WORKSHOP

In the framework of the research infrastructure NanoEnviCz novel nanomaterials were synthesized for the application in environmental photocatalysis and catalysis, photoelectrochemistry and sensorics.
An optimized quantitative electrophoretic deposition technique was developed for the preparation of composite graphene oxide/titanium dioxide porous layers. Compared to the pristine TiO2, the composite layers exhibited a three-fold increase in the degradation reaction rate with almost complete mineralization of chlorophenols. Owing to their stability and photocatalytic performance, these layers are suitable for a broad range of environmental applications.
Significant achievements have been reached in organization of the 2D graphene carbon layers into 3D graphene like materials offering unique potential for adsorption and catalytic applications relevant for environmental protection. A new class of 3D graphene catalysts was created characterized by outstanding high both specific surface area and thermal stability.
Heavy-fermion compound Ce2PdIn8 was synthesized which exhibits superconducting behavior with Tc ranging from 0.4 to 0.7 K. Combination of litography and FIB microstructuring, which allowed to precisely measure electrical resistivity, showed different Tc along different crystalographic directions, due to strain induced by substrate-sample coupling.
The first systematic study of the attachment of a donor-acceptor organic chromophore to the surface of H-terminated boron-doped diamond surface was carried out. An improved photochemical grafting protocol was developed leading to a three-fold enhancement in photocurrent on comparable diamond electrodes.
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

The NanoEnviCz project is a great infrastructure project which proposes to study the materials from a different point of view. The project opens an easy way how to get in contact with a professional person who has experience in the field of nanomaterials and nanotechnologies for environmental protection. The applicant has excellent opportunities to apply for the chemical analyses with large scale of instrumentation, morphology measurements, toxicology studies and everything within one infrastructure.
The results of selected applied projects were from different fields. There were studied the methodologies for preparation of thin films with magnetic properties where the XRD powder diffraction and AFM were used as basic methods. The 2D nanomaterials as graphene oxide were studied in solvents miscible with water as an important information for further application in the next project. In this case additional techniques were used to characterize the samples. Other interesting project was on the topic of binary oxides which were prepared and characterized by support of infrastructure and the part of the catalytic studies was done by the home institution. Finally, few of diploma theses were partly supported by this project for the special preparation of the samples as glass, solidified aluminium alloys, metal materials as titanium etc.
The IIC CAS is offering within the NanoEnviCZ the technics as for example: FTIR+DRIFT, HRSEM, HRTEM, Photocatalytic degradation in liquid phase, Surface Area and Pore Size Analyzer-BET etc.
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

Techniques based on solid phase microextraction (SPME) represent a large part of green sample preparation techniques in organic analysis, ranging from pollutants, pesticides and their metabolites to residual pharma and personal care products, flavours, toxins of microbial origin and other biomarkers [1], [2]. Even if SPME based techniques lack the exceptional performance (accuracy, preciseness) of exhaustive extraction techniques, they currently draw attention due to low solvent consumption and high degree of possible automation. Both main separation platforms, liquid and gas chromatography, can today be coupled to sophisticated samplers, that can independently conduct operations as buffer or internal standard additions, derivatizations, sample shaking, heating and cooling, SPME extractions and finally sample injections.
There is a wide spectrum of SPME “geometries” or “configurations” containing a common feature: polymeric sorbent in a form of thin film coating, fibres, particles or a micromonolith. Next to these traditional SPME configurations, some minor modifications such as “arrow” SPME or cold fiber (CF SPME) appeared recently, as well as new concepts like dispersed magnetic nanoparticles (d SPME) and stir bar sorptive extraction (SBSE) [3]. Traditional fibre or blade design of the sorbent support are changed to small magnetic particles or immersed bars.
The two main topics researched at TUL in SPME area will be covered in presentation: utilization of thermally stable polymers in a form of nanofibers for fibre SPME and magnetic particles for d SPME. There is an ongoing research of electrospun polymeric nano/micro fibres for fibre GC-MS-SPME design at TUL [4]. Polyetherimide (PEI), polyethersulfone (PES) and polysulfone (PSU) analytic long-term performance tests were finished and results can be compared to classic PDMS and PDMS/DVB fibres. On the other hand, analytic utilization of para- or diamagnetic particles for SPME related purposes is right at its beginning.
REFERENCES: [1] G. Ouyang and J. Pawliszyn, “SPME in environmental analysis,” Anal. Bioanal. Chem., vol. 386, no. 4, pp. 1059-1073, May 2006.; [2] C.-H. Xu, G.-S. Chen, Z.-H. Xiong, Y.-X. Fan, X.-C. Wang, and Y. Liu, “Applications of solid-phase microextraction in food analysis,” TrAC Trends Anal. Chem., vol. 80, pp. 12-29, Jun. 2016.; [3] N. Reyes-Garcés et al., “Advances in Solid Phase Microextraction and Perspective on Future Directions,” Anal. Chem., vol. 90, no. 1, pp. 302-360, Jan. 2018.; [4] V. Antoš et al., “Polyetherimide Nanofibres as Sorbents for Organochlorinated Pesticides Determination,” J. Nanomater., vol. 2016, p. e1390345, Jun. 2016; [5] M. Assis, E. Cordoncillo, R. Torres-Mendieta, H. Beltran, G. Minguez-Vega, A.F. Gouveia, E. R. Leite, J. Andrés and E.Longo, Phys. Chem. Chem. Phys., 2018.

