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Influence of molecular weight of polycation polydimethyldiallylammonium and carbon nanotube content on electric conductivity of layer-by-layer films

2022, Neuber, Sven, Sill, Annekatrin, Efthimiopoulos, Ilias, Nestler, Peter, Fricke, Katja, Helm, Christiane A.

For biological and engineering applications, nm-thin films with high electrical conductivity and tunable sheet resistance are desirable. Multilayers of polydimethyldiallylammonium chloride (PDADMA) with two different molecular weights (322 and 44.3 kDa) and oxidized carbon nanotubes (CNTs) were constructed using the layer-by-layer technique. The surface coverage of the CNTs was monitored with a selected visible near infrared absorption peak. Both the film thickness and the surface coverage of the CNTs increased linearly with the number of CNT/PDADMA bilayers deposited (film thickness up to 80 nm). Atomic force microscopy images showed a predominantly surface-parallel orientation of CNTs. Ohmic behavior with constant electrical conductivity of each CNT/PDADMA film and conductivity up to 4 · 103 S/m was found. A change in PDADMA molecular weight by almost a factor of ten has no effect on the film thickness and electrical conductivity, only the film/air roughness is reduced. However, increasing CNT concentration in the deposition dispersion from 0.15 up to 0.25 mg/ml results in an increased thickness of a CNT/PDADMA bilayer (by a factor of three). The increased bilayer thickness is accompanied by a decreased electrical conductivity (by a factor of four). The decreased conductivity is attributed to the increased monomer/CNT ratio.

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Spontaneous fluctuations in a plasma ion assisted deposition – correlation between deposition conditions and vanadium oxide thin film growth

2021, Frank, Anna, Dias, Miguel, Hieke, Stefan, Kruth, Angela, Scheu, Christina

In this work correlations between thin film crystallinity of plasma ion assisted electron beam evaporated vanadium oxide (VOx) and fluctuations of the deposition parameters during the growth process could be observed by in situ monitoring deposition conditions and electron microscopy studies. In the presented case, unintentional fluctuations in the gas flow at the plasma source caused by inhomogeneous melting of the target material lead to an increase in discharge current and therefore a decrease of the oxygen flow in the plasma source, resulting in the formation of highly crystalline bands due to a temporary increase in energy flux. The major part of the VOx thin film consists of a large number of nanocrystals embedded in an amorphous phase. In-depth structural analysis confirms a mixture of V2O5, in different modifications, VO2, as well as the mixed-valence oxides V4O9 and V6O13, for nanocrystalline parts and crystalline bands. These differ mainly in the degree of crystallinity being influenced by variations in discharge current, and partly in the amount of higher oxidized vanadium oxides. In future, precisely controlled variation of plasma source conditions will open up pathways to control and tailor crystallinity of electron beam evaporated thin films, allowing for production methods for patterned thin films or layers with graduated crystallinity. This may give rise to a new class of coatings of nanohybrids combining amorphous VOx with low electrical conductivity and crystalline domains providing a higher electrical conductivity which is useful for electrochromic displays, smart windows, and solar cells.

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Platelets are key in cold physical plasma-facilitated blood coagulation in mice

2017, Bekeschus, Sander, Brüggemeier, Janik, Hackbarth, Christine, Woedtke, Thomas von, Partecke, Lars-Ivo, van der Linde, Julia

Purpose: Surgical interventions inevitably lead to destruction of blood vessels. This is especially dangerous in anticoagulated patients. Electrocauterization is a frequently used technique to seal incised tissue. However, leading to a superficial layer of necrotic tissue, the treated area evolves a high vulnerability to contact, making it prone to detachment. As a result, dangerous postoperative bleeding may occur. Cold physical plasma was previously suggested as a pro-coagulant treatment method. It mainly acts by expelling a delicate mixture of oxidants. We therefore tested the suitability of an atmospheric pressure plasma jet (kINPen MED) as a new medical device for sufficient blood coagulation in a murine model of liver incision. Methods: Plasma treatment of murine blood ex vivo induced sufficient coagula. This effect did not affect any tested parameter of plasmatic coagulation cascade, suggesting the mechanism to be related to cellular coagulation. Indeed, isolated platelets were significantly activated following exposure to plasma, although this effect was less pronounced in whole blood. To analyze the biological effect of plasma-on blood coagulation in vivo, mice were anticoagulated (clopidogrel inhibiting cellular and rivaroxaban inhibiting plasmatic hemostasis) or received vehicle only. Afterwards, a partial resection of the left lateral liver lobe was performed. The quantification of the blood loss after liver incision followed by treatment with kINPen MED plasma or electrocauterization revealed a similar and significant hemostatic performance in native and rivaroxaban but not clopidogrel-treated animals compared to argon gas-treated controls. In contrast to electrocauterization, kINPen MED plasma treatment did not cause necrotic cell layers. Conclusion: Our results propose a prime importance of platelets in cold physical plasma-mediated hemostasis and suggest a clinical benefit of kINPen MED plasma treatment as coagulation device in liver surgery.

