Inhibition of the kinetics of chelation of nickel (II) with malonate ion by β-cyclodextrin

Relaxation times, determined by the pressure-jump technique, for the kinetics of chelation of nickel (II) by malonate ion are significantly prolonged by the addition of β-cyclodextrin to aqueous solutions.The effect is due to inclusion of the malonate into the β-cyclodextrin cavity. In fact addition of glucose in a 7:1 ratio to malonate ion does not affect the kinetics of complexation with Ni²⁺. The effect is also specific to the size of the ring since α-cyclodextrin and γ-cyclodextrin do not show any effect on the above relaxation times.The kinetic data are interpreted to indicate a competitive inhibition process. β-cyclodextrin is bound to the anion and prevents its chelation reaction with Ni²⁺. The mechanism treats the data quantitatively with an inclusion formation constant between malonate and β-cyclodextrin of the order of 10²M^?1.     

Physics and technique of stochastic cooling

A survey of the theory of stochastic cooling is presented followed by a report on experiments in this field. It is shown that the results of these experiments agree with the theoretical predictions.     

Reply to “Comment on ‘Piezonuclear decay of thorium’ [Phys. Lett. A 373 (2009) 1956]” [Phys. Lett. A 374 (2009) 696]

In a Letter appearing in this issue of Physics Letters A, Kowalski raises some critical comments on the experiment [F. Cardone, R. Mignani, A. Petrucci, Phys. Lett. A 373 (2009) 1956] that we carried out by cavitating a solution of Thorium-228. The experiment highlighted the anomalous decay of Thorium, thus confirming the results previously obtained by Urutskoev et al. by explosion of titanium foils in solutions. In this Letter, we reply to these comments. We agree with Kowalski that critical comments are one of the key factors of the process to improve the quality of experiments and the interpretation of results. However we do hope that these comments together with the details provided in the replies will promote further and better experiments which are certainly worth performing in order to shed a brighter light on this issue, as Kowalski himself suggests in his comment.     

Applicability of Spectroscopic Methods to the Determination of Aluminium in Biological Samples

A comparative investigation was carried out of the suitability of atomic absorption spectrometry and of emission spectrography with hollow cathode and arc excitation sources for determination of aluminium in biological samples. The three methods give reliable results. Hollow cathode emission spectrography was found to be influenced to a lesser extent by matrix effects than the other two techniques. On the other hand atomic absorption spectrometry presents some remarkable advantages insofar rapidity of analysis and detection limits are concerned.     

Unraveling the dynamics of the C(3P,1D) + C2H2 reactions by the crossed molecular beam scattering technique

A detailed investigation of the dynamics of the reactions of ground- and excited-state carbon atoms, C(3P) and C(1D), with acetylene is reported over a wide collision energy range (3.6-49.1 kJ mol-1) using the crossed molecular beam (CMB) scattering technique with electron ionization mass spectrometric detection and time-of-flight (TOF) analysis. We have exploited the capability of (a) generating continuous intense supersonic beams of C(3P, 1D), (b) crossing the two reactant beams at different intersection angles (45, 90, and 135 degrees ) to attain a wide range of collision energies, and (c) tuning the energy of the ionizing electrons to low values (soft ionization) to suppress interferences from dissociative ionization processes. From angular and TOF distribution measurements of products at m/z=37 and 36, the primary reaction products of the C(3P) and C(1D) reactions with C2H2 have been identified to be cyclic (c)-C3H + H, linear (l)-C3H + H, and C3 + H2. From the data analysis, product angular and translational energy distributions in the center-of-mass (CM) system for both the linear and cyclic C3H isomers as well as the C3 product from C(3P) and for l/c-C3H and C3 from C(1D) have been derived as a function of collision energy from 3.6 to 49.1 kJ mol-1. The cyclic/linear C3H ratio and the C3/(C3 + c/l-C3H) branching ratios for the C(3P) reaction have been determined as a function of collision energy. The present findings have been compared with those from previous CMB studies using pulsed beams; here, a marked contrast is noted in the CM angular distributions for both C3H- and C3-forming channels from C(3P) and their trend with collision energy. Consequently, the interpretation of the reaction dynamics derived in the present work contradicts that previously proposed from the pulsed CMB studies. The results have been discussed in the light of the available theoretical information on the relevant triplet and singlet C3H2 ab initio potential energy surfaces (PESs). In particular, the branching ratios for the C(3P) + C2H2 reaction have been compared with the available theoretical predictions (approximate quantum scattering calculations and quasiclassical trajectory calculations on ab initio triplet PESs and, very recent, statistical calculations on ab initio triplet PESs as well as on ab initio triplet/singlet PESs including nonadiabatic effects, that is, intersystem crossing). While the experimental branching ratios have been corroborated by the statistical predictions, strong disagreement has been found with the results of the dynamical calculations. The astrophysical implications of the present results have been noted.     

