Modeling the Solvent Extraction of Cadmium(II) from Aqueous Chloride Solutions by 2-pyridyl Ketoximes: A Coordination Chemistry Approach.

The goal of this work is to model the nature of the chemical species [CdCl2(extractant)2] that are formed during the solvent (or liquid-liquid) extraction of the toxic cadmium(II) from chloride-containing aqueous media using hydrophobic 2-pyridyl ketoximes as extractants. Our coordination chemistry approach involves the study of the reactions between cadmium(II) chloride dihydrate and phenyl 2-pyridyl ketoxime (phpaoH) in water-containing acetone. The reactions have provided access to complexes [CdCl2(phpaoH)2]∙H2O (1∙H2O) and {[CdCl2(phpaoH)]}n (2); the solid-state structures of which have been determined by single-crystal X-ray crystallography. In both complexes, phpaoH behaves as an N,N'-bidentate chelating ligand. The complexes have been characterized by solid-state IR and Raman spectra, and by solution 1H NMR spectra. The preparation and characterization of 1∙H2O provide strong evidence for the existence of the species [CdCl2(extractant)2] that have been proposed to be formed during the liquid-liquid extraction process of Cd(II), allowing the efficient transfer of the toxic metal ion from the aqueous phase into the organic phase.

Collagen orientation probed by polarized Raman spectra can serve as differential diagnosis indicator between different grades of meniscus degeneration.

The purpose of the present study was to analyze normal and degenerated menisci with Raman methodology on thin sections of formalin fixed paraffin embedding tissues and to correlate the Raman findings with the grade of meniscus degeneration. Menisci (n = 27) were removed from human knee joints after total knee replacement or meniscectomy. Following routine histopathological analysis to determine the grade of meniscal lesions obtained from healthy and degenerated formaline fixed paraffin embedded (FFPE) meniscal sections, Raman polarization approach was applied to evaluate the orientation of collagen fibrils in different levels of the same 5 µm thick FFPE meniscal tissue sections, used for histopathological assessment. We collected Raman spectra in two different polarization geometries, v-HH and v-VV, and calculated the mean value of the v-HH/v-VV intensity ratio of two Raman bands, sensitive and non-sensitive to the molecular orientation. The collagen specific amide I band at 1665 cm-1, has the higher sensitivity dependence on the Raman polarization. The mean values of ratio v-HH/v-VV of the 1665 cm-1 peak intensity was significantly higher in healthy, mean ± SD: 2.56 ± 0.46, compared to degenerated menisci, mean ± SD: 1.85 ± 0.42 (p = 0.0014). The mean values of v-HH/v-VV intensity ratio were 2.18 and 1.50 for low and high degenerated menisci, respectively (p < 0.0001). The difference of peak intensities in the two laser polarizations is decreased in the degenerated meniscus; this difference is diminishing as the degeneration increases. The v-HH/v-VV ratio was also of significant difference in low as compared to control and high grade meniscus lesions (p = 0.036 and p < 0.0001, respectively) offering valuable information for the approach of its biology and function. In the present study we showed that the 5 µm thick sections can be used for Raman analysis of meniscal tissue with great reliability, in terms of sensitivity, specificity, false-negative and false-positive results. Our data introduce the interesting hypothesis that compact portable Raman microscopy on tissue sections can be used intra-operatively for fast diagnosis and hence, accurate procedure design in the operating room.

Quantitative analysis via Surface Enhanced Raman Scattering from Ag nano-colloids utilizing an oscillating cell and right-angle collection geometry.

We examine the application of an oscillating cell in combination with right-angle Raman scattered light collection geometry for quantitative Surface Enhanced (Resonance) Raman Scattering (SER(R)S) measurements from nano-colloidal noble metal solutions. This excitation/collection Raman configuration allows specific SERS and SERRS signatures of aqueous solutions of mitoxantrone, an antitumor drug, to be easily resolved at (sub)-ng/mL and (sub)-pg/mL concentration levels. A partial least-squares (PLS) chemometric algorithm was applied to predict the concentration of 25 microL of aqueous solutions of mitoxantrone added in 0.5 mL of a silver colloidal solution in a test tube attached to the oscillating cell. For SERS (514.5 nm) measurements, this was performed over the range from 0 to 13 ng/mL with a correlation coefficient R(2) of 98.5% and RMS error of prediction equal to 0.5 ng/mL. SERRS (632.8 nm) measurements performed over a range of 0 to 7 pg/mL gave R(2) = 98.92% and RMSE = 0.2 pg/mL.