Currently, there are 13 ongoing projects and 8 finalized projects within Workpackage 9 focused on the adverse effects of NPs and using equipment involved in NanoEnviCz. This year we will demonstrate the results of the succesful international project using the research infrastructure and analyzing the effects of ultrafine particles in diesel exhaust (DEP). Exposure to (DEP) is carcinogenic in humans. Exposure to DEP is also associated with respiratory and cardiovascular diseases. The project aimed to assess biological effect markers related to occupational exposure to DEP in Norwegian tunnel finishing workers (TFW). TFW (n=69) and referents (n=69) were investigated for PAH-DNA adducts (postlabeling) and deregulated miRNAs (RNA-sequencing) in peripheral blood mononuclear cells (PBMC), as well as altered circulating free arachidonic acid (AA) and eicosanoid profiles in plasma (LC/MS/MS). PBMC from TFW showed significantly higher levels of PAH-DNA adducts compared with referents. Levels of PAH-DNA adducts were also related to smoking habits in both groups. 16 miRNAs were significantly deregulated in TFW. Several of these miRNAs are related to carcinogenesis, apoptosis and antioxidant effects. Analysis of miRNA-gene targets reveal deregulation of pathways associated with cancer, alterations in lipid molecules and focal adhesion. Plasma profiles show higher levels of free AA, PGF2α, and 15-HETE, and lower levels of PGD2 in TFW compared with referents. Occupational exposure to DEP is associated with biological alterations in TFW potentially affecting lung homeostasis, inflammation status and the cardiovascular system.
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

Functional nanofibrous membranes have been prepared for antimicrobial air filtration and for medical applications (wound cover and tissue engineering). Polyamid 6 and dodecyltrimethyl ammomnium bromide as antimicrobial agent was used to prepare electrospun nanofibrous membrane for air filtration. Effect of modifying agent on spinning conditions, morphology of nanofibres and utility properties of membrane have been analysed. Special air blowing tests have been used to demonstrate the stability of antimicrobial activity during air filtration.
For medical applications we developed the composite membrane (PEO, chitosan, gelatine) stabilized by photocroslinking. This membrane is designed to cover wounds with possibility to anchor the drug molecules on nanofibers with gradual release.
Biosensors for liquid biopsy and circulating tumor cell analysis in body fluids have been developed i.e. development of novel microdevices for detection of protein markers and circulating tumor cells in blood (or urine) of patients by use of recombinant protein binders.
Nanocrystalline metal oxides and metallo-organic compounds (“reactive sorbents”) have been synthesized for destruction of highly toxic chemicals including chemical warfares.
For environmental applications we prepared the magnetically separable sorbents and investigated unusual high-temperature ferromagnetic behaviour of non-magnetic metal oxides.
For applications in bio-sciences and medicine we optimized the preparation of cerium oxide capable of biologically and environmentally relevant interactions.
The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

In this contribution, the exceptional properties and applications of a broad scale of carbon materials including graphene derivatives, carbon dots, and hybrid carbon nanostructures will be presented as examples of the collaborative research recently (2018) realized with various partners while exploiting the facilities of “NANOENVICZ” Research Infrastructure [1-8]. The possibilities of the state-of-the-art techniques enabling a complex description of properties, reactivity, and applicability of carbon based materials will be demonstrated. Different concepts towards high-performance supercapacitors based on ultrathin hierarchical porous carbon and zwitterionic network of covalently functionalized graphene with molecular systems will be discussed [2,3]. Special attention will be devoted to the development of carbon quantum dots with controllable photoluminescence, which provide a high application potential in advanced bio-imaging and theranostics [4,5]. The composites of reduced graphene oxide with selenium will be highlighted as hybrid materials exhibiting stable and high-capacity sodium storage [6]. Finally, a new strategy allowing to control the graphene magnetism through the sheet morphology will be presented [7]. Such a strategy extends currently used approaches based on nano-architecture of edges, imprinting of defects/dopants into a 2D structure or controlled sp3 functionalization [8].
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.
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