Ultrasonic Formation of Fe3O4‑Reduced Graphene Oxide−Salicylic Acid Nanoparticles with Switchable Antioxidant Function

We demonstrate a single-step ultrasonic in situ complexation of salicylic acid during the growth of Fe3O4-reduced graphene oxide nanoparticles (∼10 nm) to improve the antioxidant and antiproliferative effects of pristine drug molecules. These nanoparticles have a precisely defined electronic molecular structure with salicylic acid ligands specifically complexed to Fe(III)/Fe(II) sites, four orders of magnitude larger electric surface potential, and enzymatic activity modulated by ascorbic acid molecules. The diminishing efficiency of hydroxyl radicals by Fe3O4-rGO-SA nanoparticles is tenfold higher than that by pristine salicylic acid in the electro-Fenton process. The H+ production of these nanoparticles can be switched by the interaction with ascorbic acid ligands and cause the redox deactivation of iron or enhanced antioxidation, where rGO plays an important role in enhanced charge transfer catalysis. Fe3O4-rGO-SA nanoparticles are nontoxic to erythrocytes, i.e., human peripheral blood mononuclear cells, but surpassingly inhibit the growth of three cancer cell lines, HeLa, HepG2, and HT29, with respect to pristine salicylic acid molecules

Электромагнитная активизация салициловой кислоты в комплексе с оксидированной цинк-графеновой структурой

This work aims at the development of a method of electromagnetic activation of salicylic acid molecules per se (SA) through the ultrasonic (20 kHz) complexation with oxidized zinc-graphene structure. The result of this work implies synthesized nanopartiсles “ZnO – partially restored graphene oxide (rGO) – SA” with the average size of (5.53 ± 0.11) nm and hexagonal wurtzite zinc oxide structure with complexed SA molecules. Complexation of SA with “ZnO – rGO” matrix causes magnification of electromagnetic field of SA by 102 times with the local enhancement at the contact with ZnO by 103 times, and therefore allowing selective electromagnetic activation of drug molecules. The developed method of “ZnO – rGO – SA” nanoparticles formation can be applied to many different drugs and drug-based devices, thereby introducing a great interest in medicinal electronics and nanomedicine.  Представлен метод электромагнитной активизации молекул салициловой кислоты per se (СК) посредством ультразвукового (20 кГц) комплексообразования с оксидированной цинк-графеновой структурой. Результатом разработки явились сформированные наночастицы «ZnO – частично восстановленный кислородсодержащий графен (кГ) – СК» со средним размером (5,53 ± 0,11) нм и гексагональной сингонией типа вюрцита оксида цинка с комплексами молекул салициловой кислоты. Комплексообразование салициловой кислоты с матрицей «ZnO – кГ» приводит к усилению электромагнитного поля салициловой кислоты в 102 раза с локальным увеличением при контакте с ZnO в 103 раза и, как следствие, к избирательной электромагнитной активизации молекул лекарственного вещества. Разработанный метод формирования наночастиц с составом «ZnO – кГ – СК» можно применить ко многим другим лекарственным соединениям и устройствам на их основе, что представляет большой интерес для медицинской электроники и наномедицины.

Potent E. coli M‑17 Growth Inhibition by Ultrasonically Complexed Acetylsalicylic Acid−ZnO−Graphene Oxide Nanoparticles

A single-step ultrasonic method (20 kHz) is demonstrated for the complexation of acetylsalicylic acid (ASA)−ZnO− graphene oxide (GO) nanoparticles with an average size of <70 nm in aqueous solution. ASA−ZnO−GO more e ffi ciently inhibits the growth of probiotic Escherichia coli strain M-17 and exhibits enhanced antioxidant properties than free ASA and ASA−ZnO in neutralization of hydroxyl radicals in the electro-Fenton process. This improved function of ASA in the ASA −ZnO GO can be attributed to the well-de fi ned cone-shaped morphology, the surface structure containing hydroxyl and carboxylate groups of ZnO−GO nanoparticles, which facilitated the complexation with ASA

Vertically oriented graphene based walls and columns obtained by ICP CVD method on moving substrates as prior stage of the roll-to-roll technology

Superior optoelectronic properties of graphene have made this material as a special applicant in displays, touch and graphene-based screens with smaller and long-lasting batteries including the field of mobile telephony. Recently we have introduced the process for the formation of vertically oriented graphene (VOG) walls with a curved morphology by ICP CVD method. Such VOG walls represent a very promising material for different applications (e.g. miniature batteries and other optoelectronic devices) due to its unique orientation and open carbon network structure. For the first time such VOG walls have been grown directly on a moving substrate that is a prerequisite for its production by the roll-to-roll technology providing higher yield of the production process at lower cost of the product

Properties of Nitrogen/Silicon Doped Vertically Oriented Graphene Produced by ICP CVD Roll-to-Roll Technology