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First insights on plasma orthodontics - Application of cold atmospheric pressure plasma to enhance the bond strength of orthodontic brackets

2016, Metelmann, Philine H., Quooß, Alexandra, Woedtke, Thomas von, Krey, Karl-Friedrich

Objective: The development of an ideal adhesive system has long been subject of research. Recent studies show that treatment with cold atmospheric pressure plasma (CAP) positively affects the bonding properties of enamel. Conditioning with CAP could therefore improve the mechanical and physical properties of bracket adhesives, e.g. Glass ionomer cement (GIC). Material and methods: Laser-structured brackets (Dentaurum, Ispringen) were bonded onto 60 bovine mandibular incisors using different orthodontic adhesives. For 20 specimens FujiOrthoLC (GC America Corp, Alsip, USA) was used according to manufacturer's instructions. Another 20 specimens received a 60 s CAP-treatment (kINPen med, Neoplas tool, Greifswald, Germany) before bracket bonding, of which 10 were re-moistened before applying FujiOrthoLC and 10 remained dry. Onto 20 specimens, brackets were bonded with the Composite Transbond XT (3M/Unitek, St. Paul, USA) following manufacturer's instructions. The shear bond strength of brackets on the teeth was determined with the universal testing machine Zwick BZ050/TH3A (Zwick, Ulm, Germany). Results: Brackets bonded with FujiOrthoLC in standard method, showed average shear bond strength of 5.58±0.46 MPa. Specimens treated with plasma showed clinically unacceptable adhesion values (re-moistened group: 2.79±0.38 MPa, dry group: 1.01±0.2 MPa). Bonding onto dried out teeth also led to spontaneous bracket losses (4 of 10 specimens). The composite group (Transbond XT) showed clinically acceptable adhesion values (7.9±1.03 MPa). Conclusions: Despite promising potential, surface conditioning with CAP could not improve the adhesive properties of GIC. By contrast, a decrease in shear bond strength was noticed after CAP treatment. Further investigations have to show whether it is possible to increase the retention values ​​of other orthodontic adhesives by CAP application and thus take advantage of positive characteristics and reduce side effects.

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Liquid assisted plasma enhanced chemical vapour deposition with a non-thermal plasma jet at atmospheric pressure

2016, Schäfer, Jan, Fricke, Katja, Mika, Filip, Pokorná, Zuzana, Zajíčková, Lenka, Foest, Rüdiger

The present study introduces a process for the synthesis of functional films onto substrates directly from the liquid phase. The reported method is based on the initialization of the synthesis by means of an atmospheric pressure plasma jet operating with argon above a thin liquid film of the starting material. The process is demonstrated by the formation of a thin, solid SiOx film from siloxane-based liquid precursors. Changes in the chemical properties of the precursor were studied in-situ during the polymerization process on the diamond crystal by using Fourier transform infrared spectroscopy The elemental composition of the SiOxCy films was analyzed by X-ray photoelectron spectroscopy (XPS). Furthermore, XPS was applied to study the effect of post-annealing processes on the composition of the films. The obtained deposits exhibit a low concentration of carbon groups. The amount of hydroxyl groups and interstitial water can be reduced significantly by post-process annealing of the films.

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Significance of the Resonance Condition for Controlling the Seam Position in Laser-assisted TIG Welding

2016, Emde, B., Huse, M., Hermsdorf, J., Kaierle, S., Wesling, V., Overmeyer, L., Kozakov, R., Uhrlandt, D.

As an energy-preserving variant of laser hybrid welding, laser-assisted arc welding uses laser powers of less than 1 kW. Recent studies have shown that the electrical conductivity of a TIG welding arc changes within the arc in case of a resonant interaction between laser radiation and argon atoms. This paper presents investigations on how to control the position of the arc root on the workpiece by means of the resonant interaction. Furthermore, the influence on the welding result is demonstrated. The welding tests were carried out on a cooled copper plate and steel samples with resonant and non-resonant laser radiation. Moreover, an analysis of the weld seam is presented.

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Can the effect of cold physical plasma-derived oxidants be transported via thiol group oxidation?

2019, Heusler, Thea, Bruno, Giuliana, Bekeschus, Sander, Lackmann, Jan-Wilm, Woedtke, Thomas von, Wende, Kristian

Purpose: Intra- and intercellular redox-signaling processes where found responsible in various physiological and pathological processes with cellular thiol groups as important signal transducers. Using cold atmospheric plasma (CAP), a similar oxidation pattern of thiol groups can be achieved. Hence, it must be clarified which role extracellular thiol groups play in mediating CAP effects and whether or not the effects of short-lived reactive species can be preserved in a molecule like cysteine. Methods: Physiological buffer solutions containing the amino acid cysteine were treated by an MHz argon plasma jet with molecular gas admixtures (kINPen) and transferred to cultured human keratinocytes. Cell proliferation, migratory activity, and metabolism were investigated. High-resolution mass spectrometry was used to estimate the impact of plasma generated species on thiol groups. Results: While treated physiologic cysteine concentrations showed no impact on cell behavior, artificially high concentrations decreased proliferation, migration and lactate secretion. GSH levels inside cells were stabilized. Conclusion: Extracellular thiol groups scavenge plasma-generated species and form a multitude of covalent modifications. Unexpectedly, human keratinocytes show only small functional consequences for treated physiologic cysteine concentrations. Results for high concentrated cysteine solutions indicate an improved cytostatic/cytotoxic impact by plasma treatment suggesting a potential application as a “preserving agent” of the chemical energy of plasma-derived species. © 2019 The Authors

