modulated radio frequency (RF) atmospheric pressure glow discharge (APGD) are studied using a two-dimensional self-consistent numerical fluid model. The ignition of an RF discharge burst is demonstrated by the increase in RF current amplitude and evolution of the discharge spatial profile from a bell shape to a double-hump shape. With a time interval of 80 µs between two consecutive RF discharge bursts, the electron dissipation after an RF discharge burst is shown, whose reduction slope changes from 1.7 × 1022 m−3s−1 to 9.1 × 1019 m−3s−1 with a time delay. The corresponding electron dissipation mechanism is proposed to be the electron loss due to reactions in the discharge bulk and the drift of electrons across the discharge gap, which explains the continuum and discrete operation modes in pulse modulated RF APGD.

Application of Oil-in-Water Nanoemulsion Carrying Size-Defined Gold Nanoparticles Synthesized by Non-thermal Plasma for the Human Breast Cancer Cell Lines Migration and Apoptosis

In this work, the gold nanoparticles (AuNPs) were synthesized using pulse-modulated radio-frequency atmospheric pressure glow discharge (pm-rf-APGD). By tailoring selected operating parameters of the pm-rf-APGD reaction-discharge system, the experimental conditions for the synthesis of raw-AuNPs with controlled optical and structural properties were found. The colloidal suspension of the size-controlled raw-AuNPs was mixed with an aqueous solution of gelatine and turmeric oil to produce an oil-in-water (O/W) nanoemulsion. AuNPs loaded into the nanoemulsion were characterized using ultraviolet–visible absorption spectrophotometry, dynamic light scattering, scanning electron microscopy supported by energy dispersive X-ray spectroscopy, and transmission electron microscopy equipped with selected area X-ray diffraction. Additionally, attenuated total reflectance Fourier-transform infrared spectroscopy was used to confirm the efficient functionalization of the AuNPs by nanoemulsion component. It was revealed that AuNPs were mostly spherical with an average size of 4.6 ± 1.0 nm and a face-centered cubic crystal system. The developed O/W nanoemulsion carrying AuNPs was applied towards the human breast cancer cell lines MCF7 and MDA-MB-231. It was found that it exhibited the cytotoxicity towards the breast cancer cells while were non-cytotoxic towards the non-tumour breast cells MCF10A. Moreover, it also inhibited the migration of the invasive cancer breast cells (line MDA-MB-231) and hence, could prevent the breast cancer metastasis.

Characteristics of a radio-frequency cold atmospheric plasma jet produced with a hybrid cross-linear-field electrode configuration

Cold atmospheric plasma (CAP) jet has wide applications in various fields including advanced materials synthesis and modifications, biomedicine, environmental protection and energy saving, etc. Appropriate control on the volume, temperature and chemically reactive species concentrations of the CAP jet is of great importance in actual applications. In this paper, an radio-frequency atmospheric-pressure glow discharge (RF-APGD) plasma generator with a hybrid cross-linear-field electrode configuration is proposed. The experimental results show that, with the aid of the copper mesh located at the downstream of the traditional co-axial-type plasma generator with a cross-field electrode configuration, a linear field between the inner powered electrode of the traditional plasma generator and the copper mesh can be established. This liner-field can, to some extent, enhance the discharges at the upstream of the copper mesh, resulting in small increments (all less than 12.5%) of the species emission intensities, electron excitation temperatures and gas temperatures by keeping other parameters being unchanged. And due to the intrinsic transparent and conducting features of the grounded copper mesh to the gas flowing, electric current and heat flux of the plasma plumes, a plasma region with higher concentrations of chemically reactive species and larger plasma plume diameters is obtained at the downstream of the grounded copper mesh on the same level of the gas temperature and electron excitation temperature compared to those of the plasma free jet. In addition, the charged particle number densities at the same downstream axial location of the grounded copper mesh decrease significantly compared to those of the plasma free jet. This means that the copper mesh is also, to some extent, helpful for separating the chemically reactive neutral species from the charged particles inside a plasma environment. The preceding results indicate that the cross-linear-field electrode configuration of the plasma generator is an effective approach for tuning the characteristics of the RF-APGD plasma jet in order to obtain an appropriate combination of the plasma jet properties with higher chemically reactive species concentrations, especially relative higher number densities of neutral species, larger plasma volumes and lower gas temperatures.

