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Aiming toward a novel, noninvasive technique, with a real-time potential application in the monitoring of the complexation of steroidal neuromuscular blocker drugs Vecuronium ( Vec ) and Rocuronium ( Roc ) with sugammadex ( SDX , medication for the reversal of neuromuscular blockade induced by Vec or Roc in general anesthesia), we developed proof-of-principle methodology based on surface-enhanced Raman spectroscopy (SERS). Silver nanoparticles prepared by the reduction of silver ions with hydroxylamine hydrochloride were used as SERS-active substrates, additionally aggregated with calcium nitrate as needed. The Vec and Roc SERS spectra were obtained within the biorelevant 5 × 10 -7 -1 × 10 -4 M range, as well as the SERS of SDX , though the latter was observed only in the presence of the aggregating agent. SDX /drug complexes at a 1/1 molar ratio revealed significant spectral changes in the vibrational bands of the SDX glucose rings and the drug steroid rings, implying that the insertion of Vec and Roc molecules into the SDX cavity was not only driven by attractive electrostatic interactions between the positively charged cyclic unit of the drug and the negative carboxylate groups of cyclodextrin but also supported by hydrophobic interactions between the host cyclodextrin and the guest drug molecule. The observed changes in SERS signals are applicable in biorelevant conditions and support further studies of SDX /drug complexes in vivo.

Since 2010, EURADOS Working Group 9 (Radiation Dosimetry in Radiotherapy) has been involved in the investigation of secondary and scattered radiation doses in X-ray and proton therapy, especially in the case of pediatric patients. The main goal of this paper is to analyze and compare out-of-field neutron and non-neutron organ doses inside 5- and 10-year-old pediatric anthropomorphic phantoms for the treatment of a 5-cm-diameter brain tumor. Proton irradiations were carried out at the Cyclotron Centre Bronowice in IFJ PAN Krakow Poland using a pencil beam scanning technique (PBS) at a gantry with a dedicated scanning nozzle (IBA Proton Therapy System, Proteus 235). Thermoluminescent and radiophotoluminescent dosimeters were used for non-neutron dose measurements while secondary neutrons were measured with track-etched detectors. Out-of-field doses measured using intensity-modulated proton therapy (IMPT) were compared with previous measurements performed within a WG9 for three different photon radiotherapy techniques: 1) intensity-modulated radiation therapy (IMRT), 2) three-dimensional conformal radiation therapy (3D CDRT) performed on a Varian Clinac 2300 linear accelerator (LINAC) in the Centre of Oncology, Krakow, Poland, and 3) Gamma Knife surgery performed on the Leksell Gamma Knife (GK) at the University Hospital Centre Zagreb, Croatia. Phantoms and detectors used in experiments as well as the target location were the same for both photon and proton modalities. The total organ dose equivalent expressed as the sum of neutron and non-neutron components in IMPT was found to be significantly lower (two to three orders of magnitude) in comparison with the different photon radiotherapy techniques for the same delivered tumor dose. For IMPT, neutron doses are lower than non-neutron doses close to the target but become larger than non-neutron doses further away from the target. Results of WG9 studies have provided out-of-field dose levels required for an extensive set of radiotherapy techniques, including proton therapy, and involving a complete description of organ doses of pediatric patients. Such studies are needed for validating mathematical models and Monte Carlo simulation tools for out-of-field dosimetry which is essential for dedicated epidemiological studies which evaluate the risk of second cancers and other late effects for pediatric patients treated with radiotherapy., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Knežević, Stolarczyk, Ambrožová, Caballero-Pacheco, Davídková, De Saint-Hubert, Domingo, Jeleń, Kopeć, Krzempek, Majer, Miljanić, Mojżeszek, Romero-Expósito, Martínez-Rovira, Harrison and Olko.)

