Solvolysis of 1,1-dimethyl-4-alkenyl chlorides: evidence for pi-participation

Tertiary 1,1-dimethyl-4-alkenyl chloride (1) solvolyzes with significantly reduced secondary beta-deuterium kinetic isotope effect (substrate with two trideuteromethyl groups) and has a lower entropy and enthalpy of activation than the referent saturated analogue 4 (k(H)/k(D) = 1.30 +/- 0.03 vs k(H)/k(D) = 1.79 +/- 0.01; Delta Delta H(++) = -9 kJ mol(-1), Delta Delta S(++) = -36 J mol(-1) K(-1), in 80% v/v aqueous ethanol), indicating participation of the double bond in the rate-determining step. Transition structure 1-TS computed at the MP2(fc)/6-31G(d) level of theory revealed that the reaction proceeds through a late transition state with considerably pronounced double bond participation and a substantially cleaved C-Cl bond. The doubly unsaturated compound 3 (1,1-dimethyl-4,8-alkadienyl chloride) solvolyzes with further reduction of the isotope effect, and a drastically lower entropy of activation (k(H)/k(D) = 1.14 +/- 0.01; DeltaS(++) = -152 +/- 12 J mol(-1) K(-1), in 80% v/v aqueous ethanol), suggesting that the solvolysis of 3 proceeds by way of extended pi-participation, i.e., the assistance of both double bonds in the rate-determining step.     

Review: Hamiltonian Linearization of the Rest-Frame Instant Form of Tetrad Gravity in a Completely Fixed 3-Orthogonal Gauge: A Radiation Gauge for Background-Independent Gravitational Waves in a Post-Minkowskian Einstein Spacetime

In the framework of the rest-frame instant form of tetrad gravity, where the Hamiltonian is the weak ADM energy , we define a special completely fixed 3-orthogonal Hamiltonian gauge, corresponding to a choice of non-harmonic 4-coordinates, in which the independent degrees of freedom of the gravitational field are described by two pairs of canonically conjugate Dirac observables (DO) . We define a Hamiltonian linearization of the theory, i.e. gravitational waves, without introducing any background 4-metric, by retaining only the linear terms in the DO's in the super-hamiltonian constraint (the Lichnerowicz equation for the conformal factor of the 3-metric) and the quadratic terms in the DO's in . We solve all the constraints of the linearized theory: this amounts to work in a well defined post-Minkowskian Christodoulou-Klainermann space-time. The Hamilton equations imply the wave equation for the DO's , which replace the two polarizations of the TT harmonic gauge, and that linearized Einstein's equations are satisfied. Finally we study the geodesic equation, both for time-like and null geodesics, and the geodesic deviation equation.     

Kinetics of the conversion reaction of gypsum with ammonium carbonate

The reactivity of flue gas desulphurization gypsum with ammonium carbonate has been studied in the temperature range (20–50) °C. Mechanism of this reaction was suggested and the kinetics parameters characterizing the reaction were determined. A mathematical model suitable for the prediction of the conversion of gypsum was proposed. The reaction is of the second order. Influence of the size of gypsum particles on the relationship between the surface and volume of the particles is not significant. From the obtained experimental results, it follows that the reaction does not proceed at the surface of the solid gypsum particles, but in the liquid phase between dissolved gypsum and ammonium carbonate. The diffusion of the dissolved gypsum through the liquid film formed at the surface of the solid gypsum particles is the rate-limiting step of the conversion reaction.     

One-step solid-phase UV spectrophotometric method for phenol determination in vaccines: Development and quality assessment

A solid-phase spectrophotometric technique was used to develop very sensitive, inexpensive, onestep procedure for determination of phenol (UV-SPS procedure). The proposed procedure is based on simultaneous sorption of phenol on an anion exchanger QAE Sephadex A-25 (40 mg), within 10 min at pH 11 and measurement of the intrinsic absorbance of the solid phase in a 1-mm cell at 289 and 500 nm, without previous derivatization. The optimum experimental conditions were investigated and comprehensive quality control of the new procedure was carried out using a prevalidation strategy accompanied by a very informative system of diagnosis. The UV-SPS procedure is characterized with both ideal calibration and analytical evaluation function within analyte working range from 0.3 to 3.0 μmol (6.0 to 60.0 nmol/mL). Random deviations (from ±0.3 to ±5.0%) and systematic deviations (from ?3.0 to +4.9%) confirmed the favourable precision and accuracy of the UV-SPS method. Evaluated limiting values (L _D = 1.0 μM, L _Q = 6.0 μM) showed that this method enables determination of very low levels of phenol. The sensitivity of UV-SPS procedure is 50 times higher than that provided by the corresponding method in solution. The UV-SPS method was successfully applied to the determination of phenol in vaccines (recovery 95.6–103.4%).     