Effect of a novel cold atmospheric plasma jet treatment with different temperatures on resin-dentin bonding

To investigate the effect of different treatment temperatures of a novel cold atmospheric plasma jet treatment on the resin-dentin bonding. (1) Fifty-two freshly extracted, non-carious and intact third molars were collected. The occlusal one-third of the crown was removed by means of a water-cooled low-speed Isomet saw. One dentin disc [(900 ±100) μm] was prepared for each tooth. The fifty-two dentin discs were randomly divided into control group and experimental groups, of which four were in control group, and forty-eight were divided into four experimental groups according to the different treatment temperatures (4 °C, 10 °C, 20 °C and 30 °C) of the novel radio-frequency atmospheric-pressure glow discharge (RF-APGD) plasma jet, twelve in each group. Each experimental group was divided into three subgroups according to different treatment time (10 s, 20 s and 30 s), with four in each subgroup. The occlusal one-third of the crown was removed by means of a water-cooled low-speed Isomet saw. The morphology of demineralized dentin surfaces was analyzed using field emission scanning electron microscopy. (2) Twenty unerupted, non-carious and intact third molars were randomly divided into five groups, four in each group: control group, untreated; 4 °C, 10 °C, 20 °C and 30 °C experimental groups, each group was treated with the RF-APGD plasma jet for 20 s. The micro-tensile resin dentin bond strength was tested after 20 s RF-APGD plasma jet treatment with different temperatures, using a universal mechanical machine. (1) The field emission scanning electron microscopy results indicated that when compared with the control group, a 10 s RF-APGD plasma jet treatment with 30 °C and 20 °C collapsed the collagen scaffold. Collagen fibrils maintained an uncollapsed three-dimensional structure after the 4 °C RF-APGD plasma jet treatment for even 30 s treatment. (2) The microtensile resin dentin bond strength results of the 4 °C RF-APGD plasma jet treatment group (57.8±0.7) MPa were significantly higher than that of the control group [(47.4±0.5) MPa] and 10 s, 20 s and 30 s RF-APGD plasma treatment group [(51.9±0.7) MPa,(29.7±1.0) MPa and (22.2±1.5) MPa] with statistically significant difference (P<0.05). Compared with the control group, the micro-tensile bond strength increased about 21.9% and 9.5% after 4 °C and 10 °C RF-APGD plasma jet treatment, respectively. Compared with other treatment temperatures, this novel RF-APGD plasma jet treatment with the temperature of 4 °C can preserve the three-dimensional morphology of demineralized dentin better, and can improve the resin-dentin bonding.

Electrical features of radio-frequency atmospheric pressure helium discharge with and without dielectric electrodes

A comparative study of radio-frequency atmospheric pressure glow discharge (rf APGD) generated in helium with and without dielectric electrodes to investigate the effect of electrodes insulation on electrical features of APGD is presented. In the α mode, both the rf APGDs remain volumetric, stable and uniform. In the γ mode, the APGD without dielectric electrodes shrinks into a constricted plasma column whereas APGD with dielectric electrodes remains stable and retains the same volume without plasma constriction even at higher densities of discharge current. A comparison of electrical features of both rf APGDs in normal and abnormal glow discharge regimes is presented. In both APGDs with and without dielectric electrodes, impedance measurements have been performed and compared with equivalent circuit models. The measured impedance data is found to be in good agreement with simulated data.

Numerical and Experimental Studies on the Interactions Between the Radio-Frequency Glow Discharge Plasma Jet and the Shielding Gas at Atmosphere

It is a useful method to lengthen the cold atmospheric plasma jet with the aid of gas shielding. In this paper, the interactions between the shielding gas and the radio-frequency atmospheric-pressure glow discharge plasma jet are studied numerically and experimentally. The modeling results show that both the chemical compositions and flowrates of the shielding gas strongly influence the characteristics of the plasma jets. A long helium-shielding plasma jet with a length of 34-35 mm is obtained. The predicted lengths of the plasma shielding jets under specified operating conditions are qualitatively consistent with the experimental measurements.

Effects of a modified cold atmospheric plasma jet treatment on resin-dentin bonding.

The radio-frequency atmospheric-pressure glow discharge (RF-APGD) plasma is a novel cold atmospheric plasma (CAP) source, which has low energy characteristic. This study investigated the effect of RF-APGD plasma on the mechanical properties of dentin collagen and resin-dentin bonding. The scanning electron microscopy analysis was performed before and after a novel RF-APGD plasma and a conventional CAP treatment and a tensile test was carried out for the stiffness of dentin collagen. The microtensile resin-dentin bond strength was tested either immediately or after a 50,000-cycle thermocycling process. Dentin collagen maintained an intact structure after a 45-s RF-APGD plasma treatment, whereas even a 10-s treatment with the conventional CAP collapsed the collagen scaffold. When compared with control groups, the RF-APGD plasma treatment showed: (i) an improved stiffness of dentin collagen; (ii) a significant improvement in the bonding strength before/after artificial aging. Thus, RF-APGD plasma treatment has excellent prospects as a resin-dentin bonding protocol.