Simultaneous mass production of high quality vertically oriented graphene nanostructures and doping them by using an inductively coupled plasma chemical vapor deposition (ICP CVD) is a technological problem because little is understood about their growth mechanism over enlarged surfaces. We introduce a new method that combines the ICP CVD with roll-to-roll technology to enable the in-situ preparation of vertically oriented graphene by using propane as a precursor gas and nitrogen or silicon as dopants. This new technology enables preparation of vertically oriented graphene with distinct morphology and composition on a moving copper foil substrate at a lower cost. The technological parameters such as deposition time (1–30 min), gas partial pressure, composition of the gas mixture (propane, argon, nitrogen or silane), heating treatment (1–60 min) and temperature (350–500 °C) were varied to reveal the nanostructure growth, the evolution of its morphology and heteroatom’s intercalation by nitrogen or silicon. Unique nanostructures were examined by FE-SEM microscopy, Raman spectroscopy and energy dispersive X-Ray scattering techniques. The undoped and nitrogen- or silicon-doped nanostructures can be prepared with the full area coverage of the copper substrate on industrially manufactured surface defects. Longer deposition time (30 min, 450 °C) causes carbon amorphization and an increased fraction of sp3-hybridized carbon, leading to enlargement of vertically oriented carbonaceous nanostructures and growth of pillars

Sonochemical Formation of Copper/Iron-modified Graphene Oxide Nanocomposites for Ketorolac Delivery

A feasible sonochemical approach is described for the preparation of copper/iron-modified graphene oxide nanocomposites by using ultrasound (20 kHz, 18 W/cm2) in aqueous solution containing copper and iron ion precursors. Unique copper-, copper/iron- and iron-modified graphene oxide nanocomposites have a submicron size that is smaller than pristine GO and a higher surface area enriched with Cu2O, CuO, Fe2O3 of multiform phases (α-, β-, ε- or γ), FeO(OH) and sulfur- or carbon-containing compounds. These nanocomposites are sonochemically intercalated with the nonsteroidal anti-inflammatory drug ketorolac resulting in formation of nanoscale carriers. Ketorolac monotonically disintegrates from these nanoscale carriers in aqueous solution adjusted to pH from 1 to 8. The disintegration of ketorolac proceeds at a slower rate from the copper/iron-modified graphene oxide at increased pH, but at a faster rate from the iron-modified graphene oxide starting from acidic conditions

The properties of the sonochemically functionalized nonsteroidal anti-inflammatory drug ketorolac in an Fe3O4–graphene oxide nanocomposite

Metallodrugs are in clinical use for the treatment of some diseases. A feasible sonochemical method is described for the complexation of the nonsteroidal anti-inflammatory drug, ketorolac, with an Fe3O4–graphene oxide nanocomposite. The extraction of ketorolac from this nanocomposite was studied in aqueous solutions at pH = 1, 5 and 8, imitating the gastrointestinal medium

Ultrasonic Formation of Copper/Iron Graphene Oxide for Ketorolac Delivery

New accessible sonochemical methods were developed for the functionalization of synthesized graphene oxide (GO) with copper/iron compounds and drug intercalation into their structure in aqueous solution at ambient conditions by using ultrasound (20 kHz) treatment. The sonochemical formation mechanism of a new nanomaterial was revealed through the structural analysis of three types of nanocomposites: (i) copper@graphene oxide, (ii) copper/iron@-graphene oxide and (iii) iron@graphene oxide. Unique copper/iron-modied graphene oxide nanocomposites can be used as nanocarriers for the anti-in°ammatory drug (ketorolac) delivery in aqueous solution due to the reduced submicron size and enlarged surface area. Disintegration of the ultrasonically intercalated ketorolac followed the exponential decay curve fit at higher pH values of the aqueous solution with a higher decay constant observed in copper/iron-modifed graphene oxide nanocomposites

Sonochemically Assembled Photoluminescent Copper Modified Graphene Oxide Microspheres

New accessible sonochemical assembly method is developed for the preparation of photoluminescent oil-filled silica@CuS/Cu2O/CuO-GO microspheres with green, yellow and red colors of emitted light. This method is based on the ultrasonic emulsification of a biphasic mixture consisting of CuS/Cu2O/CuO-graphene oxide (GO) nanocomposites with polyvinyl alcohol (PVA) (aqueous phase) and tetraethyl orthosilicate with sunflower oil (organic phase). CuS/Cu2O/CuO-GO nanocomposites are composed of sonochemically formed three phases of copper: covellite CuS (p-type semiconductor), cuprite Cu2O (Bloch p-type semiconductor) and CuO (charge transfer insulator). The photoluminescence property of microspheres results from the H-bridging between PVA and CuS/Cu2O/CuO-GO nanostructures, light absorption ability of Cu2O and charge transfer insulation by CuO. Substitution of PVA by S-containing methylene blue quenches fluorescence by enhanced dye adsorption on CuS/Cu2O/CuO-GO because of CuS and induced charge transfer. Non-S-containing malachite green is in non-ionized form and tends to be in the oil phase, prohibiting the charge transfer on CuS/Cu2O/CuO-GO