Purpose: Craniospinal irradiation (CSI) has greatly increased survival rates for patients with a diagnosis of medulloblastoma and other primitive neuroectodermal tumors. However, as it includes exposure of a large volume of healthy tissue to unwanted doses, there is a strong concern about the complications of the treatment, especially for the children. To estimate the risk of second cancers and other unwanted effects, out-of-field dose assessment is necessary. The purpose of this study is to evaluate and compare out-of-field doses in pediatric CSI treatment using conventional and advanced photon radiotherapy (RT) and advanced proton therapy. To our knowledge, it is the first such comparison based on in-phantom measurements. Additionally, for out-of-field doses during photon RT in this and other studies, comparisons were made using analytical modeling., Methods: In order to describe the out-of-field doses absorbed in a pediatric patient during actual clinical treatment, an anthropomorphic phantom, which mimics the 10-year-old child, was used. Photon 3D-conformal RT (3D-CRT) and two advanced, highly conformal techniques: photon volumetric-modulated arc therapy (VMAT) and active pencil beam scanning (PBS) proton RT were used for CSI treatment. Radiophotoluminescent and poly-allyl-diglycol-carbonate nuclear track detectors were used for photon and neutron dosimetry in the phantom, respectively. Out-of-field doses from neutrons were expressed in terms of dose equivalent. A two-Gaussian model was implemented for out-of-field doses during photon RT., Results: The mean VMAT photon doses per target dose to all organs in this study were under 50% of the target dose (i.e., <500 mGy/Gy), while the mean 3D-CRT photon dose to oesophagus, gall bladder, and thyroid, exceeded that value. However, for 3D-CRT, better sparing was achieved for eyes and lungs. The mean PBS photon doses for all organs were up to three orders of magnitude lower compared to VMAT and 3D-CRT and exceeded 10 mGy/Gy only for the oesophagus, intestine, and lungs. The mean neutron dose equivalent during PBS for eight organs of interest (thyroid, breasts, lungs, liver, stomach, gall bladder, bladder, prostate) ranged from 1.2 mSv/Gy for bladder to 23.1 mSv/Gy for breasts. Comparison of out-of-field doses in this and other phantom studies found in the literature showed that a simple and fast two-Gaussian model for out-of-field doses as a function of distance from the field edge can be applied in a CSI using photon RT techniques., Conclusions: PBS is the most promising technique for out-of-field dose reduction in comparison to photon techniques. Among photon techniques, VMAT is a preferred choice for most of out-of-field organs and especially for the thyroid, while doses for eyes, breasts, and lungs are lower for 3D-CRT. For organs outside the field edge, a simple analytical model can be helpful for clinicians involved in treatment planning using photon RT but also for retrospective data analysis for cancer risk estimates and epidemiology in general., (© 2022 American Association of Physicists in Medicine.)

We report four new luminescent tetracationic bis-triarylborane DNA and RNA sensors that show high binding affinities, in several cases even in the nanomolar range. Three of the compounds contain substituted, highly emissive and structurally flexible bis(2,6-dimethylphenyl-4-ethynyl)arene linkers (3: arene=5,5'-2,2'-bithiophene; 4: arene=1,4-benzene; 5: arene=9,10-anthracene) between the two boryl moieties and serve as efficient dual Raman and fluorescence chromophores. The shorter analogue 6 employs 9,10-anthracene as the linker and demonstrates the importance of an adequate linker length with a certain level of flexibility by exhibiting generally lower binding affinities than 3-5. Pronounced aggregation-deaggregation processes are observed in fluorimetric titration experiments with DNA for compounds 3 and 5. Molecular modelling of complexes of 5 with AT-DNA, suggest the minor groove as the dominant binding site for monomeric 5, but demonstrate that dimers of 5 can also be accommodated. Strong SERS responses for 3-5 versus a very weak response for 6, particularly the strong signals from anthracene itself observed for 5 but not for 6, demonstrate the importance of triple bonds for strong Raman activity in molecules of this compound class. The energy of the characteristic stretching vibration of the C≡C bonds is significantly dependent on the aromatic moiety between the triple bonds. The insertion of aromatic moieties between two C≡C bonds thus offers an alternative design for dual Raman and fluorescence chromophores, applicable in multiplex