Observation of water molecules bound to a protein using cold-spray ionization mass spectrometry.

The characterization of water molecules bound to ribonuclease T1 (RNase T1) was carried out using cold-spray ionization mass spectrometry (CSI-MS). CSI-MS is a variant of electrospray ionization mass spectrometry (ESI-MS) operating at low temperature, and is particularly suitable for investigating the weaker molecular associations, since the temperature at the spray interface is much lower than that in the conventional ESI-MS. In this approach, ion peaks due to the addition of nine water molecules were identified at a spray temperature of 48 degrees C. This result showed good agreement with that inferred by the combinational analysis of NMR and X-ray crystallography, indicating that CSI-MS is capable of rapidly providing reliable information to characterize the number of water molecules bound to a macromolecule.     

Quality Assessment of Two Spectrophotometric Procedures for Polyphenol Determination and Application in Moltkia petraea Species

A comparison study of quality of two spectrophotometric procedures: Schneider’s (T‐Sch) and 4‐aminoantipyrine (T‐AAP) procedures for total polyphenols determination was carried out using informative prevalidation strategy. Good quality of the measurements at the lower analyte level, excellent resolution of signals, homogenous data material, ideal linear calibration and analytical evaluation functions, very low limit of quantitation (0.13 μg/mL), and high precision (from ±0.60 % to ±3.43 %) and accuracy (from ?4.26 % to +4.00 %) confirmed the high quality of the T‐Sch procedure. Although favorable performance characteristics of T‐AAP procedure were obtained, the signal resolution, sensitivity, precision and accuracy are somewhat lower than in T‐Sch procedure. Both prevalidated procedures were successfully applied to determine total polyphenols in leaves, stems, and flowers in three populations of endemic Illyric? Balkan species Moltkia petraea (Tratt.) Griseb. growing in Croatia. Total concentrations of polyphenols obtained by T‐Sch procedure in all plant organs of all populations were somewhat lower than determined by T‐AAP procedure. However, the relative abundance of polyphenols obtained by both methods is the same. Prevalidation results demonstrated the reliability of the T‐AAP and T‐Sch procedures as valuable tools in polyphenols analysis and their application provided new information regarding phytochemical characterization of endemic M. petraea.     

Pseudo 1-homogeneous distance-regular graphs

Let Γ be a distance-regular graph of diameter d≥2 and a ₁≠0. Let θ be a real number. A pseudo cosine sequence for θ is a sequence of real numbers σ ₀,…,σ _d such that σ ₀=1 and c _i σ _i−1+a _i σ _i +b _i σ _i+1=θ σ _i for all i∈{0,…,d−1}. Furthermore, a pseudo primitive idempotent for θ is E _θ =s ∑ _i=0 ^d σ _i A _i , where s is any nonzero scalar. Let be the characteristic vector of a vertex v∈VΓ. For an edge xy of Γ and the characteristic vector w of the set of common neighbours of x and y, we say that the edge xy is tight with respect to θ whenever θ≠k and a nontrivial linear combination of vectors , and Ew is contained in . When an edge of Γ is tight with respect to two distinct real numbers, a parameterization with d+1 parameters of the members of the intersection array of Γ is given (using the pseudo cosines σ ₁,…,σ _d , and an auxiliary parameter ε). Let S be the set of all the vertices of Γ that are not at distance d from both vertices x and y that are adjacent. The graph Γ is pseudo 1-homogeneous with respect to xy whenever the distance partition of S corresponding to the distances from x and y is equitable in the subgraph induced on S. We show Γ is pseudo 1-homogeneous with respect to the edge xy if and only if the edge xy is tight with respect to two distinct real numbers. Finally, let us fix a vertex x of Γ. Then the graph Γ is pseudo 1-homogeneous with respect to any edge xy, and the local graph of x is connected if and only if there is the above parameterization with d+1 parameters σ ₁,…,σ _d ,ε and the local graph of x is strongly regular with nontrivial eigenvalues a ₁ σ/(1+σ) and (σ ₂−1)/(σ−σ ₂).