Pulse-Modulated Radio-Frequency Alternating-Current-Driven Atmospheric-Pressure Glow Discharge for Continuous-Flow Synthesis of Silver Nanoparticles and Evaluation of Their Cytotoxicity toward Human Melanoma Cells.

An innovative and environmentally friendly method for the synthesis of size-controlled silver nanoparticles (AgNPs) is presented. Pectin-stabilized AgNPs were synthesized in a plasma-reaction system in which pulse-modulated radio-frequency atmospheric-pressure glow discharge (pm-rf-APGD) was operated in contact with a flowing liquid electrode. The use of pm-rf-APGD allows for better control of the size of AgNPs and their stability and monodispersity. AgNPs synthesized under defined operating conditions exhibited average sizes of 41.62 ± 12.08 nm and 10.38 ± 4.56 nm, as determined by dynamic light scattering and transmission electron microscopy (TEM), respectively. Energy-dispersive X-ray spectroscopy (EDS) confirmed that the nanoparticles were composed of metallic Ag. Furthermore, the ξ-potential of the AgNPs was shown to be −43.11 ± 0.96 mV, which will facilitate their application in biological systems. Between 70% and 90% of the cancerous cells of the human melanoma Hs 294T cell line underwent necrosis following treatment with the synthesized AgNPs. Furthermore, optical emission spectrometry (OES) identified reactive species, such as NO, NH, N2, O, and H, as pm-rf-APGD produced compounds that may be involved in the reduction of the Ag(I) ions.

Influences of the cold atmospheric plasma jet treatment on the properties of the demineralized dentin surfaces

Improvement of the bonding strength and durability between the dentin surface and the composite resin is a challenging job in dentistry. In this paper, a radio-frequency atmospheric-pressure glow discharge (RF-APGD) plasma jet is employed for the treatment of the acid-etched dentin surfaces used for the composite restoration. The properties of the plasma treated dentin surfaces and the resin–dentin interfaces are analyzed using the x-ray photoemission spectroscopy, contact angle goniometer, scanning electron microscope and microtensile tester. The experimental results show that, due to the abundant chemically reactive species existing in the RF-APGD plasma jet under a stable and low energy input operating mode, the contact angle of the plasma-treated dentin surfaces decreases to a stable level with the increase of the atomic percentage of oxygen in the specimens; the formation of the long resin tags in the scattered clusters and the hybrid layers at the resin–dentin interfaces significantly improve the bonding strength and durability. These results indicate that the RF-APGD plasma jet is an effective tool for modifying the chemical properties of the dentin surfaces, and for improving the immediate bonding strength and the durability of the resin-dentin bonding in dentistry.

Alpha to Gamma Mode Transitions in Pulse-Modulated Radio Frequency Atmospheric Pressure Glow Discharges

In pulse-modulated (PM) radio frequency (RF) atmospheric pressure glow discharges (APGDs), the alpha–gamma mode transition is analyzed and confirmed with $I$ – $V$ characteristic curve. The behaviors of alpha–gamma mode transition in PM RF APGDs are more complicated than that in continuous wave (CW) RF APGDs. In terms of amplitude of applied RF voltage just before a pulse falling edge ( $V_{\mathrm {appls}}$ ), the critical $V_{\mathrm {appls}}$ at the alpha–gamma mode transition in a PM RF APGD increases with the decreasing duty ratio and is higher than that of a CW RF APGD. The feature of the alpha–gamma mode transition in a PM RF APGD is attributed to the gas temperature rise depending on both the RF voltage and duty ratio. The alpha–gamma mode transition is verified to occur at the initial phase of a PM RF APGD and the onset is earlier at a higher transient RF voltage. As the mode transition occurs, a RF voltage spike is formed in the pulse waveform.

Electric field development in γ-mode radiofrequency atmospheric pressure glow discharge in helium

Time development of electric field strength during radio-frequency sheath formation was measured using Stark polarization spectroscopy in a helium γ-mode radio-frequency (RF, 13.56 MHz) atmospheric pressure glow discharge at high current density (3 A cm−2). A method of time-correlated single photon counting was applied to record the temporal development of spectral profile of He I 492.2 nm line with a sub-nanosecond temporal resolution. By fitting the measured profile of the line with a combination of pseudo-Voigt profiles for forbidden (2 1P–4 1F) and allowed (2 1P–4 1D) helium lines, instantaneous electric fields up to 32 kV cm−1 were measured in the RF sheath. The measured electric field is in agreement with the spatially averaged value of 40 kV cm−1 estimated from homogeneous charge density RF sheath model. The observed rectangular waveform of the electric field time development is attributed to increased sheath conductivity by the strong electron avalanches occurring in the γ-mode sheath at high current densities.