biological Raman imaging., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The coordination properties of N'-(2-hydroxy-3-methoxyphenylmethylidene)-3-pyridinecarbohydrazide (H 2 L1), N'-(2-hydroxy-4-methoxyphenylmethylidene)-3-pyridinecarbohydrazide (H 2 L2) and N'-(2-hydroxy-5-methoxyphenylmethylidene)-3-pyridinecarbohydrazide (H 2 L3) toward Fe(III) ions were studied by computational, spectrometric (MS) and spectroscopic methods (UV-Vis, IR and Raman spectroscopy) in solid state and in solution. Free ligands were present in keto-amine form with intramolecular H-bond. In MeOH:H 2 O 1:1 system, the 1:1 complexes with Fe(III) were formed, characterized by lgK ≥ 6. The coordination to the metal ion was achieved via oxygen and azomethine nitrogen since the hydrolysis of hydrazone bond was suppressed. Unlike the 1:1 stoichiometry in methanolic solution, the composition of the complexes extracted to chloroform was Fe(L)(HL). The release of three protons upon complexation was determined by independent spectrophotometric measurements. The complexes isolated from MeOH/EtOH solution have also stoichiometry 1:2. However, depending on the position of the methoxy substituent, two types of complexes were formed. In Fe(H 2 L1) 2 Cl 3 and Fe(H 2 L3) 2 Cl 3 , hydrazones acted as neutral ligands, while in Fe(HL2) 2 Cl the keto-enol tautomeric interconversion and release of one proton per ligand took place. All complexes were analyzed in gas phase as well, using triple quadrupole, ion trap and H/D exchange for determination of labile hydrogens. Based on the fragmentation pathways, the structural isomers were distinguished.

A bis-triarylborane tetracation (4-Ar 2 B-3,5-Me 2 C 6 H 2 )-C≡C-C≡C-(3,5-Me 2 C 6 H 2 -4-BAr 2 [Ar=(2,6-Me 2 -4-NMe 3 -C 6 H 2 ) + ] (2 4+ ) shows distinctly different behaviour in its fluorimetric response than that of our recently published bis-triarylborane 5-(4-Ar 2 B-3,5-Me 2 C 6 H 2 )-2,2'-(C 4 H 2 S) 2 -5'-(3,5-Me 2 C 6 H 2 -4-BAr 2 ) (3 4+ ). Single-crystal X-ray diffraction data on the neutral bis-triarylborane precursor 2 N confirm its rod-like dumbbell structure, which is shown to be important for DNA/RNA targeting and also for BSA protein binding. Fluorimetric titrations with DNA/RNA/BSA revealed the very strong affinity of 2 4+ and indicated the importance of the properties of the linker connecting the two triarylboranes. Using the butadiyne rather than a bithiophene linker resulted in an opposite emission effect (quenching vs. enhancement), and 2 4+ bound to BSA 100 times stronger than 3 4+ . Moreover, 2 4+ interacted strongly with ss-RNA, and circular dichroism (CD) results suggest ss-RNA chain-wrapping around the rod-like bis-triarylborane dumbbell structure like a thread around a spindle, a very unusual mode of binding of ss-RNA with small molecules. Furthermore, 2 4+ yielded strong Raman/SERS signals, allowing DNA or protein detection at ca. 10 nm concentrations. The above observations, combined with low cytotoxicity, efficient human cell uptake and organelle-selective accumulation make such compounds intriguing novel lead structures for bio-oriented, dual fluorescence/Raman-based applications., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Sodium copper chlorophyllin (CHL) is a food colorant that exhibits many beneficial properties, including potential for use in radiotherapy. Nevertheless, genotoxicity studies investigating radioprotective properties against γ-radiation on human cells are rather scarce. The aim of this study was to assess the cytotoxicity, genotoxicity and induction of malondialdehyde formation on CHL pre-treated whole blood cells after an absorbed dose of 5 Gy γ-radiation. Irradiated whole blood cells pre-treated with 100, 500, and 1000 μg/mL CHL showed less DNA-strand breaks (10.92 ± 0.74%, 10.69 ± 0.68%, and 8.81 ± 0.69%, respectively) than untreated irradiated cells (12.58 ± 0.88%). At the same time, the level of malondialdehyde was lower in CHL pre-treated samples with 100, 500, and 1000 μg/mL CHL (14.11 ± 0.43, 16.35 ± 2.82, and 13.08 ± 1.03 μmol/L, respectively) compared to untreated irradiated samples (24.11 ± 0.25 μmol/L). Regarding cytotoxicity, no changes were observed in the samples tested. Another important finding is that CHL had no cyto/genotoxic properties toward human blood cells. Taken together, since CHL had no cyto/genotoxic effects and showed good radioprotective properties in human blood cells, further studies should be conducted in order to find its possible application in radiotherapy., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Human telomeric G-quadruplexes are emerging targets in anticancer drug discovery