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1.
Sr incorporation in the molecules of amorphous calcium phosphate, apatitic tricalcium phosphate, hydroxyapatite, octacalcium phosphate and dicalcium phosphate dihydrate was investigated. The concentration of Sr ranged from 225 to 1010 μ g / g, i.e. it overlapped with the physiological range of Sr concentrations in human bone. The leading experimental technique was extended X-ray absorption fine structure (EXAFS) at the Sr K edge. Results of these studies demonstrated the following: (1) Sr incorporation in the calcium phosphates is compound-dependent, (2) the coordination of incorporated Sr atoms in the Ca-P molecules is similar to that of Ca atoms, but interatomic distances are ≈0.015 nm larger, (3) in apatitic tricalcium phosphate, hydroxyapatite and octacalcium phosphate lattices Sr atoms may occupy selected Ca sites, which was not the case for dicalcium phosphate dihydrate, (4) in the apatite lattice Sr atoms are coordinated by 6 PO4 tetrahedrals and (5) EXAFS spectra at the K edge of the incorporated Sr may be used to distinguish the structures of amorphous calcium phosphate, dicalcium phosphate dihydrate as well as apatite and its derivatives (apatitic tricalcium phosphate, octacalcium phosphate). 相似文献
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Tomasz Rok Eugeniusz Rokita Grzegorz Tatoń Tomasz Guzik Tomasz Śliwa 《Journal of Thermal Analysis and Calorimetry》2017,127(2):1163-1170
Allergen sensitization is being diagnosed by commonly available methods in clinical practice—skin prick tests (SPTs) and specific immunoglobulin E test (sIgE). Recently, a new thermographic (TH) method for the assessment of SPT was developed, and it was demonstrated that the TH measurements of forearm temperature distribution during SPT, supported by a mathematical model, offer a new quantification method of allergen-induced skin reactions. The aim of this study is a comprehensive comparison of the TH method with SPT and sIgE techniques. The studies were performed for a group of 51 patients. The SPT and sIgE examinations were done in a routine way. For TH analyses, set of thermograms of both forearms were acquired after prick and analyzed with the use of developed software. All results were converted into categorized scale for comparison. The collected results indicate high correlation coefficients between methods equal to 0.76–0.99. Sensitivity and accuracy of TH assessment in respect of both SPT and sIgE methods is at good level (0.72–0.93). Acceptable level of specificity 0.60–0.88 was also achieved for most allergic responses. Excellent agreement between SPT and sIgE methods was observed which makes the TH assessment competitive. Due to higher precision and sensitivity of digital infrared technology, possibility of making error in diagnosis is significantly reduced. Additional advantage of the TH method relies on an estimation of the skin reactivity which allows highlighting the hypersensitivity patients and automatic correction of the diagnosis. 相似文献
3.
Bekzat ABDIKADYR Alp KILI Onur ALEV Serkan BÜYÜKK
SE Zafer Ziya
ZTÜRK 《Turkish Journal of Chemistry》2021,45(2):295
Pristine and WO3 decorated TiO2 nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO2 NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO2 NRs and thermally oxidised to obtain WO3 nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO2 NRs with WO3. 相似文献
4.
An assay based on photoinduced reaction and subsequent cleavage of duplex DNA containing a bromodeoxyuridine ((Br)U) residue and an abasic site was developed to screen aromatic amines for their ability to initiate charge transfer by reductive electron donation. Two candidates, N,N,N',N'-tetramethyl-1,5-diaminonaphthalene (TMDN) and 1,5-diaminonaphthalene (DAN), expressed the desired activity, and an oligodeoxynucleotide-TMDN conjugate was subsequently prepared to identify additional variables affecting the efficiency of electron injection and transfer into DNA. This system demonstrated only mild sensitivity to molecular oxygen but was strongly inhibited by high concentrations of 2-mercaptoethanol. The nucleobase counter to the attached TMDN strongly modulated charge transfer as evident by a 60-fold decrease in reduction of the distal (Br)U when the counterbase A was substituted for C. An inverse relationship between this reduction and quenching of TMDN fluorescence by the counterbase was also discovered and is consistent with a competition between radical recombination and electron migration away from the initial site of its injection into DNA. 相似文献
5.
