Oleh Smutok

Clarkson University · Department of Chemistry & Biomolecular Science

This study investigates the controlled release of α-chymotrypsin from an alginate hydrogel matrix. When protein molecules entrapped in the hydrogel matrix have a size smaller than the hydrogel pores, their hold/release in/ from the polymer matrix is controlled by the electrostatic interaction between the guest molecules and host polymer. α-Chymotry...

β-Glucosidase (EC 3.2.1.21) from sweet almond was encapsulated into pH-responsive alginate−polyethylenimine (alginate−PEI) hydrogel. Then, electrochemically controlled cyclic local pH changes resulting from ascorbate oxidation (acidification) and oxygen reduction (basification) were used for the pulsatile release of the enzyme from the composite hy...

The past decade has demonstrated an increasing interest in the development of new magnetic systems for bioanalytical and biomedical purposes. Due to their magnetic properties, such systems are very well controllable, resulting in the development of accurate approaches for testing many human biomarkers in clinical diagnostics and for the controlled...

Network properties on local free volume and biosensor parameters of polymers based on acrylated epoxidized soybean oil (AESO), a combination of AESO with vanillin dimethacrylate (VDM) in ratio 1:0.25 mol, and its combination with vanillin diacrylate (VDA) with the same molar ratio, used as laccase-holding matrixes for the construction of amperometr...

The paper provides a detailed overview of heterogeneous chemical reactions leading to the electrode surface modification and further reactivity of various functionalized surfaces. Notably, the present paper is different from other typical reviews and books about chemically modified electrodes—it is not aimed at highlighting the recent achievements...

A metal‐organic framework (MOF), ZIF‐8, which is stable at neutral and slightly basic pH values in aqueous solutions and destabilized/dissolved under acidic conditions was loaded with a pH‐insensitive fluorescent dye, rhodamine‐B isothiocyanate, as a model payload species. Then, the MOF species were immobilized at an electrode surface. The local (i...

Binary operating (YES/NO) biosensors based on unconventional biocomputing concept represent a novel approach to the analysis of various biomarkers and environmental signals. The binary biosensors with implemented Boolean logic process analyte input signals using chemical means without electronic computers. They can be used for extension of the anal...

In this work, the influence of aromatic rings on the local free volume of cured mixtures of acrylate epoxidized soybean oil (AESO) and vanillin dimethacrylate (VDM) was investigated. Cross-linking took place under the influence of UV light in the presence or absence of a photoinitiator. The local free volume and its homogeneity were characterized u...

The paper provides a detailed overview of the scientific background, mostly published in 1970s–1990s, which resulted in tremendous success in preparation of modified electrodes, later used for bioelectrochemical, (bio)catalytic, photoelectrocatalytic, and other applications. The systems overviewed in the paper are focused on the chemisorption of su...

The construction and assembly of artificial allosteric protein switches into information and energy processing networks connected to both biological and non-biological systems is a central goal of synthetic biology and bionanotechnology. However, designing protein switches with the desired input, output and performance parameters is challenging. He...

Here we describe a multianalyte biosensor platform for fluorescent analysis of different human state biomarkers (α-amylase, phenylalanine, glucose, lactate/pyruvate, alcohol) and some immunosuppressive drugs (cyclosporine A, tacrolimus, methotrexate, rapamycin) using chimeric PQQ-and natural NAD+-dependent enzymes. The principle of the approach is...

The development of controlled “Smart” drug release systems is one of the leading directions of modern biomedicine. Electrochemically-triggered payload release has a number of advantages as a fast and well-controlled approach. However, it has serious drawbacks for practical application as the integration of the electrodes into living organisms is an...

This review is a historic collection of old electrochemical and electroanalytical instruments, mostly concentrated on polarographs, potentiostats, pH meters, and titrators designed and commercially available from the 1920s to 1970s. The review briefly explains their operation and shows their photos. It is addressed to electrochemists who want to kn...

Protein biosensors hold a promise to transform the way we collect physiological data by enabling quantification of biomarkers outside of specialized laboratory environment. However, achieving high specificity and sensitivity in homogeneous assay format remains challenging. Here we report construction of fluorescent biosensor arrays based on artific...