Characteristics in the jet region of helium radio-frequency atmospheric-pressure glow discharge with array generators

The two-dimensional spatially extended atmospheric plasma arrays by many parallel radio-frequency glow discharge plasma jets packed densely, represent a feature option of large-scale low-temperature atmospheric plasma technologies with distinct capability of directed delivery of reactive species and good insusceptibility to sample variations. However, it is still a challenge to form plasma jet with large area of uniform active species on a downstream substrate due to the complex interactions between individual jets. This paper proposes to numerically study the strategy and mechanism of control/modulation for the array discharge to produce two-dimensional plasma uniformity in the downstream working area. In this work, a two dimensional fluid model is employed to investigate the characteristics in the jet region of helium radio-frequency atmospheric-pressure glow discharge (RF APGD) with array generators. The influences of upstream discharge characteristics, gas flow and their cooperative effects on the distribution of species densities, gas temperatures and the uniformity of active species in the material treating area is studied, and the essential strategy for the modulation method is acquired. The results will be significant for deep understanding of coupling behaviors of multiple plasma plumes in the RF APGD array and applications of the technology.

Contrasting Characteristics of Radio-Frequency Atmospheric Argon Discharges With and Without Dielectric Barriers

In this paper, the fundamental characteristics of glow discharge operation modes in radio frequency (RF) atmospheric argon discharges with and without dielectric barriers were studied by experiments. It is found that the RF dielectric-barrier discharge (DBD) in atmospheric argon operates more stable in alpha mode than RF atmospheric pressure glow discharge in argon. The ratios of oxygen and nitrogen to argon are achieved to be 9.5% and 6% in stable RF DBD in atmospheric argon, respectively. The plasmas chemistry, measured by optical emission spectra and intensity, explains that the stable alpha mode discharge range is larger with mixture of oxygen than nitrogen.

Diffuse α-mode atmospheric pressure radio-frequency discharge in neon

In this work, a radio-frequency (RF) atmospheric pressure glow discharge burning in neon between planar metal electrodes is achieved for the first time. The RF discharge can operate in two stable modes: in a diffuse α-mode with uniformly covered electrode surfaces and in a constricted γ-mode. Similarities are revealed when the discharge is compared against the RF atmospheric pressure glow discharge in helium, namely both discharges show a discontinuity and a hysteresis in the current–voltage characteristic at the mode transition; the spatio-temporal profiles of the light emission in the α-mode from neon, helium and atomic oxygen are also similar.

Atmospheric and room temperature plasma (ARTP) as a new powerful mutagenesis tool.

Developing rapid and diverse microbial mutation tool is of importance to strain modification. In this review, a new mutagenesis method for microbial mutation breeding using the radio-frequency atmospheric-pressure glow discharge (RF APGD) plasma jets is summarized. Based on the experimental study, the helium RF APGD plasma jet has been found to be able to change the DNA sequences significantly, indicating that the RF APGD plasma jet would be a powerful tool for the microbial mutagenesis with its outstanding features, such as the low and controllable gas temperatures, abundant chemically reactive species, rapid mutation, high operation flexibility, etc. Then, with the RF APGD plasma generator as the core component, a mutation machine named as atmospheric and room temperature plasma (ARTP) mutation system has been developed and successfully employed for the mutation breeding of more than 40 kinds of microorganisms including bacteria, fungi, and microalgae. Finally, the prospect of the ARTP mutagenesis is discussed.

Influences of gas flowing on the features of a helium radio-frequency atmospheric-pressure glow discharge

In this paper, a zoning model is employed to investigate the influences of gas flowing on the characteristics of the high-purity helium radio-frequency atmospheric-pressure glow discharge (RF APGD) plasma. The modeling results show that the influences of the gas flowing on the plasma features in the discharge region and the jet region are different. In the discharge region, the heavy-particle temperature decreases with the increase of helium flow rate, while the variations of the electron energy and the species concentrations are less than 0.5%. In the plasma jet region, the variation of the heavy-particle temperature shows a non-monotonous form with the gas flow rate, while the species concentrations become higher within a certain distance (e.g., smaller than 2 mm away from the plasma generator exit) at a higher helium flow rate. The modeling results are also qualitatively validated by comparing with the measured gas temperatures in both the discharge region and the plasma jet region.