Global Forcing Number of Benzenoid Graphs

A global forcing set in a simple connected graph G with a perfect matching is any subset S of E(G) such that the restriction of the characteristic function of perfect matchings of G on S is an injection. The number of edges in a global forcing set of the smallest cardinality is called the global forcing number of G. In this paper we prove several results concerning global forcing sets and numbers of benzenoid graphs. In particular, we prove that all catacondensed benzenoids and catafused coronoids with n hexagons have the global forcing number equal to n, and that for pericondensed benzenoids the global forcing number is always strictly smaller than the number of hexagons.     

Can multivalency be expressed kinetically? The answer is yes

Inspired by the concept of multivalency and in pursuit of ever more intricate artificial molecular machines, we investigated the strict self-assembly of a triply threaded two-component superbundle, starting from a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core and a trifurcated trication wherein three bipyridinium units are linked 1,3,5 to a central benzenoid core. The result of the investigation was quite unexpected and surprising. It transpired that the rapid formation of a doubly threaded two-component complex was followed by an extremely slow conversion (a week at 253 K in CD3COCD3 to reach equilibrium) of this kinetically controlled product into a thermodynamically controlled one, namely a triply threaded two-component superbundle. This intriguing observation begs the question: are there instances in nature where multivalency is expressed as a kinetically controlled process, prior to an equilibrium state being reached, and if so, what are the biological implications, if any?     

Tetraphenylporphyrins monosubstituted with a crown ether in one phenyl ring. Synthesis and characterization

Summary The synthesis and spectroscopic characterization of seven new tetraphenyl-porphyrins (1–7) derivatized with 12-crown-4, 14-crown-4, 15-crown-5, or 18-crown-6 ether units inortho orpara position of one of the phenyl rings is described.

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In einem Phenylring mit Kronenethern monosubstituierte Tetraphenylporphyrine. Synthese und Charakterisierung

Zusammenfassung Die Synthese und die spektroskopische Charakterisierung sieben neuer Tetraphenylporphyrine (1–7), die mit 12-Krone-4, 14-Krone-4, 15-Krone-5 oder 18-Krone-6 in derortho-oderpara-Position eines Phenylrings substituiert sind, werden beschrieben.

     

Cadmium and zinc determination by neutron activation analysis and biochemical tests in tissues of workers professionally exposed to cadmium

Cadmium and zinc levels in urine, serum, hair obtained from workers professionally exposed to cadmium oxide dust and from a control, nonoccupationally exposed group were determined by neutron activation analysis. The study was completed by biochemical monitoring tests such as the ₂ (₂-MG) determination in urine and serum and the -aminolevulinic acid dehydratase (ALAD) determination in blood. Significantly increased levels of cadmium in urine, serum, and hair, ₂-MG in urine and serum, ALAD in blood and decreased levels of zinc in serum were found in the exposed group compared to the control group. The most distinct differences of the parameters studied were observed for cadmium in hair. Correlations among the parameters were preliminary evaluated, too. For quality assurance purposes, the cadmium and zinc concentrations were determined in biological (standard) reference materials NBS SRM-1577 Bovine Liver, Bowen's Kale, IAEA A-11 Milk Powder, and IAEA H-8 Horse Kidney.     

Improvement of electron capture efficiency by resonant excitation

A novel pulse sequence improving the efficiency for electron capture dissociation (ECD) of an unmodified Fourier transform ion cyclotron resonance (FTICR) mass spectrometer by more than an order of magnitude is presented. Commercially available FTICR instruments are usually equipped with a filament-based electron source producing an electron beam that has a rather small cross section. An ideal overlap between the rotating ion cloud and the electron beam appears to be a prerequisite for a high ECD efficiency. A reduced interception of the ion cloud and the electron beam is probably due to the contribution of the magnetron motion to the trajectory of the ions, resulting in a precession about the z-axis of the instrument. By increasing the kinetic energy and therefore increasing the cyclotron radii of the precursor ions by resonant excitation, the overlap of the rotating ion cloud with the electron beam is improved. By use of this protocol the efficiency of electron capture is substantially increased and consequently the acquisition time of ECD spectra is reduced significantly. The capability of resonant excitation of the precursor ions during the irradiation with electrons is demonstrated for standard peptides. This approach is particularly valuable for analysis and characterization of O-glycosylated peptides. In addition to amino acid sequence information, the attachment site of the labile glycan moiety is determined, and also radical-site-induced fragmentations of the glycosidic bonds are observed.     