The hybrid periodic mesoporous organosilica (PMO) with APTES/DAR Schiff-based precursor 3-aminopropyltriethoxysilane (APTES) and 4,6-diacetylresorcinol (DAR) was synthesized in the presence of a structure-directing agent cetyltrimethylammonium bromide and tetraethoxysilane. Then, Pd (II) ions, as well as Pd nanoparticles, were incorporated inside t...

This review provides a general overview of different biosensors, mostly concentrating on electrochemical analytical devices, while briefly explaining general approaches to various kinds of biosensors, their construction and performance. A discussion on how all required components of biosensors are brought together to perform analytical work is offe...

The electrochemically controlled release of proteins was studied in a Ca2+-cross-linked alginate hydrogel deposited on an electrode surface. The electrochemical oxidation of ascorbate or reduction of O2 was achieved upon applying electrical potentials +0.6 or -0.8 V (vs Ag/AgCl/KCl 3 M), respectively, resulting in decreasing or increasing pH locall...

A micro/nanoshaped system composed of alginate microspheres (microgels) decorated with silica oxide nanoparticles functionalized with nitroavidin was used for on-demand biomolecule release stimulated by different input signals. Enzymes preloaded in the microgels processed the applied signals producing either basic pH locally near the microspheres o...

Precision analysis of the key biological metabolites such as L-lactate has great practical importance for many technological processes in food technology, including beverage production. Here we describe a new, highly selective, and sensitive biosensor for accurate L-lactate assay based on a combination of peroxidase-mimetic nanozymes with microbial...

Electrochemically‐triggered payload release as a potential method for signal‐responsive “smart drug” development has been increasingly utilized in the field of modern pharmaceuticals. Among the various approaches to design electrochemically‐triggered payload release systems, the basis of using electrochemical reactions to develop sensing and releas...

The Cover Feature illustrates a multichannel biosensing device with the optical output recorded and processed with a smartphone for performing logic operations. More information can be found in the Research Article by Yacob Melman, Evgeny Katz and Oleh Smutok.

The investigated polymeric matrixes consisted of epoxidized linseed oil (ELO), acrylated epoxidized soybean oil (AESO), trimethylolpropane triglycidyl ether (RD1), vanillin dimethacrylate (VDM), triarylsulfonium hexafluorophosphate salts (PI), and 2,2-dimethoxy-2-phenylacetophenone (DMPA). Linseed oil-based (ELO/PI, ELO/10RD1/PI) and soybean oil-ba...

A new nano-structured platform for fluorescent analysis using PQQ-dependent glucose dehydrogenase (PQQ-GDH) was developed, particularly using a smartphone for transduction and quantification of optical signals. The PQQ-GDH enzyme was immobilized on SiO2 nanoparticles deposited on glass microfiber filter paper, providing a high load of the biocataly...

Local pH changes were produced upon electrochemical reactions. Cyclic application of reductive and oxidative potentials resulted in formation of pH waves in the form of distinct solution layers. Multiple layers with basic and acidic pH values were visualized with a fluorescent confocal microscope following fluorescence of pH-dependent dyes.

Bovine serum albumin (BSA), used as a model protein, was immobilized at a buckypaper electrode by formation of pH-sensitive affinity bonds produced between avidin/iminobiotin or nitroavidin/biotin. Local (interfacial) pH was changed electrochemically. The pH was decreased upon electrochemical oxidation of ascorbate or increased upon electrochemical...

Concatenated enzyme‐based Boolean logic gates activated with 5 chemical input signals were analyzed with a smartphone photo camera. Simultaneous detection of 32 input combinations was conveniently performed using enzyme‐modified fiberglass sensing spots generating fluorescence with different intensities for the 0 and 1 binary outputs. The developed...

The search for new nanoscale materials with predictable properties to target the timely and fast detection of toxic components in wastewater is one of the most promising directions of modern biosensorics. We have shown that TiO2 nanoparticles modified with sulfur significantly improve the main operational parameters of laccase-based electrodes when...

We propose a novel approach to develop, validate and demonstrate new electrochemical methods and corresponding devices for global analysis of the redox state of biological systems. The study included methods and associated devices developed at three levels of complexity: i) modified electrodes for electrochemical analysis of individual biological r...