A quasi-monochromatic X-rays source for art painting pigments investigation

Monochromatic X-ray sources can be used for several applications, like in medicine or in studying our cultural heritage. We are investigating imaging systems based on a tuneable energy band X-ray source, to obtain an element mapping of painting layers using the K-edge technique. The narrow energy band beams are obtained with conventional X-ray source via Bragg diffraction on a mosaic crystal; such an analysis has been performed at different diffraction angles, tuning the energy to investigate spectra of interest from the artistic point of view, like zinc and copper. In this paper the characteristics of the system in terms of fluence rate are reported, and first results of this technique on canvas samples and painting are presented.     

Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) equipped with a high-efficiency sample introduction system

A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulization system (APEX-IR) was employed to determine 17 elements (Al, As, Ba, Cd, Co, Cr, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, V, and Zr) in blood samples. Ammonia (for Al, Cr, Mn, and V) and O₂ (for As and Se) were used as reacting gases. Selection of the best flow rate of the gases and optimization of the quadrupole dynamic bandpass tuning parameter (RPq) were carried out, using digested blood diluted 1 + 9 with deionized water and spiked with 1 μg L⁻¹ of Al, Cr, Mn, V and 5 μg L⁻¹ of As and Se. Detection limits were determined in digested blood using the 3σ criterion. The desolvating system allowed a sufficient sensitivity to be achieved to determine elements at levels of ng L⁻¹ without detriment of signal stability. The accuracy of the method was tested with the whole blood certified reference material (CRM), certified for Al, As, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, and V, and with indicative values for Ba, Li, Sn, Sr, and Zr. The addition calibration approach was chosen for analysis. In order to confirm the DRC data, samples were also analyzed by means of sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), operating in medium (m/Δm = 4000) and high (m/Δm = 10,000) resolution mode and achieving a good agreement between the two techniques.     

Ultrasonic and Raman Scattering Spectroscopy of Zinc Thiocyanate Complexes in Water at 25<Superscript>∘</Superscript>C: Kinetics of Complex Formation Determined by Multivariate Analysis

Advances have been made recently in broadening the accessible ultrasonic absorption frequency range and improving the detectability of minor species present in solution using Raman spectroscopy. Development of chemometric techniques in these areas needs to keep pace with the improvement of these experimental methods. Refinements in the analysis of ultrasonic and Raman data based on multivariable least squares and factor analysis, respectively, are examined to investigate the kinetics of zinc thiocyanate complex formation in water. Analysis of ultrasonic absorption relaxation spectra verified that the observed process in aqueous Zn(SCN)₂ involves substitution of water from the first coordination shell of Zn²⁺. Use of a multivariable least-squares error surface is described that enhances the reliability of assigned frequencies of ultrasonic absorption maxima. Factor analysis of Raman scattering data provided direct evidence that at least four complex species, such as Zn(SCN)⁺ and Zn(SCN)₂, are simultaneously present in the aqueous zinc thiocyanate solutions.