Further progress in the characterisation of complex radiation fields

One of the topics which forms part of CONRAD project addresses the problems related to the dosimetry of complex-mixed radiation fields at workplaces. This topic was included in work package (WP) 6. WP 6 was established to co-ordinate research activities in two areas:the development of new techniques and the improvement of current techniques for characterisation of complex workplace fields (including high-energy fields and pulsed fields): measurement and calculation of particle energy and direction distributions (Subgroup A); and model improvements for dose assessment of solar particle events (Subgroup B). In both cases in order to aid the research, WP 6 increases the efficiency of resource utilisation, and facilitates the technology transfer to practical application and for the development of standards. This contribution presents a general overview of activities of SG A; specific results related to the benchmark experiment at GSI Darmstadt are presented separately, and will be published in other way. As far as the results acquired in the frame of the SG B activities, these are presented in the meeting held as part of EURADOS AM 2008.     

Monolithic porous polymer layer for the separation of peptides and proteins using thin-layer chromatography coupled with MALDI-TOF-MS

Plates for thin-layer chromatography (TLC) with an attached layer of porous polymer monolith have been prepared and used for the separation of small molecules, peptides, and proteins. The 50-200-mum. thin poly(butyl methacrylate-co-ethylene dimethacrylate) layers were prepared in situ using UV-initiated polymerization. Precise control of the reaction conditions enables the preparation of monolithic layers with a well-defined porous structure that determines the chromatographic performance. Compared to conventional TLC and high-performance TLC using precoated layers based on silica, the small layer thickness and absence of any binder is expected to improve both retention characteristics and separation efficiency of the polymer-based monolithic thin-layer chromatographic plates. Spots of the separated compounds were first detected using typical UV imaging. Since the monolithic thin layers can be also prepared directly on the stainless steel MALDI carrier plate, the separation in TLC format can be coupled with MALDI-TOF-MS. Application of a conventional MALDI matrix facilitated desorption and ionization of peptides and proteins for molecular weight determination of the separated compounds.     

New CSPs based on peptidomimetics: efficient chiral selectors in enantioselective separations

Summary Two different families of peptidomimetics have been synthesized and used as chiral selectors for enantioselective chromatography. The functionalization of compounds with multiple nitrogen atoms allows their use in the preparation of chiral stationary phases (CSPs), with acrylic or styril comonomers, in both bead and monolithic formats. Some of these separation media, having the appropriate morphological properties for their use in chromatographic columns, were able to efficiently discriminate enantiomers of aminoacid derivatives and pharmaceuticals such as Oxazepam. Received: 24 September 2001/Revised version: 2 January 2002/ Accepted: 21 January 2002     

Implementation of best available techniques in the sanitation of relict burdens

The paper deals with the elimination of highly toxic and persistent relict burdens caused by polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, hexachlorobenzene, γ-isomer of hexachlorocyclohexane and other organic halogen derivatives. The technology is used in eliminating the aforementioned contaminants from soil, rubble and metal parts of former machinery with the use of best available techniques. Such a technology has been implemented in the northern part of the town of Neratovice and the Spolana company, plc, which formerly used to be a significant producer of pesticides in the Czech Republic.     

Microwave-Enhanced Thermal Desorption of Polyhalogenated Biphenyls from Contaminated Soil

The effect of microwave (MW) field on the rate of thermal desorption of polychlorinated biphenyls (PCBs) from long-term contaminated soil was examined in the laboratory environment. For these purposes a modified MW oven was used, with a uniformly extended MW field and a power consumption of 200–600 W. The weight of the soil samples was 100 g, the sum of concentrations of seven indicative congeners of PCB Nos. 28, 52, 101, 118, 153, 138, and 180 was, on average, 264 mg/kg of dry matter. It was experimentally proven that the efficiencies of PCB desorptions were high, over 99.9%. The maximal desorption temperature of 600°C was reached within 15–17 min. It came to light that the presence of alkaline additives in the soil (such as carbonates and alkaline metal hydroxides) did not have an apparent effect on the desorption of PCBs under those conditions. The results concerning the efficiency of PCB separations are in agreement with our previous findings regarding the efficiency of thermal desorption without using MWs in the pilot (input 35 kg) and industrial (input 15 t) desorption chambers with a stationary layer of the same type of contaminated soil. The main disadvantage of experiments with thermal desorption without the action of MWs was the low rate of heating up the soil. This study was focused to solve the problem of contamination in a complex way; we also studied the effect of MWs on the rate of the deterioration of the separated PCBs in aqueous condensates, the deterioration of PCBs in contaminated waste water containing alkaline agents (soda and lye), and on the catalytic reductive dechlorination of PCBs in the system Pd supported on active coal with sodium formate as the hydrogen donor. Experiments with the MW-enhanced catalytic reductive oxidation show over 98.5% reduction in the concentration of PCBs. An important and new finding is the more than 98% reduction in the concentration of PCBs when the MW field was applied on the contaminated water into which only 2.5% of Na2CO3 was added. Further studies on possible influences of MWs on the reaction kinetic are needed. Meanwhile we attribute the positive MW effects to their thermal properties rather than to their influence on the reaction mechanism.     

