Development and prevalidation of a method for phenol determination by solid-phase spectrophotometry

A simple, sensitive and rapid solid-phase spectrophotometric procedure was developed for the determination of traces of phenol with 4-aminoantipyrine as a reagent (AAP-SPS), and the optimal experimental conditions were established. This method was performed by sorption and direct absorbance measurements of the product phenol-AAP sorbed on the anion-exchanger Dowex 1-X4 (0.2 g) at 495 nm (absorption maximum) and 700 nm (non-absorption wavelength). The sensitivity offered by the AAP-SPS procedure was higher by a factor of 40 compared with the respective conventional spectrophotometric method. Metrological characteristics were established using a prevalidation strategy. The AAP-SPS procedure is characterized by a linear calibration function in the working range of 0.05–0.50 μmol, low standard deviation of procedure (±0.012), low limit of determination (0.021 μmol), and favorable random (±0.85 to ±11.27%) and systematic deviations (−4.55 to +11.50%). Moreover, the accuracy of the system investigated by the recovery test is acceptable (99–102%). Favorable working and performance characteristics make the new SPS method ideal for phenol monitoring in pharmaceutical preparations as well as other matrices.     

A synthesis, including asymmetric synthesis, of α-quaternary α-amino aldehydes from ketones and chloromethyl p-tolyl sulfoxide via sulfinylaziridines

Treatment of 1-chlorovinyl p-tolyl sulfoxides, prepared from ketones and chloromethyl p-tolyl sulfoxide, with N-lithio arylamines resulted in the formation of sulfinylaziridines in good to high yields. The sulfinylaziridines were treated with N-lithio aniline or N-lithio p-chloroaniline to afford α-quaternary α-amino aldehydes in good yields. From α-quaternary α-amino aldehydes, α-quaternary α-amino acid esters and β-quaternary β-amino alcohols were obtained. When optically active chloromethyl p-tolyl sulfoxide was used in this procedure, a method for the synthesis of optically active α-quaternary α-amino aldehydes was realized. The reaction mechanism, including asymmetric induction, for the formation of the sulfinylaziridines is described.     

Microcolumns with self-assembled particle frits for proteomics

LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles bridged the outlet with 0.3 pl dead volume and perfect success rate. In peptide analysis by LC-MS, the peak width at half height was normally less than 6 s, compared to 12 s without SAPs. The LC-MS-MS system provided 37% sequence coverage (21 matched peptides) for a tryptically-digested sample of 10 fmol bovine serum albumin. We also describe application of the SAP principle to make disposable pipette tip columns with short pieces of fused-silica capillary as the outlet.     

Modelling day‐ahead electricity prices

A production‐based approach is introduced to take into account different attitudes and liabilities of market participants to discuss the equilibrium day‐ahead prices on electricity. Conditions ensuring the existence of the equilibrium are given and price distribution is considered. A discussion of reasons for high price volatility is given.     

Stereoselective Csp3−Csp2 Cross‐Couplings of Chiral Secondary Alkylzinc Reagents with Alkenyl and Aryl Halides

We report palladium‐catalyzed cross‐coupling reactions of chiral secondary non‐stabilized dialkylzinc reagents, prepared from readily available chiral secondary alkyl iodides, with alkenyl and aryl halides. This method provides α‐chiral alkenes and arenes with very high retention of configuration (dr up to 98:2) and satisfactory overall yields (up to 76 % for 3 reaction steps). The configurational stability of these chiral non‐stabilized dialkylzinc reagents was determined and exceeded several hours at 25 °C. DFT calculations were performed to rationalize the stereoretention during the catalytic cycle. Furthermore, the cross‐coupling reaction was applied in an efficient total synthesis of the sesquiterpenes (S)‐ and (R)‐curcumene with control of the absolute stereochemistry.     

1-Homogeneous Graphs with Cocktail Party μ-Graphs

Let be a graph with diameter d 2. Recall is 1-homogeneous (in the sense of Nomura) whenever for every edge xy of the distance partition{{z V() | (z, y) = i, (x, z) = j} | 0 i, j d}is equitable and its parameters do not depend on the edge xy. Let be 1-homogeneous. Then is distance-regular and also locally strongly regular with parameters (v,k,,), where v = k, k = a ₁, (v – k – 1) = k(k – 1 – ) and c ₂ + 1, since a -graph is a regular graph with valency . If c ₂ = + 1 and c ₂ 1, then is a Terwilliger graph, i.e., all the -graphs of are complete. In [11] we classified the Terwilliger 1-homogeneous graphs with c ₂ 2 and obtained that there are only three such examples. In this article we consider the case c ₂ = + 2 3, i.e., the case when the -graphs of are the Cocktail Party graphs, and obtain that either = 0, = 2 or is one of the following graphs: (i) a Johnson graph J(2m, m) with m 2, (ii) a folded Johnson graph J¯(4m, 2m) with m 3, (iii) a halved m-cube with m 4, (iv) a folded halved (2m)-cube with m 5, (v) a Cocktail Party graph K _{m × 2} with m 3, (vi) the Schläfli graph, (vii) the Gosset graph.     

Nonexistence of some Antipodal Distance-regular Graphs of Diameter Four

We find an inequality involving the eigenvalues of a regular graph; equality holds if and only if the graph is strongly regular. We apply this inequality to the first subconstituents of a distance-regular graph and obtain a simple proof of the fundamental bound for distance-regular graphs, discovered by Juri i , Koolen and Terwilliger. Using this we show that for distance-regular graphs with certain intersection arrays, the first subconstituent graphs are strongly regular. From these results we prove the nonexistence of distance-regular graphs associated to 20 feasible intersection arrays from the book Distance-Regular Graphs by Brouwer, Cohen and Neumaier .