since they are able to efficiently inhibit telomerase, an enzyme which is greatly involved in telomere instability and immortalization process in malignant cells. G-quadruplex (G4) DNA is highly polymorphic and can adopt different topologies upon addition of electrolytes, additives, and ligands. The study of G-quadruplex forms under various conditions, however, might be quite challenging. In this work, surface-enhanced Raman scattering (SERS) spectroscopy has been applied to study G-quadruplexes formed by human telomeric sequences, d[A 3 G 3 (TTAGGG) 3 A 2 ] (Tel26) and d[(TTAGGG) 4 T 2 ] (wtTel26), under dilute and crowding conditions. The SERS spectra distinctive of hybrid-1 and hybrid-2 G-quadruplexes of Tel26 and wtTel26, respectively, were observed for the sequences folded in the presence of K + ions (110 mM) in a buffered solution, representing the diluted medium. Polyethylene glycol (5, 10, 15, 20, and 40% v/v PEG) was used to create a molecular-crowded environment, resulting in the formation of the parallel G-quadruplexes of both studied human telomeric sequences. Despite extensive overlap by the crowding agent bands, the SERS spectral features indicative of parallel G4 form of Tel26 were recognized. The obtained results implied that SERS of G-quadruplexes reflected not only the primary structure of the studied human telomeric sequence, including its nucleobase composition and sequence, but also its secondary structure in the sense of Hoogsteen hydrogen bonds responsible for the guanine tetrad formation, and finally its tertiary structure, defining a three-dimensional DNA shape, positioned close to the enhancing metallic surface. Graphical abstract.

The purpose of this study was to develop a NIR spectroscopic method for assessment of drug dissolution from allopurinol immediate release tablets. Thirty three different batches of allopurinol immediate release tablets containing constant amount of the active ingredient, but varying in excipients content and physical properties were introduced in a PLS calibration model. Correlating allopurinol dissolution reference values measured by the routinely used UV/Vis method, with the data extracted from the NIR spectra, values of correlation coefficient, bias, slope, residual prediction determination and root mean square error of prediction (0.9632, 0.328%, 1.001, 3.58, 3.75%) were evaluated. The obtained values implied that the NIR diffuse reflectance spectroscopy could serve as a faster and simpler alternative to the conventional dissolution procedure, even for the tablets with a very fast dissolution rate (>85% in 15minutes). Apart from the possibility of prediction of the allopurinol dissolution rate, the other multivariate technique, PCA, provided additional data on the non-chemical characteristics of the product, which could not be obtained from the reference dissolution values. Analysis on an independent set of samples confirmed that a difference between the UV/Vis reference method and the proposed NIR method was not significant. According to the presented results, the proposed NIR method may be suitable for practical application in routine analysis and for continuously monitoring the product's chemical and physical properties responsible for expected quality., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Purpose: To develop a simple model of therapeutic and stray absorbed dose for a variety of treatment machines and techniques without relying on proprietary machine-specific parameters., Methods: Dosimetry measurements conducted in this study and from the literature were used to develop an analytical model of absorbed dose from a variety of treatment machines and techniques in the 6 to 25 MV interval. A modified one-dimensional gamma-index analysis was performed to evaluate dosimetric accuracy of the model on an independent dataset consisting of measured dose profiles from seven treatment units spanning four manufacturers., Results: The average difference between the calculated and measured absorbed dose values was 9.9% for those datasets on which the model was trained. Additionally, these results indicate that the model can provide accurate calculations of both therapeutic and stray radiation dose from a wide variety of radiotherapy units and techniques., Conclusions: We have developed a simple analytical model of absorbed dose from external beam radiotherapy treatments in the 6 to 25 MV beam energy range. The model has been tested on measured data from multiple treatment machines and techniques, and is broadly applicable to contemporary external beam radiation therapy., (© 2017 American Association of Physicists in Medicine.)