Воздействие ультразвука на нестероидные противовоспалительные лекарства в комплексных соединениях нанокомпозитов на основе оскидов меди, железа, цинка и графена

This work aims at the formation of nanocomposites based on graphene and metal oxides (copper-iron, zinc and iron) through ultrasonic interaction (20 kHz) and investigation of their electromagnetic properties by scanning electron microscopy, Raman and absorption spectroscopy, and fluorescence methods. The output of this work implies the development of a single-step ultrasound method to form functional Cu/Fe-, ZnO-and Fe3O4-polyvinyl alcohol nanocomposites, and the ultrasonic conjugation of these nanocomposites with pristine drugs, such as ketorolac and acetylsalicylic acid. We established that formed Cu/Fe-graphene-ketorolac, ZnO-grapheneacetylsalicylic acid and Fe3O4-ketorolac obtain optical and superparamagnetic properties of nanoparticles with improved electromagnetic characteristics due to ultrasonic conjugation. Cu/Fe-graphene-ketorolac nanocomposites are revealed to have a spherical shape (&lt; 100 nm) and acquire improved optoelectronic properties due to copper and iron atoms in the matrix of graphene. It is demonstrated that ZnO-graphene-acetylsalicylic acid nanocomposites obtain properties of fluorescence mainly for electromagnetic interaction with the ZnO phase formed on the surface of graphene. Ultrasonic conjugation of ketorolac with magnetite proved to increase the electron density of Fe3O4-ketorolac that obtains superparamagnetic properties, and its biocompatibility can be improved when coated with polyvinyl alcohol. In general, formed nanocomposites are of great interest in medical electronics and nanomedicine as functional materials with electromagnetic properties being controlled at the molecular and atomic levels. Such nanocomposites can also find application as components in electronic devices for diagnosis and treatment of serious inflammatory disorders. Industries will find the singlestep ultrasound method of special interest because it is eco-friendly and can be scaled up by a versatile spectrum of inorganic and organic materials and drugs.Целью работы является формирование нанокомпозитов на основе оксидированного графена и оксидов металлов (медь-железо, цинк и железо) посредством взаимодействия с ультразвуком (20 кГц) и исследование их электромагнитных свойств с помощью методов сканирующей электронной микроскопии, спектроскопии комбинационного рассеяния света, поглощения электромагнитного излучения и флуоресценции. Результатом работы является разработка одношагового метода ультразвука для формирования функциональных нанокомпозитов Cu/Fe-, ZnO- и Fe3O4-поливиниловый спирт и метода ультразвукового коньюгирования исходных лекарственных соединений, таких как кеторолак и ацетилсалициловая кислота, с данными нанокомпозитами. Установлено, что сформированные лекарственные нанокомпозиты Cu/Fe-графен-кеторолак, ZnO-графен-ацетилсалициловая кислота и Fe3O4-кеторолак приобретают оптические и суперпарамагнитные свойства наночастиц с улучшенными электромагнитными характеристиками благодаря ультразвуковой коньюгации. Выявлено, что нанокомпозиты Cu/Fe-графен-кеторолак имеют сферическую форму и размер, не превышающий 100 нм, на поверхности послойной структуры оксидированного графена. Сформированные нанокомпозиты Cu/Fe-графен-кеторолак приобретают улучшенные оптоэлектронные свойства благодаря наличию атомов меди и железа в матрице графена. Показано, что нанокомпозиты ZnO-графен-ацетилсалициловая кислота приобретают улучшенные свойства флуоресценции преимущественно за счет электромагнитного взаимодействия с фазой оксида цинка, сформированной на поверхности графена. Доказано, что коньюгирование кеторолака с магнетитом увеличивает электронную плотность нанокомпозита Fe3O4-кеторолак, который приобретает суперпарамагнитные свойства, а его покрытие поливиниловым спиртом может улучшить биосовместимость. В целом сформированные нанокомпозиты представляют большой интерес в области медицинской электроники и наномедицины в качестве функциональных материалов с улучшенными электромагнитными свойствами, контролируемыми на молекулярном и атомном уровне. Данные нанокомпозиты могут найти применение как в качестве материалов, так и компонентов в электронных устройствах для диагностики и лечения воспалительных заболеваний. Для промышленной области особый интерес представляет одношаговый экологически чистый метод ультразвука, применение которого можно расширить разнообразным спектром неорганических и органических материалов и лекарственных веществ