Supplementation with Magnesium Salts—A Strategy to Increase Nutraceutical Value of Pleurotus djamor Fruiting Bodies

The use of substrates supplemented with minerals is a promising strategy for increasing the nutraceutical value of Pleurotus spp. The current research was performed to analyze the effect of substrate supplementation with magnesium (Mg) salts on the Mg content, biomass, and chemical composition of pink oyster mushroom (Pleurotus djamor) fruiting bodies. Before inoculation, substrate was supplemented with MgCl₂ × 6 H₂O and MgSO₄, both salts were applied at three concentrations: 210, 420, and 4200 mg of Mg per 2 kg of substrate. The harvest period included three flushes. Substrate supplementation with 4200 mg of Mg caused the most significant decrease in mushroom productivity, of about 28% for both Mg salts. The dry matter content in fruiting bodies was significantly lower in the treatment in which 210 mg of Mg was applied as MgSO₄ in comparison to the control. Supplementation effectively increased the Mg content in fruiting bodies of P. djamor by 19–85% depending on the treatment, and significantly affected the level of remaining bioelements and anions. One hundred grams of pink oyster fruiting bodies, supplemented with Mg salts, provides more than 20% of the Mg dietary value recommended by the Food and Drug Administration (FDA); thus, supplementation can be an effective technique for producing mushrooms that are rich in dietary Mg. Although P. djamor grown in supplemented substrate showed lower productivity, this was evident only in the fresh weight because the differences in dry weight were negligible. Mg supplementation increased the antioxidant activity of the fruiting bodies, phenolic compounds, and some amino acids, including L-tryptophan, and vitamins (thiamine and l-ascorbic acid).     

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.     

Isotachophoretic analysis of the dihydrofolate reductase reaction in the presence of methotrexate and ascorbic acid

The antifolate methotrexate (MTX) is widely used in cancer chemotherapy. In this study, we show that MTX (MTX-Glu1) and MTX-polyglutamates (MTX-Glu2-5) strongly inhibited the growth of the leukemic cell line MOLT-4. This effect, however, was mitigated by ascorbic acid. We investigated whether ascorbic acid is able to reduce dihydrofolic acid (DHF) to tetrahydrofolic acid (THF) directly or by circumventing the MTX inhibition of dihydrofolate reductase (DHFR). The inhibition of this NADPH-dependent reduction of DHF by MTX-Glun in the absence or presence of ascorbate, was determined by analytical isotachophoresis. Using 0.01 M HCl/histidine, pH 6.0, as a leading electrolyte (L) and 0.005 M 2-(N-morpholino)ethanesulfonic acid (MES)/histidine, pH 6.0, as a terminating electrolyte (T), MTX-Glun derivatives including MTX-Glu1 could be easily separated, whereas the quantitative estimation of THF was not possible. A quantitative characterization of the DHFR reaction by measuring NADPH, NADP+ and ascorbate was achieved with another system (L: 0.01 M HCI/beta-alanine, pH 3.73; T: 0.01 M caproic acid, pH 3.27). Nanomolar concentrations of MTX-Glu1-5 inhibited consumption of NADPH and production of NADP+. Ascorbic acid was not able to reduce DHF, neither directly nor after inhibition of DHFR by MTX. However, ascorbic acid seemed to diminish the oxidation of THF and this may account for its capacity to reduce the inhibitory effect of MTX on MOLT-4 cells.     

Cyclic chronopotentiometry of nickel(II) at mercury electrodes in acidic perchlorate solutions: Case of higher order nonregenerative reactions following electron transfer

The reduction of Ni²⁺ ions at mercury electrodes in acidic perchlorate solutions, at perchlorate concentrations below 0.2 M, is characterized by absence of kinetic control in the preceding step, and by a complex reaction mechanism following the electron transfer. This reaction sequence is known to involve intermetallic compound formation between Ni and Hg and is best described, as shown here, by a parallel second and third order kinetic scheme. Apparent rate coefficients for this kinetic scheme were determined using cyclic chronopotentiometric data and fitting by digital simulation. A linearization test of computed kinetic rate coefficients versus the number of transitions permits quantitative tests of validity of assumptions made.     

Mössbauer spectroscopic and X-ray diffraction study of the thermal decomposition of natural siderite and goethite

Thermal decomposition of natural siderite and goethite has been studied using Mössbauer spectroscopy and X-ray diffraction. Hematite and magnetite were the principal compounds formed during high temperature treatment of siderite. Natural goethite transformed to hematite at high temperatures. The crystal structures, stoichiometry and the nuclear magnetic properties of Fe-oxides formed are discussed.