Minicomputer-controlled,background-subtracted anodic stripping voltammetry: evaluation of parameters and performance

A new minicomputer-controlled anodic stripping voltammetry technique is described. The technique uses differential voltammetry at one electrode, and uses a rapid data-averaging algorithm to avoid the need for scan averaging; this allows excellent sensitivities and short analysis times, with adequate reproducibilities. Both linear-scan and staircase waveforms are discussed in conjunction with the technique, and the approximate Roe—Toni theory for linear-scan voltammetry is shown to apply. The system response is investigated for film thickness, scan rate, deposition time, electrode rotation rate, and metal concentration. Results were used to optimize the sensitivity of the technique. The metal ions Cd, Pb and Cu could be determined in solutions as dilute as 1–10 pg/ml^-1 in 15 min. The viability of the technique in solutions showing a large background is also discussed, and a comparison is made with scan-averaged techniques.     

Molar excess enthalpies and volumes of mixtures of 2,4,6-trimethyl-pyridine with some aliphatic alcohols

The relationship enthalpy of mixing and excess molar volume of mixing versus composition were studied at 313.15 K for binary systems of 2,4,6-collidine with normal aliphatic alcohols. It was found that at this temperature the values ofH ^E andV ^E are negative and change with the length of the alkyl group of the alcohol.     

Four-Body Bound-States Systems in Relativistic Scalar Quantum Field Theory: Variational Basis-State Approach

The variational method within the Hamiltonian formalism of quantum field theory has been used in order to investigate the effect of virtual pairs for four-body scalar systems consisting of two particles and two antiparticles of the same mass. The scalar particles and antiparticles interact via a massive or massless mediating scalar field. The ground state energy solutions of Fock-space variational trial states (\(|N{\bar {N}}N{\bar {N}}{ \rangle }+|N{\bar {N}}N{\bar {N}}N{\bar {N}\rangle }\)) of the relativistic wave equations have been studied. We have compared these results with the previous work of four-body system (variational trial states of the form \(|N{ \bar {N}}N{\bar {N}}{\rangle }\)) and we have shown that the inclusion of virtual pairs has a noticeable effect at low coupling and at high coupling the energy of the system is changed by an important amount. In other words, the calculations show that the inclusion of virtual pairs augments the binding energy of the four-body system by a substantial amount at strong coupling. This study can pave the way for some new ideas in order to investigate the effect of virtual pairs, for example, for a bound-states quark-antiquark or tetraquark systems in future.     

Infrared emission spectroscopy of liquid samples with multivariate calibration as a model for process analytical applications

Infrared emission spectroscopy and multivariate calibration are used to provide a method for the quantitative analysis of liquid samples. Differing forms of the data including second derivative and interferogram representation are used for prediction of sample composition, thickness and temperature. Comparisons are made with transmission measurements of the same samples. In some situations emission measurements may be the preferred method of analysis.     

Spin hamiltonian parameters for Cu(II)-prion peptide complexes from L-band electron paramagnetic resonance spectroscopy

Cu(II) is an essential element for life but is also associated with numerous and serious medical conditions, particularly neurodegeneration. Structural modeling of crystallization-resistant biological Cu(II) species relies on detailed spectroscopic analysis. Electron paramagnetic resonance (EPR) can, in principle, provide spin hamiltonian parameters that contain information on the geometry and ligand atom complement of Cu(II). Unfortunately, EPR spectra of Cu(II) recorded at the traditional X-band frequency are complicated by (i) strains in the region of the spectrum corresponding to the g(∥) orientation and (ii) potentially very many overlapping transitions in the g(⊥) region. The rapid progress of density functional theory computation as a means to correlate EPR and structure, and the increasing need to study Cu(II) associated with biomolecules in more biologically and biomedically relevant environments such as cells and tissue, have spurred the development of a technique for the extraction of a more complete set of spin hamiltonian parameters that is relatively straightforward and widely applicable. EPR at L-band (1-2 GHz) provides much enhanced spectral resolution and straightforward analysis via computer simulation methods. Herein, the anisotropic spin hamiltonian parameters and the nitrogen coordination numbers for two hitherto incompletely characterized Cu(II)-bound species of a prion peptide complex are determined by analysis of their L-band EPR spectra.     

