Chemical ionization mass spectrometry of complex molecules—VI: Peptides

The chemical ionization mass spectra of a series of simple peptides containing six or fewer amino acids have been studied. Using methane as the reactant gas we found cleavage of the peptide bond occurs in two ways, yielding either the acyl carbonium ion or the complementary ammonium ion. The observation of both types of fragments permits the determination of the amino acid sequence of the peptide. The ammonium ions provide an additional sequence determining route compared to that available from electron-impact spectra. ‘Sequence-determing ions,’ especially the quasimolecular ion at m/e [M+1] are usually more intense than in the electron-impact mass spectra.     

Pyrrolopyrimidine nucleosides. XIII. Synthesis and chemical reactivity of certain selenopyrrolo[2,3-d]pyrimidine nucleosides

5-Cyano-7-(β-D-ribofuranosyl)pyrrolo[2,3-d]pyrimidin-4-selone ( 1 ) has been prepared via a reaction of the appropriate 4-chloro compound with sodium hydrogen selenide. Alkylation of 2 under basic conditions has provided certain 4-substitutedseleno-5-cyano-7-(β-D-ribofuranosyl)-pyrrolo[2,3-d]pyrimidines. 5-Cyano-4-methylseleno-7-(β-D-ribofuranosyl)pyrrolo[2,3-d]pyrimidine was allowed to react with hydroxylamine and hydrazine. The products obtained and reaction course were compared to those obtained from identical reactions using the corresponding sulfur analog.     

Unraveling the Intrinsic Color of Chlorophyll

The exact color of light absorbed by chlorophyll (Chl) pigments, the light‐harvesters in photosynthesis, is tuned by the protein microenvironment, but without knowledge of the intrinsic color of Chl it remains unclear how large this effect is. Experimental first absorption energies of Chl a and b isolated in vacuo and tagged with quaternary ammonium cations are reported. The energies are largely insensitive to details of the tag structure, a finding supported by first‐principles calculations using time‐dependent density functional theory. Absorption is significantly blue‐shifted compared to that of Chl‐containing proteins (by 30–70 nm). A single red‐shifting perturbation, such as axial ligation or the protein medium, is insufficient to account even for the smallest shift; the largest requires pigment–pigment interactions.     

Fragment molecular orbital investigation of the role of AMP protonation in firefly luciferase pH-sensitivity

Firefly bioluminescence displays a sensitivity to pH changes through an alteration of the energy of the emitted photon leading to yellow-green light above ～pH 6.5 and red light below this value. Calculations using the fragment molecular orbital method have been performed on the active site of the luciferase enzyme from the Japanese firefly Luciola cruciata in order to investigate both the importance of different protonation states and tautomeric forms of the lumophore, oxyluciferin, and the role played by protonation of the active site AMP molecule. The results suggest that whilst an equilibrium between several protonation/tautomeric states of oxyluciferin is possible, a single oxyluciferin species (the phenolate-keto form) may be mostly responsible for both emission colours, with changes in polarization by the active site caused by protonation of the AMP molecule playing an important role in mediating the pH-dependent shift.     

On one-dimensional superlinear indefinite problems involving the $$\phi $$-Laplacian

Let \(\Omega := ( a,b ) \subset \mathbb {R}\), \(m\in L^{1} ( \Omega ) \) and \(\phi :\mathbb {R\rightarrow R}\) be an odd increasing homeomorphism. We consider the existence of positive solutions for problems of the form

$$\begin{aligned} \left\{ \begin{array} [c]{ll} -\phi ( u^{\prime } ) ^{\prime }=m ( x ) f ( u) &{}\quad \text {in } \Omega ,\\ u=0 &{}\quad \text {on } \partial \Omega , \end{array} \right. \end{aligned}$$

where \(f: [ 0,\infty ) \rightarrow [ 0,\infty ) \) is a continuous function which is, roughly speaking, superlinear with respect to \(\phi \). Our approach combines the Guo-Krasnoselski? fixed-point theorem with some estimates on related nonlinear problems. We mention that our results are new even in the case \(m\ge 0\).

     

Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter

Ultrasonic frequencies of 20 kHz, 382 kHz, 584 kHz, 862 kHz (and 998 kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862 kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862 kHz is around 10% more efficient at generating hydroxyl radicals than the 382 kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42 °C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382 kHz and 862 kHz, though 582 kHz is substantially lower, when the power levels are set at approximately 9 W for all systems. An equivalent power level of 9 W could not be obtained for the 998 kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound.     

Preparation and characterization of MgB2 superconductor

The MgB₂ superconductor, synthesized using solid-state and liquid-phase sintering methods, have been characterized for various properties. The upper critical field, irreversibility line and critical current density have been determined using magnetization data. The current-voltage characteristics recorded under an applied magnetic field revealed the existence of vortex glass transition. The surface analysis using X-ray photoelectron spectroscopy shows that MgB₂ is sensitive to atmospheric degradation.