Advances in protein engineering resulted in increased efforts to create protein biosensors that can replace instrumentation-heavy analytical and diagnostic methods. Sensitivity, amenability to multiplexing, and manufacturability remain to be among the key issues preventing broad utilization of protein biosensors. Here, we attempt to address these b...

Gold screen printed electrodes (Au‐SPEs) were treated electrochemically to produce a micro‐rough pattern increasing the real electrode surface. The procedure included electrochemical deposition of Au layers onto the surface of the Au‐SPEs, followed by a reductive process at ‐3 V (vs. Ag/AgCl) leading to formation of H2 bubbles, which produced pores...

The latest trends in analytical technology are focused on the development of miniaturized, portable systems for on-site analysis of the most important human health biomarkers. These analytical devices should be sensitive, selective, cheap, and simple in usage for the end-point user. Here we describe the construction of a new L-phenylalanine biosens...

The biocatalytic activity of electrode-immobilized luciferase followed by bioluminescence emitted from the electrode surface was reversibly tuned and switched by applying electrochemical signals. When a reductive potential (-0.9 V vs. Ag/AgCl) was applied, O2 was consumed at the electrode resulting in its depletion in a thin film near the electrode...

Immobilized avidin–biotin complexes were used to release biotinylated (bio)molecules upon producing local pH changes near an electrode surface by electrochemical reactions. Nitro-avidin complex with biotin was dissociated by increasing local pH with electrochemical O2 reduction. Avidin complex with iminobiotin was split by decreasing local pH with...

A nanostructured surface composed of SiO2 nanoparticles (200 nm) deposited on fiberglass was used as a platform for immobilization of NAD⁺-dependent enzymes (alcohol and glucose dehydrogenases). The surface functionalized with the enzymes was further loaded with NAD(P)⁺cofactor and 1-methoxy-5-methylphenazinium methyl sulfate (MPMS) redox species....

A biocatalytic cascade based on concerted operation of pyruvate kinase and luciferase with a bioluminescent output was switched reversibly between the low and high activity by applying external magnetic field at different positions or removing it. The enzymes participating in the reaction cascade were bound to magnetic nanoparticles to allow their...

Among the known types of electrochemical biosensors, the third generation based on an ability of some enzymes to direct electron transfer (DET) is the most promising one. The enzyme property to DET is depending on its capability to electron transfer from enzymatically reduced built-in native cofactor (FMN, FAD, PQQ or heme) to the conductive surfac...

Protein biosensors play an increasingly important role as reporters for research and clinical applications. Here we present an approach for the construction of fully integrated but modular electrochemical biosensors based on the principal component of glucose monitors PQQ‐glucose dehydrogenase (PQQ‐GDH). We designed allosterically regulated circula...

Natural evolution produced polypeptides that selectively recognize chemical entities and their polymers, ranging from ions to proteins and nucleic acids. Such selective interactions serve as entry points to biological signaling and metabolic pathways. The ability to engineer artificial versions of such entry points is a key goal of synthetic biolog...

The development of new approaches for monitoring of the dangerous substances in environment is a topical present problem to improve human life quality. In this point of view, electrochemical biosensors have received increased attention due to their high specificity, sensitivity, reliability, portability and simplicity in operation. Nowadays, there...

Lactic acid, being in natural L‐form, is an almost universal metabolite of all living organisms. It is also an important biotechnological product used as a food additive, component of many industrial products, pharmaceuticals, cosmetics and, recently, as a monomer for the production of biodegradable poly‐L‐lactate. D‐Lactate is another stereoisomer...

The DNA-release activated by light in the self-powered bioelectronic system has been studied. The system was composed of two connected electrodes: one photo-active electrode was modified with photosynthetic thylakoid membranes and another electrode was modified with O2-reducing bilirubin oxidase and nanoparticles functionalized with molecules chang...

Protein biosensors play an increasingly important role as reporters for research and clinical applications. Here we present an approach for the construction of fully integrated but modular electrochemical biosensors based on the principal component of glucose monitors PQQ‐glucose dehydrogenase (PQQ‐GDH). We designed allosterically regulated circula...