G-Quadruplex (G4) structures of a human telomeric 24-mer (5'-TTAGGGTTAGGGTTAGGGTTAGGG-3') sequence (Tel24) stabilized by sodium and potassium ions have been assessed using surface-enhanced Raman scattering (SERS) spectroscopy. The distinctive SERS spectra of Tel24 in the presence of 100 mM Na + and 100 mM K + were obtained and the SERS bands characteristic of the antiparallel basket-type and the mixed hybrid (3+1) structures, respectively, were identified and assigned. The influence of the SERS - active substrate on the scattering enhancement was studied using citrate- and chloride-covered silver nanoparticles, in the absence and presence of the aggregating agent (0.1 M Na 2 SO 4 and 0.1 M K 2 SO 4 ). The highly reproducible SERS spectra of Tel24 obtained in various SERS active media indicated the same adsorption mechanism of the cation - stabilized G-quadruplexes onto the metal surface, regardless of the silver colloid. The remarkable resemblance between the circular dichroism (CD) spectra of the Tel24 structures with and without the colloid confirmed that interaction with the enhancing silver surface did not affect the stability of the formed G4 structures. The presented study pointed to a great potential of the SERS spectroscopy for the sensitive structural analysis of various G4 topologies. Graphical Abstract SERS spectroscopy allowed identification of Na + stabilized antiparallel basket-type and K + stabilized hybrid (3+1) structures of the same 24-mer human telomeric sequence.

Since autumn 2012, the European Radiation Dosimetry Group (EURADOS) has been developing its Strategic Research Agenda (SRA), which is intended to contribute to the identification of future research needs in radiation dosimetry in Europe. The present article summarises-based on input from EURADOS Working Groups (WGs) and Voting Members-five visions in dosimetry and defines key issues in dosimetry research that are considered important for the next decades. The five visions include scientific developments required towards (a) updated fundamental dose concepts and quantities, (b) improved radiation risk estimates deduced from epidemiological cohorts, (c) efficient dose assessment for radiological emergencies, (d) integrated personalised dosimetry in medical applications and (e) improved radiation protection of workers and the public. The SRA of EURADOS will be used as a guideline for future activities of the EURADOS WGs. A detailed version of the SRA can be downloaded as a EURADOS report from the EURADOS website (www.eurados.org)., (© The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Surface-enhanced Raman scattering (SERS) of four RNA mononucleotides (AMP, GMP, CMP and UMP) has been studied on the citrate-reduced silver colloid aggregated with sodium sulfate. Concentration dependent spectra in the range of 1×10(-7)-1×10(-4) mol dm(-3) were obtained, assigned and interpreted according to the surface selection rules. For purine mononucleotides, AMP and GMP, adsorption onto the silver nanoparticles through the six-membered ring of the nitrogenous base was suggested. Concentration dependent splitting of the ring breathing band in the spectra of AMP indicated coexistence of two species on the silver surface, which differed in contribution of the adenine N1 atom and the exocyclic NH2 group in binding. Unlike the AMP spectra, the spectra of GMP implied only one mode of adsorption of the molecules onto the silver nanoparticles, taking place through the guanine N1H and C=O group. Weak SERS spectra of pyrimidine mononucleotides, CMP and UMP, pointed to involvement of carbonyl oxygen in adsorption process, whereby the molecules adopted the position on the nanoparticles with ribose close to the metal surface. Intense bands in the low wavenumber region, associated with stretching of the formed Ag-N and/or Ag-O bonds, supported chemical binding of the RNA mononucleotides with the silver surface., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Due to their broad-spectrum antimicrobial activity, silver nanoparticles (AgNPs) have been used in a large number of commercial and medical products. Such proliferated AgNP production poses toxicological and environmental issues which need to be addressed. The present study aimed to investigate the effects of AgNPs on acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), important enzymes in areas of neurobiology, toxicology and pharmacology. Three different AgNPs, prepared by the chemical reduction using trisodium citrate, hydroxylamine hydrochloride (Cl-AgNPs), and borohydride following stabilization with poly(vinyl alcohol), were purified and characterised with respect to their sizes, shapes and optical properties. Their inhibition potential on AChE and BChE was evaluated in vitro using an enzyme assay with o-nitrophenyl acetate or o-nitrophenyl butyrate as substrates, respectively. All three studied AgNPs were reversible inhibitors of ChEs. Among tested nanoparticles, Cl-AgNP was found to be the most potent inhibitor of both AChE and BChE. Although the detailed mechanism by which the AgNPs inhibit esterase activities remains unknown, structural perturbation of the enzyme may be the common mode of ChE inhibition by AgNPs.

