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71.
The necessity for inspection and assessment of glued laminated timber structures in service has raised interest in the evaluation of the glue lines. Glue line spectra were analysed and are discussed in detail with respect to spectral contributions from the adhesive, the hardener, the wood lamella below the adhesive, the curing temperature as well as ageing-related spectral changes. The combination of near infrared (NIR) spectroscopy and principal component analysis (PCA) allowed distinguishing between aged and non-aged samples and different copper azole preservative treatment levels of phenol-resorcinol-formaldehyde (PRF) glue lines. NIR-based partial least squares (PLS) regression modelling was performed for the glue line shear strength and for the curing temperature. These findings show that NIR spectroscopy is a fast and useful technique to evaluate the degradation on the PRF glue lines of untreated and copper azole treated laminated timber. 相似文献
72.
Maria Helena Garcia Pedro Florindo Maria de Fátima M. Piedade Stefano Maiorana Emanuela Licandro 《Polyhedron》2009
A series of organometallic complexes possessing new tetrathia-[7]-helicene nitrile derivative ligands [TH-7] as chromophores, of general formula [MCp(P–P)(NC{TH-[7]-Y}Z)][PF6] (M = Ru, Fe, P–P = DPPE, Y = H, NO2, Z = H, C≡N; M = Ru, L–L = 2PPh3, Y = H, Z = H) has been synthesized and fully characterized. 1H NMR, FT-IR and UV–Vis. spectroscopic data were analyzed with in order to evaluate the existence of electronic delocalization from the metal centre to the coordinated ligand to have some insight on the potentialities of these new compounds as non-linear optical molecular materials. Slow crystallization of compound [RuCp(PPh3)2(NC{TH-[7]-H}H)][PF6] 2Ru revealed an interesting isomerization of the helical ligand with formation of two carbon-carbon bonds between the two terminal thiophenes, leading to the total closure of the helix (2*Ru). 相似文献
73.
Slejkovec Z Falnoga I Goessler W van Elteren JT Raml R Podgornik H Cernelc P 《Analytica chimica acta》2008,607(1):83-91
Urine and blood samples of cancer patients, treated with high doses of arsenic trioxide were analysed for arsenic species using HPLC-HGAFS and, in some cases, HPLC-ICPMS. Total arsenic was determined with either flow injection-HGAFS in urine or radiochemical neutron activation analysis in blood fractions (in serum/plasma, blood cells). The total arsenic concentrations (during prolonged, daily/weekly arsenic trioxide therapy) were in the μg mL−1 range for urine and in the ng g−1 range for blood fractions. The main arsenic species found in urine were As(III), MA and DMA and in blood As(V), MA and DMA.With proper sample preparation and storage of urine (no preservation agents/storage in liquid nitrogen) no analytical artefacts were observed and absence of significant amounts of alleged trivalent metabolites was proven. On the contrary, in blood samples a certain amount of arsenic can get lost in the speciation procedure what was especially noticeable for the blood cells although also plasma/serum gave rise to some disappearance of arsenic. The latter losses may be attributed to precipitation of As(III)-containing proteins/peptides during the methanol/water extraction procedure whereas the former losses were due to loss of specific As(III)-complexing proteins/peptides (e.g. cysteine, metallothionein, reduced GSH, ferritin) on the column (Hamilton PRP-X100) during the separation procedure. Contemporary analytical protocols are not able to completely avoid artefacts due to losses from the sampling to the detection stage so that it is recommended to be careful with the explanation of results, particularly regarding metabolic and pharmacokinetic interpretations, and always aim to compare the sum of species with the total arsenic concentration determined independently. 相似文献
74.
Keith B. Dillon Judith A. K. Howard Philippa K. Monks Michael R. Probert Helena J. Shepherd 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(4):m111-m114
The title compound, cis‐dichloridobis(triethylphosphane)platinum(II) chloroform monosolvate, [PtCl2(C6H15P)2]·CHCl3, has been obtained from ligand scrambling in the cis‐[PtCl2(Cyp2PCl)(PEt3)] (Cyp = cyclopentyl) system in CHCl3 solvent. Unlike the two previously reported unsolvated polymorphs, which are both monoclinic, the compound crystallizes in an orthorhombic setting. Furthermore, the system exhibits a reversible temperature‐dependent structural phase transition, coupling a reduction in anisotropic displacement parameters and a reduction in crystallographic symmetry on cooling. The high‐temperature phase adopts space group Pnma with the complex and solvent molecules sitting across a crystallographic mirror plane (Z′ = 0.5). The low‐temperature phase adopts the space group P212121 with Z′ = 1. 相似文献
75.
João Paulo R.F. André Hugh D. Burrows Carlos F.G.C. Geraldes Maria Da Graça M. Miguel M.Helena S.F. Teixeira L.F. Vilas Boas 《Polyhedron》1996,15(24):4331-4340
Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, 1H and 13C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M−1 and 12 M−1 for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of 1H and 13C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed. 相似文献
76.
Cui X Delgado R Carapuça HM Drew MG Félix V 《Dalton transactions (Cambridge, England : 2003)》2005,(20):3297-3306
A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl(-), PF(6)(-), HSO(4)(-), H(2)PO(4)(-) and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). (1)H NMR titrations in CD(3)OD indicated that this receptor is not suitable for recognizing HSO(4)(-) and H(2)PO(4)(-), but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3)(CH(3))(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the (1)H NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF(6)(-), ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS(2) stoichiometry are formed with the first three anions, but RS(4) with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H...O=C hydrogen bonds for carboxylate anions and N-H...F hydrogen bonds for the PF(6)(-) anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe...Fe intramolecular distances ranging from 10.125(14) to 12.783(15)A. 相似文献
77.
We address the probability that k or more Consecutive Customer Losses take place during a busy period of a queue, the so-called k-CCL probability, for oscillating GI
X
/M//n systems with state dependent services rates, also denoted as GI
X
/M(m)−M(m)//n systems, in which the service rates oscillate between two forms according to the evolution of the number of customers in
the system. We derive an efficient algorithm to compute k-CCL probabilities in these systems starting with an arbitrary number of customers in the system that involves solving a linear
system of equations. The results derived are illustrated for specific sets of parameters. 相似文献
78.
We derive fast recursions to compute the probability that k or more consecutive customer losses take place during a busy period of a queue, the so called k-CCL probability, for regular and oscillating M
X
/G/1/n systems. 相似文献
79.
80.