Chemical Composition and Mechanical Characteristic of Nitrogen Ion Beam Mixed Carbon Nanolayer

Ion beam methods for modification of nanohardness of surface nanolayers of the titanium alloy Ti6AI4V were applied. After deposition of carbon nanolayers by electron beam evaporation, the ion implantation of nitrogen into samples was carried out. The chemical composition of the modified surface area was investigated by AES （auger electron spectroscopy）. The nanohardness of resulted ion beam modified surface nanolayers were investigated by nanoindentation testing. The measured concentration profiles indicate the atomic mixing of carbon into the substrate. It was found that the modified samples had a markedly higher nanohardness than the unmodified samples. The increased nanohardness is attributed to the newly created phases in the surface area.     

Lipid Nanoparticles for Broad-Spectrum Nucleic Acid Delivery

Lipid nanoparticles (LNPs) are the most advanced nonviral modality for nucleic acid (NA) delivery, and have recently gained enormous attention in the fields of RNA therapeutics and vaccine development. Here, ionizable adamantane-based lipidoids named XMaNs, which circumvent the usual need for laborious optimization of LNP components for highly diverse types of NAs, are described. The non-toxic XMaN6 lipidoid is highly versatile in entrapment and delivery of siRNA, mRNA, plasmid DNA, and a cyclic dinucleotide. XMaN6-based LNPs efficiently deliver: 1) siRNA into human primary hepatocytes and cell lines that are hard-to-transfect; 2) mRNA into mouse liver; 3) plasmid DNA; 4) 2′,3′-cGAMP into cells and activated the cGAS-STING pathway three orders of magnitude more efficiently than 2′,3′-cGAMP alone. To our knowledge, such universality in delivering different NA types has not been previously described and can accelerate translation of LNPs into the clinic.     

Hierarchical Micro‐ and Mesoporous Zn‐Based Metal–Organic Frameworks Templated by Hydrogels: Their Use for Enzyme Immobilization and Catalysis of Knoevenagel Reaction

Encapsulation of enzymes in metal–organic frameworks (MOFs) is often obstructed by the small size of the orifices typical of most reported MOFs, which prevent the passage of larger‐size enzymes. Here, the preparation of hierarchical micro‐ and mesoporous Zn‐based MOFs via the templated emulsification method using hydrogels as a template is presented. Zinc‐based hydrogels featuring a 3D interconnecting network are first produced via the formation of hydrogen bonds between melamine and salicylic acid in which zinc ions are well distributed. Further coordination with organic linkers followed by the removal of the hydrogel template produces hierarchical Zn‐based MOFs containing both micropores and mesopores. These new MOFs are used for the encapsulation of glucose oxidase and horseradish peroxidase to prove the concept. The immobilized enzymes exhibit a remarkably enhanced increased operational stability and enzymatic activity with a k_cat/k_m value of 85.68 mm s^–1. This value is 7.7‐fold higher compared to that found for the free enzymes in solution, and 2.7‐fold higher than enzymes adsorbed on conventional microporous MOFs. The much higher catalytic activity of the mesoporous conjugate for Knoevenagel reactions is demonstrated, since the large pores enable easier access to the active sites, and compared with that observed for catalysis using microporous MOFs.     

Microfabricated devices: A new sample introduction approach to mass spectrometry

Instrument miniaturization is one way of addressing the issues of sensitivity, speed, throughput, and cost of analysis in DNA diagnostics, proteomics, and related biotechnology areas. Microfluidics is of special interest for handling very small sample amounts, with minimal concerns related to sample loss and cross-contamination, problems typical for standard fluidic manipulations. Furthermore, the small footprint of these microfabricated structures leads to instrument designs suitable for high-density, parallel sample processing, and high-throughput analyses. In addition to miniaturized systems designed with optical or electrochemical detection, microfluidic devices interfaced to mass spectrometry have also been demonstrated. Instruments for automated sample infusion analysis are now commercially available, and microdevices utilizing chromatographic or capillary electrophoresis separation techniques are under development. This review aims at documenting the technologies and applications of microfluidic mass spectrometry for the analysis of proteomic samples.