Structural forms of aroylhydrazones derived from nicotinic acid hydrazide have been studied in the solid state by FT-IR spectroscopy and in solution by NMR, UV-Vis and ATR spectroscopy. The studied compounds were N'-benzylidene-3-pyridinecarbohydrazide (1), N'-(2,4-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N'-(5-chloro-2-hydroxyphenylmethylidene)-3-pyridinecarbohydrazide (3), and N'-(3,5-dichloro-2-hydroxymethoxyphenylmethylidene)-3-pyridinecarbohydrazide (4). The compound 1 adopted the most stable ketoamine form (form I, -CO-NH-N=C-) in the solid state as well as in various organic solvents. In mixtures of organic solvents with water the UV-Vis and ATR spectra implied intermolecular hydrogen bonding of 1 with water molecules. The presence of both tautomeric forms I and II (form II, -COH=N-N=C-) was proposed for the solid substance and highly concentrated solutions of 2, whereas form I was detected as the predominant one in diluted solutions. For compounds 3 and 4 a coexistence of forms I and III (form III, -CO-NH-NH-C=C-CO-) was noticed in the solid state and in polar protic organic solvents. The conversion to form III was induced by increasing the water content in the solvent mixtures. This process was the most pronounced for compound 4. When exposed to daylight, an appearance of a new band was observed during time in the UV-Vis spectrum of 4 in organic solvent/water 1/1 mixtures, which implied that tautomeric interconversion was most likely followed by E/Z isomerisation., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Surface-enhanced Raman spectroscopy (SERS) and partial least squares (PLS) regression have been applied for the quantification of entacapone isomers E and Z in solution. Nine mixtures of isomers Z and E in ethanol ranging from 0% to 100% w/w were analyzed, for a total entacapone concentration of 1 × 10(-3) mol L(-1). Upon deposition onto commercially available Klarite® gold plates, highly intense and reproducible SERS spectra were obtained from the entacapone isomers. Based on the spectral measurements, a two-component PLS model for correlation of predicted and real content of the isomers mixtures was developed. Root-mean-square error of the predicted composition was found to be 8% of isomer Z in the isomers mixture, corresponding to the absolute concentration of 8 × 10(-5) mol L(-1) of isomer Z in solution.

Molecular structures of aroylhydrazones derived from salicylaldehyde, o-vanilin and nicotinic acid hydrazide in DMSO and DMSO/H(2)O mixtures have been studied by NMR, UV-Vis, ATR and Raman spectroscopy. The addition of water to the system did not induce the tautomeric conversion of the existing form constituted of the ketoamino hydrazide part and the enolimino aldehyde part, but it was involved in the formation of hydrated molecules. Vibrational spectra (ATR and Raman) clearly indicated hydrogen bonding of the studied hydrazones through the carbonyl, amino and hydroxyl groups with water molecules. Increasing the water content conversion from E to Z isomer was not observed., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Low-dose ionizing radiation used for medical purposes is one of the definite risk factors for cancer development, and children exposed to ionizing radiation are at a relatively greater cancer risk as they have more rapidly dividing cells than adults and have longer life expectancy. Since cytokinesis-block micronucleus cytome (CBMN Cyt) assay has become one of the standard endpoints for radiation biological dosimetry, we used that assay in the present work for the assessment of different types of chromosomal damage in children exposed to diagnostic X-ray procedures. Twenty children all with pulmonary diseases between the ages of 4 and 14 years (11.30 ± 2.74) were evaluated. Absorbed dose measurements were conducted for posterior-anterior projection on the forehead, thyroid gland, gonads, chest and back. Doses were measured using thermoluminescence and radiophotoluminescent dosimetry systems. It was shown that, after diagnostic X-rays, the mean total number of CBMN Cyt assay parameters (micronucleus, nucleoplasmic bridges and nuclear buds) was significantly higher than prior to diagnostic procedure and that interindividual differences existed for each monitored child. For the nuclear division index counted prior and after examination, no significant differences were noted among mean group values. These data suggest that even low-dose diagnostic X-ray exposure may induce damaging effect in the somatic DNA of exposed children, indicating that immense care should be given in both minimizing and optimizing radiation exposure to diminish the radiation burden, especially in the youngest population., (Copyright © 2010 John Wiley & Sons, Ltd.)