Alginate composite hydrogels that exhibit highly sensitive stimuli‐responsive behavior were used for signal‐stimulated release of pre‐loaded insulin. The alginate pores, particularly located at the periphery, were blocked by interpenetration of polyvinyl alcohol (PVA) cross‐linked with 1,3‐benzenediboronic acid (IPN), thus, significantly reducing u...

A biocompatible drug delivery system with a high-sensitive stimuli-responsive behavior is reported. Calcium alginate hydrogels interpenetrated with polyvinyl alcohol–diboronate polymer network (IPN) effectively respond to the presence of hydrogen peroxide through oxidative degradation of boronate esters. The degradation of the IPN entails the reope...

Liver fibrosis is a major cause of morbidity and mortality worldwide due to chronic liver damage and leading to cirrhosis, liver cancer, and liver failure. To date, there is no effective and specific therapy for patients with hepatic fibrosis. As a result of their various advantages such as biocompatibility, imaging contrast ability, improved tissu...

Ultrasensitive biomarker sensing has been used to develop novel strategies in detecting early stage cancer. Due to their unique characteristics, ie, ease of synthesis, conductivity and bio-compatibility, iron magnetic nanoparticles (MNPs) are exceptional nanomaterial in theragnostics. The current review focuses the critical role of iron MNPs in the...

The biopolymer matrix synthesized from acrylated epoxidized soybean oil (AESO) and vanillin dimethacrylate (VDM) was examined using the positron annihilation lifetime spectroscopy (PALS) and the amperometry. The matrix version with DMPA (2,2-dimethoxy-2-phenylacetophenone) admix- ture was also tested in order to check the influence of the admixture...

Alcohol oxidase (EC 1.1.3.13; AOX) is a flavoprotein that catalyzes the oxidation of primary short-chain alcohols to corresponding carbonyl compounds with a concomitant release of hydrogen peroxide. It is a key enzyme of methanol metabolism in methylotrophic yeasts, catalyzing the first step of methanol oxidation to formaldehyde.Here we describe th...

Flavocytochrome b2 (EC 1.1.2.3; l-lactate cytochrome: c oxidoreductase, FC b2) from the thermotolerant methylotrophic yeast Ogataea polymorpha is a thermostable enzyme—prospective for a highly selective l-lactate analysis in the medicine, nutrition sector, and quality control of commercial products. Here we describe the construction of FC b2 produc...

In this study two hybrid organic–inorganic ureasilicate monomers with different length of polymer segments were chosen for preparation of sol–gel material that includes two moieties blended on the molecular scale. The first monomer was obtained by crosslinking a double terminated polyoxyalkyleneamine with an isocyanate modified silicone ethoxide an...

Development of artificial enzymes, including nanozymes as an alternative for non-stable and expensive natural enzymes, is a booming field of modern Biosensorics and Biofuel Technology. In this study, we describe fabrication and characterization of sensitive biosensors for the detection of ethanol and glucose based on new micro/nanocomposite electro...

Development of artificial enzymes, including nanozymes as an alternative for non-stable and expensive natural enzymes, is a booming field of modern Biosensorics and Biofuel Technology. In this study, we describe fabrica- tion and characterization of sensitive biosensors for the detection of ethanol and glucose based on new micro/ nanocomposite elec...

Continuous environmental monitoring and human health diagnostics are important tasks of modern science. We are developing multifunctional biosensor equipment for solving these problems. It is essential that the appropriate devices are multifunctional, highly sensitive and convenient for practical use in everyday life and industrial conditions. As a...

The current review is devoted to nanozymes, i.e., nanostructured artificial enzymes which mimic the catalytic properties of natural enzymes. Use of the term “nanozyme” in the literature as indicating an enzyme is not always justified. For example, it is used inappropriately for nanomaterials bound with electrodes that possess catalytic activity onl...

The procedure of enzyme immobilization in biosensorics has a purpose to induce maximal activity of biological element with sufficient stability and reusability of the bioelectrodes. The entrapment of the biomaterial with a porous solid matrix looks most promising in this respect due to minimal alteration of enzyme structure and behavior. On the oth...