Rotational—vibrational dipole transitions in HD

The transition moments are computed for several lines in the X¹Σ⁺_g state of HD. The results are obtained by taking into account interactions with Σ_u and Π_u states. It is shown that the latter influence appreciably the transition probabilities in the 00 band. The permanent dipole moment is also computed for several vibrational and rotational states.     

Omega- and Omega+ production in central Pb + Pb collisions at 40 and 158A GeV

Results are presented on Omega production in central Pb+Pb collisions at 40 and 158A GeV beam energy. For the first time in heavy ion reactions, rapidity distributions and total yields were measured for the sum Omega(-) + Omega(+) at 40A GeV and for Omega(-) and Omega(+) separately at 158A GeV. The yields are strongly underpredicted by the string-hadronic UrQMD model but agree better with predictions from hadron gas models.     

Field evaluations of the VDmax approach for substantiation of a 25 kGy sterilization dose and its application to other preselected doses

The International and European standards for radiation sterilization require evidence of the effectiveness of a minimum sterilization dose of 25 kGy but do not provide detailed guidance on how this evidence can be generated. An approach, designated VD_max, has recently been described and computer evaluated to provide safe and unambiguous substantiation of a 25 kGy sterilization dose. The approach has been further developed into a practical method, which has been subjected to field evaluations at three manufacturing facilities which produce different types of medical devices. The three facilities each used a different overall evaluation strategy: Facility A used VD_max for quarterly dose audits; Facility B compared VD_max and Method 1 in side-by-side parallel experiments; and Facility C, a new facility at start-up, used VD_max for initial substantiation of 25 kGy and subsequent quarterly dose audits. A common element at all three facilities was the use of 10 product units for irradiation in the verification dose experiment.

The field evaluations of the VD_max method were successful at all three facilities; they included many different types of medical devices/product families with a wide range of average bioburden and sample item portion values used in the verification dose experiments. Overall, around 500 verification dose experiments were performed and no failures were observed. In the side-by-side parallel experiments, the outcomes of the VD_max experiments were consistent with the outcomes observed with Method 1.

The VD_max approach has been extended to sterilization doses >25 and <25 kGy; verification doses have been derived for sterilization doses of 15, 20, 30, and 35 kGy. Widespread application of the VD_max method for doses other than 25 kGy must await controlled field evaluations and the development of appropriate specifications/standards.     

TLC and HPLC Analysis of the Phenolic Acids in Silphium perfoliatum L. Leaves,Inflorescences and Rhizomes

JPC – Journal of Planar Chromatography – Modern TLC - TLC and HPLC have been used for preliminary evaluation of the phenolic acids occurring in the leaves, inflorescences, and rhizomes...     

An Autonomous Chemical Robot Discovers the Rules of Inorganic Coordination Chemistry without Prior Knowledge

We present a chemical discovery robot for the efficient and reliable discovery of supramolecular architectures through the exploration of a huge reaction space exceeding ten billion combinations. The system was designed to search for areas of reactivity found through autonomous selection of the reagent types, amounts, and reaction conditions aiming for combinations that are reactive. The process consists of two parts where reagents are mixed together, choosing from one type of aldehyde, one amine and one azide (from a possible family of two amines, two aldehydes and four azides) with different volumes, ratios, reaction times, and temperatures, whereby the reagents are passed through a copper coil reactor. Next, either cobalt or iron is added, again from a large number of possible quantities. The reactivity was determined by evaluating differences in pH, UV‐Vis, and mass spectra before and after the search was started. The algorithm was focused on the exploration of interesting regions, as defined by the outputs from the sensors, and this led to the discovery of a range of 1‐benzyl‐(1,2,3‐triazol‐4‐yl)‐N‐alkyl‐(2‐pyridinemethanimine) ligands and new complexes: [Fe(L¹)₂](ClO₄)₂ ( 1 ); [Fe(L²)₂](ClO₄)₂ ( 2 ); [Co₂(L³)₂](ClO₄)₄ ( 3 ); [Fe₂(L³)₂](ClO₄)₄ ( 4 ), which were crystallised and their structure confirmed by single‐crystal X‐ray diffraction determination, as well as a range of new supramolecular clusters discovered in solution using high‐resolution mass spectrometry.