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Targeting malignant melanoma with physical plasmas

2018, Pasqual-Melo, Gabriella, Gandhirajan, Rajesh Kumar, Stoffels, Ingo, Bekeschus, Sander

Melanoma is the deadliest form of cutaneous neoplasia. With a five-year survival rate of only 5–19%, metastatic melanoma presents severe challenges in clinical therapies. In addition, palliation is often problematic due to large numbers of fast growing metastasis. This calls for new therapeutic avenues targeting highly aggressive melanoma in palliative patients. One recently suggested innovative approach for eradication of topical tumor lesions is the application of cold physical plasma. This partially ionized gas emits a cocktail of reactive oxygen and nitrogen species (ROS/RNS). ROS/RNS have been shown to be a double-edged sword in fueling cancer growth at low doses but abrogating it at higher doses. The ROS/RNS output of plasma devices is tunable, and many studies have successfully decreased cancer cell growth in vitro and tumor burden in vivo. In general, increasing numbers of clinical trials suggest combination therapies to outperform monotherapies with regard to prognosis in patients. This review describes current challenges in melanoma treatment and highlights the concept of plasma therapy in experimental studies performed in melanoma research. Future perspectives are given that combine the usage of physical plasma with e.g. chemotherapy, immunotherapy, and ionizing radiation in melanoma medical oncology.

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Medical gas plasma augments bladder cancer cell toxicity in preclinical models and patient-derived tumor tissues

2022, Gelbrich, Nadine, Miebach, Lea, Berner, Julia, Freund, Eric, Saadati, Fariba, Schmidt, Anke, Stope, Matthias, Zimmermann, Uwe, Burchardt, Martin, Bekeschus, Sander

Introduction: Medical gas plasma therapy has been successfully applied to several types of cancer in preclinical models. First palliative tumor patients suffering from advanced head and neck cancer benefited from this novel therapeutic modality. The gas plasma-induced biological effects of reactive oxygen and nitrogen species (ROS/RNS) generated in the plasma gas phase result in oxidation-induced lethal damage to tumor cells. Objectives: This study aimed to verify these anti-tumor effects of gas plasma exposure on urinary bladder cancer. Methods: 2D cell culture models, 3D tumor spheroids, 3D vascularized tumors grown on the chicken chorion-allantois-membrane (CAM) in ovo, and patient-derived primary cancer tissue gas plasma-treated ex vivo were used. Results: Gas plasma treatment led to oxidation, growth retardation, motility inhibition, and cell death in 2D and 3D tumor models. A marked decline in tumor growth was also observed in the tumors grown in ovo. In addition, results of gas plasma treatment on primary urothelial carcinoma tissues ex vivo highlighted the selective tumor-toxic effects as non-malignant tissue exposed to gas plasma was less affected. Whole-transcriptome gene expression analysis revealed downregulation of tumor-promoting fibroblast growth factor receptor 3 (FGFR3) accompanied by upregulation of apoptosis-inducing factor 2 (AIFm2), which plays a central role in caspase-independent cell death signaling. Conclusion: Gas plasma treatment induced cytotoxicity in patient-derived cancer tissue and slowed tumor growth in an organoid model of urinary bladder carcinoma, along with less severe effects in non-malignant tissues. Studies on the potential clinical benefits of this local and safe ROS therapy are awaited.

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Potentiating anti-tumor immunity with physical plasma

2018, Bekeschus, Sander, Clemen, Ramona, Metelmann, Hans-Robert

The age of checkpoint blockage emphasizes the importance of adaptive antitumor immune responses. This arm of immune defense is key in recognizing molecules via specific receptors to distinguish between self and foreign or mutated structures. Antigen-specific T-cells identify non-self epitopes, tumor-associated antigens, or neoepitopes on tumors to carry out attacks on malignant cells. Although tumor cells are immunogenic by nature, they have developed strategies to evade an immune response that would otherwise facilitate their clearance. Several steps in antitumor immunity utilize the toxic and signaling properties of reactive oxygen and nitrogen species (ROS/RNS). Cold physical plasmas are potent generators of such ROS/RNS and are demonstrated to have profound antitumor activity in vitro and in vivo. Here we discuss recent evidence and concepts on how plasmas may boost immunity against pathological cells. Specifically, plasma treatment may enhance the immunogenicity of tumor cells by induction of the immunogenic cancer cell death (ICD) and redox regulation of the antigen-presenting machinery. These aspects provide a rationale for localized plasma-based onco-therapies enhancing systemic antitumor immunity, which eventually may target distant tumor metastasis in cancer patients in a T-cell dependent fashion.