In this study, we describe the fabrication of sensitive biosensor for the detection of phenolic substrates using laccase immobilized onto two types of microporous carbon fibers (CFs). The main characteristics of microporous CFs used for preparation of biosensors are given. Two CFs were characterized by different specific surface area, CFA (<1 m2·g−...

Amperometric laccase-based biosensors of the third generation for analysis of phenol derivates were constructed using the ureasil and photocross-linked polymers as a holding matrix. The knowledge of the properties of the microstructure of such polymer materials is important in terms of optimizing the regulated properties of the amperometric biosens...

Synthesis of gold nanoparticles (Au-NPs) was performed using method of an inorganic chemical reduction. The synthesized Au-NPs showed an intensive surface plasmon resonance band at 525 nm that is typical for corresponding Au-NPs reported in literature. The structural and morphology characterizations of the obtained Au-NPs were carried out using SEM...

Detection of the lactate content is of great importance in clinical diagnostics, fermentation industry, and control of the quality of food products. The work was aimed at the development of a sensitive element of the amperometric biosensor, based on enzyme lactate oxidase and carbon electrodes modified with platinum and palladium nanoparticles (Pt&...

Laccase-based amperometric enzyme biosensors of the third generation for analysis of phenol derivates have been constructed using graphite rods (type RW001) as working electrodes and the photocross-linked polymers as a matrix. Such matrix consisted of epoxidized linseed oil (ELO), bisphenol A diglycidyl ether (RD) as reactive diluent and 50% mixtur...

Laccase-based amperometric enzyme biosensors of the third generation for analysis of phenol derivates have been constructed using graphite rods (type RW001) as working electrodes and the photocross-linked polymers as a matrix. Such matrix consisted of epoxidized linseed oil (ELO), bisphenol A diglycidyl ether (RD) as reactive diluent and 50% mixtur...

During the recent decades, a lot of data about the significance of D‐lactate determination in food technology and quality control has been accumulated. Nowadays, the development of new methods for the determination of D‐lactate is very relevant, especially with regards to biosensors. To construct a D‐lactate‐selective biosensor, we suggest using th...

A new method of isolation, purification, and stabilization of L-lactate: cytochrome c oxidoreductase (EC 1.1.2.3; flavocytochrome b2, FC b2) from the cells of recombinant yeast Ogataea (Hansenula) polymorpha “tr1” (gcr1 catX CYB2) has been developed and physico-chemical characterization of purified preparations has been done. The strain is characte...

The optimization of conditions for synthesis of D-lactate : cytochrome c oxidoreduc­tase (EC 1.1.2.4; DLDH) by recombinant yeast strain Ogataea (Hansenula) polymorpha “tr6” (gcr1 catX Δcyb2/DLD1) was performed. The strain is characterized by impairement of glucose catabolic repression, deletion of the CYB2 gene, responsible for the synthesis of L-l...

Ureasil and ureasil-chalcogenide glass composites of different history (fresh and aged during 1 year) were used for the immobilization of laccase and the construction of amperometric biosensors. A correlation between the microscopical free-volume of the polymer matrices as revealed by low-temperature positron annihilation lifetime spectroscopy and...

Специфічні властивості наноматеріалів відкривають широкі можливості для створення нових продуктів із цінними характеристиками і практичним значенням: ефективних каталізаторів, сенсорних елементів, діагностичних препаратів, фармацевтичних засобів. Однією із основних особливостей наночастинок (НЧ) є висока хімічна активність, що обумовлена їх підвище...

Science; medicine; clinical diagnostics; biotechnologies, including those in food and beverage industries; as well as environmental technologies need highly selective, sensitive, rapid, and reliable methods of identifying the key ingredients or metabolites which determine the quality of the product or serve as markers for diseases, the physiologica...

Fabrication and characterization of a new amperometric chemosensor for accurate formaldehyde analysis based on platinized gold electrodes is described. The platinization process was performed electrochemically on the surface of 4 mm gold planar electrodes by both electrolysis and cyclic voltamperometry. The produced electrodes were characterized us...

Lactic acid (L-lactate) is among the most important analytes since it is a universal metabolite of nearly all the living organisms. The determination of the L-lactate level is used in clinical diagnostics of hypoxia, lactic acidosis, some acute heart diseases, in drug toxicity tests as well as in sports medicine, while monitoring the athletic perfo...