Raman and surface-enhanced Raman spectra of new DNA/RNA-binding compounds consisting of three imidazole (Im) and three pyridine (Py) rings connected by tripodal polyaminomethylene linkages were obtained by the near-infrared excitation at 1064 nm. Study of interactions of Im and Py polyamines with single-stranded RNA polynucleotides (poly A, poly G, poly C, poly U), double-stranded DNA polynucleotides (poly dAdT-poly dAdT, poly dGdC-poly dGdC) and calf thymus DNA (ct-DNA) by surface-enhanced Raman spectroscopy (SERS) reveals unambiguous enhancement of the Raman scattering from the small molecules as well as appearance of new bands in spectra associated mainly with nucleobases. The SERS experiments point toward comparable interactions of Im and Py polyamines with single-stranded purine and pyrimidine polynucleotides. Furthermore, SERS experiments with double stranded polynucleotides reveal the base-pair dependent selectivity of Im and Py, whereby interactions within both, major and minor groove are indicated for poly dAdT-poly dAdT, at variance to preferred binding of Im and Py to only major groove of poly dGdC-poly dGdC. SERS spectra of Im and Py with ct-DNA imply that protonated amino groups of these compounds preferentially interact with N7 atoms (adenine, guanine) while nitrogen in aromatic rings of polyamines might be attracted to C6-NH(2) (adenine), all sites being located at the major groove of the DNA helix. Wavenumber downshift of the imidazole (Im) and pyridine (Py) ring vibrations supports aromatic stacking interactions of imidazole and pyridine aromatic moieties with DNA base-pairs.

At submicromolar concentrations two novel phenanthridine biguanides exhibit distinctly different spectroscopic signals for dGdC and dAdT sequences, respectively, by opposite fluorimetric changes (quenching for dGdC and increase for dAdT) and especially the bis-biguanide derivative gives an opposite ICD response (negative ICD for dGC and strong positive for dAdT). This specific signalling was explained by the ability of compounds to switch the binding mode from intercalation into dGdC to minor groove binding into dAdT sequences. Both compounds bind to rArU by intercalation, yielding different fluorimetric and CD response in comparison to any of aforementioned ds-DNA. Moreover, both compounds revealed significantly higher affinity toward ds-polynucleotides in comparison to previously studied alkylamine- and urea-analogues. Furthermore, DNA/RNA binding properties of novel compounds could be controlled by pH, due to the protonation of heterocyclic nitrogen. Low in vitro cytotoxicity of both compounds against human cell lines makes them interesting spectrophotometric probes.