Selective Alkylation of C‐Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives
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Dr. Tuomas Lönnberg Mark Hutchinson Prof. Dr. Steven Rokita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13127-13136
A quinone methide precursor featuring a bis‐cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn2+, Ni2+ and Cd2+). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C‐rich bulges, regardless of the presence of divalent metal ions or even the bis‐cyclen anchor. This C‐selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2′‐deoxynucleosides. Only dA‐N1 and dC‐N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis. 相似文献
6.
McCrane MP Weinert EE Lin Y Mazzola EP Lam YF Scholl PF Rokita SE 《Organic letters》2011,13(5):1186-1189
Selective oxidation by bis[(trifluoroacetoxy)iodo]benzene (BTI) provides an effective trap for quenching adducts formed reversibly between dC and an ortho-quinone methide (QM) under physiological conditions. A model adduct generated by 4-methyl-o-QM and 2'-deoxycytidine is rapidly converted by intramolecular cyclization and loss of aromaticity to a characteristic product for quantifying QM alkylation. However, BTI induces a surprising rearrangement driven by overoxidation of a derivative lacking an alkyl substituent at the 4-position of the QM. 相似文献
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In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•+), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•+, DPPH•, and FRAP activities (IC50: 0.05 ± 0.0001 mg/mL, IC50: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC50: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source. 相似文献
9.
A dinuclear copper complex [CuII2(PD'O)(H2O)2]3+ (1) (where PD'OH is a pyridylalkylamine containing binucleating ligand) promotes guanine oxidation in single-stranded DNA in the presence of 3-mercaptopropionic acid and dioxygen. This reaction is detected after subsequent piperidine treatment. Little spontaneous strand scission indicative of deoxyribose oxidation is observed in contrast to the results known for other copper complexes. Chemical characterization and nanospray ionization mass spectrometry analysis of oligodeoxynucleotides treated with 1 suggest conversion of guanine residues to their 2,6-diamino-5-formamidino-4-hydroxypyrimidine (+18 amu) and possibly 5,8-dihydroxy-7,8-dihydroguanine (+34 amu) derivatives. The selectivity toward nucleobase rather than deoxyribose oxidation is discussed in terms of the specific nature of the dicopper (hydro)peroxo species formed with the PD'OH ligand versus the intermediates formed in the presence of other binucleating ligands. 相似文献
10.
Li L Murthy NN Telser J Zakharov LN Yap GP Rheingold AL Karlin KD Rokita SE 《Inorganic chemistry》2006,45(18):7144-7159
A dinuclear copper(II) complex [Cu(II)2(PD'O-)(H2O)2](ClO4)3 (5) with terminal Cu(II)-H(2)O moieties and a Cu...Cu distance of 4.13 A (X-ray structure) has been synthesized and characterized by EPR spectroscopy (ferromagnetic coupling observed) and cyclic voltammetry. Dizinc(II) and mononuclear copper(II) analogues [Zn(II)2(PD'O-)(H2O)2]3+ (7) and [Cu(II)(mPD'OH)(H2O)]2+ (6), respectively, have also been synthesized and structurally characterized. Reacting 5/MPA/O(2) (MPA = 3-mercaptopropionic acid) with DNA leads to a highly specific oxidation of guanine (G) at a junction between single- and double-stranded DNA. Mass spectrometric analysis of the major products indicates a gain of +18 and +34 amu relative to initial DNA strands. The most efficient reaction requires G at the first and second unpaired positions of each strand extending from the junction. Less reaction is observed for analogous targets in which the G cluster is farther from the junction or contains less than four Gs. Consistent with our previous systems, the multinuclear copper center is required for selective reaction; mononuclear complex 6 is not effective. Hydrogen peroxide as a substitute for MPA/O2 also does not lead to activity. Structural analysis of a [Cu(II)2(PD'O-)(G)]3+ complex (8) and dizinc analogue [Zn(II)(2)(PD'O-)(G)](ClO4)3 (9) (G = guanosine) reveals coordination of the G O6 and N7 atoms with the two copper (or zinc) centers and suggests that copper-G coordination likely plays a role in recognition of the DNA target. The Cu2-O2 intermediate responsible for guanine oxidation appears to be different from that responsible for direct-strand scission induced by other multinuclear copper complexes; the likely course of reaction is discussed. 相似文献