The aim of this work was the construction of a novel non-invasive electrochemical biosensor of the third generation for L-lactate based on yeast flavocytochrome b2 immobilized onto gold nanoclusters.

Innovative amperometric biosensors for monitoring the level of wastewater pollution have been constructed on the surface of the gold planar electrodes C220AT " DropSens " by using the organic–inorganic ureasil-based composites as host matrixes and immobilized commercial laccase from Trametes versicolor. It was found that the biosensor based on the...

Development of selective, sensitive and simultaneously, inexpensive methods for analysis of practically important analytes - biomarkers of diseases and indicators of pharmaceuticals and food quality is an actual problem nowadays. Among of these biomarkers L-lactate plays an important role as an universal metabolite of almost all living organisms. P...

Development of selective, sensitive and simultaneously, inexpensive methods for analysis of practically important analytes - biomarkers of diseases and indicators of pharmaceuticals and food quality is an actual problem nowadays. Among of these biomarkers L-lactate plays an important role as an universal metabolite of almost all living organisms. P...

The development of simple cost-effective sensitive enzymatic methods for analysis of toxic metallic ions is an actual problem. Promising tools for elaboration of such methods are Mn 2+-dependent enzymes. A novel manga-nese(II)-sensitive amperometric bi-enzyme biosensor based on of recombinant human arginase I (arginase) isolated from the gene-engin...

Flavocytochrome b 2 (fcb2) (EC 1.1.2.3) is a 4 × 58 kD homotetrameric FMN and heme containing enzyme localized in the intermembrane space of yeast mitochondria. During the catalysis, FMN oxidizes L-lactate to pyruvate. Subsequently, the reduced FMN trans­ fers electrons to the heme cofactor, which subsequently reduces cytochrome c. The kinetic prop...

D-lactate is a natural component of many fermented foods like yogurts, sour milk, cheeses, and pickles vegetable products. D-lactate in high concentrations is toxic for children and people with short bowel syndrome and provokes encephalopathy. These facts convincingly demonstrate a need for effective tools for the D-lactate removal from some food p...

D-lactate is a natural component of many fermented foods like yogurts, sour milk, cheeses, and pickles vegetable products. D-lactate in high concentrations is toxic for children and people with short bowel syndrome and provokes encephalopathy. These facts convincingly demonstrate a need for effective tools for the D-lactate removal from some food p...

АМПЕРОМЕТРИЧНИЙ ХЕМОСЕНСОР ДЛЯ АНАЛІЗУ ФОРМАЛЬДЕГІДУ Реферат: Амперометричний хемосенсор для аналізу формальдегіду у стічних водах, фармацевтичних препаратах містить графітовий електрод. Поверхню електроду покривають електрохімічно осадженою платиною і з метою підвищення селективності до формальдегіду процес окислення проводять при низькому потенц...

Patent of Ukraine 45283. 10.11.2009. Bul. Vol. № 21.

In Book: “Investigations on Sensor Systems and Technologies”. Edited by Anna V. El’skaya, Vitaliy D. Pokhodenko, - Kyiv: Institute of Molecular Biology and Genetics of NAS of Ukraine, 2006. – 51-57 p.

International PCT Patent (No PCT/US2008/069637)

In Book: “Investigations on Sensor Systems and Technologies”. Edited by Anna V. El’skaya, Vitaliy D. Pokhodenko, - Kyiv: Institute of Molecular Biology and Genetics of NAS of Ukraine, 2006. – 5-12 р.

In the recent years, nanotechnology is the most developing branch due to a wide variety of potential applications in biomedical, biotechnological and agriculture fields. The binding nanoparticles with various biological molecules makes them attractive candidates for using in sensor technologies. The particularly actual is obtaining the bionanomembr...

Hexavalent chromium Cr(VI) is widely used in different branches of industry. Cr(VI)-containing products include chromate pigments in dyes, inks, and plastics. Chromates are used in the production of stainless steel, textile dyes, wood preservation, leather tanning, and as anti-corrosion agents. Thus, soluble Cr(VI)-pollutants are distributed in was...