In-line Raman spectroscopy and multivariate analysis were used to monitor Knoevenagel condensation reaction, the final step in preparation of drug entacapone. By applying a fiber optical Raman probe immersed into a reaction vessel Raman spectra of the reaction mixture were recorded in situ during the entacapone synthesis in toluene, heptane and isobutyl acetate. Due to the complexity of the measured spectra, the obtained data were analyzed and interpreted by means of principal component analysis. It has been shown that progress of this reaction can be monitored in real-time and reaction end points can be determined in different solvents. The reaction was found to be the fastest in heptane due to the lower loss of the catalyst. For a comparison the reaction was independently monitored by off-line Raman spectroscopy and liquid chromatography which confirmed the results obtained in-line. The results presented here have shown that this in-line approach can be used as a fast, non destructive and reliable method to monitor the Knoevenagel reaction in real time. The knowledge gained in this study can further be exploited for the industrial process control., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Sorption of the cationic surfactant, hexadecyltrimethylammonium cations (HDTMA), on the solid/liquid interface of the natural mordenite tuff (MT) was studied. The examined tuff originated from Croatia consisting of 30% of mordenite. SEM observations confirmed the crystalline nature of mordenite which can be described in terms of aggregates of many small platelets with diameters in the range of 1 μm. Studying the porosity properties of MT, it was found that the average pore diameter (4.42 nm) between mordenite's platelets allows penetration of HDTMA cations. The measurements of zeta potential indicated that in MT samples with surfactant concentration in the range between 0.013 and 0.25 mmol/g, HDTMA cations fill the mesopores of MT. By further increase in HDTMA concentration, the surfactant sorbs on the external zeolite surface, as revealed by the SEM micrographs. Vibrational (FTIR and FT Raman) spectra showed that in the MT samples with initial HDTMA concentration from 0.013 to 0.25 mmol/g, alkyl chains adopt mainly gauche conformation, whereas in the MT samples with higher initial HDTMA concentrations trans conformers are predominant and form a highly ordered structure on the mordenite surface., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Surface-enhanced Raman scattering (SERS) of the cationic and the neutral form of rhodamine 19 octadecylamide (R19OA) has been studied in the silver citrate colloid using NIR excitation at 1064 nm. Cationic molecules readily adsorb onto negatively charged silver nanoparticles through a positively charged xanthene part of the molecules resulting in surface enhancement of Raman scattering. Due to a lack of the positive charge in molecular structure, SERS spectrum of neutral molecules is not observed. Nevertheless, a broad band appearing at 1240 cm(-1) in the spectrum of the cationic form indicates conversion of the cationic into the neutral species occurring close to the silver surface. The observed band most likely arises from a vibration of the ring formed in the molecular structure after conversion, but before complete desorption of the neutral molecules from the metal surface. Upon addition of HCl and NaOH in the silver sol, equilibrium is shifted toward the cationic and the neutral form of R19OA, respectively, followed by corresponding changes in the Raman spectrum. In addition, FT-SERS spectra of two rhodamine dyes, rhodamine 19 (R19) and rhodamine 6G (R6G), that are structurally related to R19OA, have been studied under the same experimental conditions for comparison., (Copyright 2009 Elsevier B.V. All rights reserved.)

In interventional radiology, for an accurate determination of effective dose to the staff, measurements with two dosemeters have been recommended, one located above and one under the protective apron. Such 'double dosimetry' practices and the algorithms used for the determination of effective dose were reviewed in this study by circulating a questionnaire and by an extensive literature search. The results indicated that regulations for double dosimetry almost do not exist and there is no firm consensus on the most suitable calculation algorithms. The calculation of effective dose is mainly based on the single dosemeter measurements, in which either personal dose equivalent, directly, (dosemeter below the apron) or a fraction of personal dose equivalent (dosemeter above the apron) is taken as an assessment of effective dose. The most recent studies suggest that there might not be just one double dosimetry algorithm that would be optimum for all interventional radiology procedures. Further investigations in several critical configurations of interventional radiology procedures are needed to assess the suitability of the proposed algorithms.

Determination of gamma ray dose in mixed neutron+gamma ray fields is still a demanding task. Dosemeters used for gamma ray dosimetry are usually in some extent sensitive to neutrons and their response variations depend on neutron energy i.e., on neutron spectra. Besides, it is necessary to take into account the energy dependence of dosemeter responses to gamma rays. In this work, several types of thermoluminescent detectors (TLD) placed in different holders used for gamma ray dose determination in the mixed fields were examined. Dosemeters were from three different institutions: Ruder Bosković Institute (RBI), Croatia, JoZef Stefan Institute (JSI), Slovenia and Autoridad Regulatoria Nuclear (ARN), Argentina. All dosemeters were irradiated during the International Intercomparison of Criticality Accident Dosimetry Systems at the SILENE Reactor, Valduc, June 2002. Three accidental scenarios were reproduced and in each irradiation the dosemeters were exposed placed on the front of phantom and 'free in air'. Following types of TLDs were used: 7LiF (TLD-700), CaF2:Mn and Al2O3:Mg,Y-all from RBI; CaF2:Mn from JSI and 7LiF (TLD-700) from ARN. Reported doses were compared with the reference values as well as with the values obtained from the results of all participants. The results show satisfactory agreement with other dosimetry systems used in the Intercomparison. The influence of different types of holders and applied corrections of dosemeters' readings are discussed.