Thermographic examination of prick test reactions with local anesthetic

Journal of Thermal Analysis and Calorimetry - The objective of this work was to examine the thermal conductivity of a stable nano-antifreeze containing cetyltrimethylammonium bromide coated cerium...     

Kinetic study of the oxidation reaction of 4-methylphenyl radical

A kinetic study of the reaction of the 4-methylphenyl radical (4-C₆H₄CH₃) with the oxygen molecule was conducted using experimental and theoretical approaches. The absorption spectrum for the λ = 266 nm photolysis of the 4-C₆H₄CH₃X (X = Cl, Br)/N₂/O₂ mixture was measured in the wavelength range of λ = 503-512 nm using N₂ as the buffer gas at a total pressure of 40 Torr using a cavity ring-down spectroscopy apparatus coupled with a pulsed laser photolysis system. Based on the absorbance of the product of the 4-C₆H₄CH₃ + O₂ reaction at λ = 504 nm, the reaction rate coefficient for the 4-C₆H₄CH₃ + O₂ reaction was determined to be k = (1.21 ± 0.10) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ and k = (1.18 ± 0.21) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ using 4-C₆H₄CH₃Cl and 4-C₆H₄CH₃Br, respectively, as the radical precursor. And there was no pressure dependence in the total pressure range of 10-90 Torr varying partial pressure of N₂ buffer gas at T = 296 ± 5 K. The geometries, vibration frequencies, and potential energy surfaces of the reactants, major products, and transition states in the 4-C₆H₄CH₃ + O₂ reaction were determined using the CBS-QB3 method. The k value at the high-pressure limit was calculated to be 1.26 × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ using the variational transition-state theory. The calculated value of k was consistent with the experimental value, which indicated that the 4-C₆H₄CH₃ + O₂ reaction reaches the high-pressure limit at 10 Torr. Therefore, the oxidation of the 4-C₆H₄CH₃ radical is almost 10 times faster than that of the benzyl radical, which has the same chemical formula, at the high-pressure limit.     

Visible-Light-Driven Photocatalyst- and Additive-Free Cross-Coupling of β-Ketothioamides with α-Diazo 1,3-Diketones: Access to Highly Functionalized Thiazolines

A photocatalyst- and additive-free, visible-light-mediated chemoselective domino protocol was devised to access fully substituted thiazoline derivatives from β-ketothioamides and α-diazo 1,3-diketones at moderate temperature in open air. The reaction proceeds through in situ generation of electrophilic carbenes from α-diazo 1,3-diketones by a low-energy blue LED (448 nm), which undergoes selective coupling with nucleophilic β-ketothioamides to give thiazolines by successive formation of C−S and C−N bonds in one stretch. Notably, the benign and clean conditions, operational simplicity, sustainability, 100 % carbon economy, high yields, and wide functional-group tolerance are further attributes of the strategy. A mechanistic rationale for this cascade reaction sequence is well supported by control experiments.     

Cross-validated bagged learning

Many applications aim to learn a high dimensional parameter of a data generating distribution based on a sample of independent and identically distributed observations. For example, the goal might be to estimate the conditional mean of an outcome given a list of input variables. In this prediction context, bootstrap aggregating (bagging) has been introduced as a method to reduce the variance of a given estimator at little cost to bias. Bagging involves applying an estimator to multiple bootstrap samples and averaging the result across bootstrap samples. In order to address the curse of dimensionality, a common practice has been to apply bagging to estimators which themselves use cross-validation, thereby using cross-validation within a bootstrap sample to select fine-tuning parameters trading off bias and variance of the bootstrap sample-specific candidate estimators. In this article we point out that in order to achieve the correct bias variance trade-off for the parameter of interest, one should apply the cross-validation selector externally to candidate bagged estimators indexed by these fine-tuning parameters. We use three simulations to compare the new cross-validated bagging method with bagging of cross-validated estimators and bagging of non-cross-validated estimators.     

Nonparametric estimation of past extropy under $$\alpha $$ -mixing dependence condition

Ricerche di Matematica - Di Crescenzo and Longobardi (J Appl Prob 39, 434–440, 2002), introduced the concept of past entropy for measuring uncertainty contained in past lifetime of random...     

Constraints onZ 1–Z 2 mixing from the decayZ 1→e− e + in the left-right symmetric model

We examine the decay ofZ ₁ in electrons with recent data from LEP. The partial width (Z ₁e^– e ⁺) is studied in the framework of a left-right symmetric model with standard electroweak corrections. Processes measured near the resonance has served to measure the neutral coupling constants very precisely, which is useful to set bounds on the parameters of the model. This partial decay occurs in the resonance zone. As a consequence the process is independent of the mass of the additionalZ ₂ heavy gauge boson which appears in this kind of models and so we have the mixing angle between the left and the right bosons as the only additional parameter. In this paper we take advantage of this fact to set a bound for : –9×10^–34×10^–3, which is in agreement with other constraints previously reported.     

Theoretical studies on the deacylation step of serine protease catalysis in the gas phase, in solution, and in elastase

The deacylation step of serine protease catalysis is studied using DFT and ab initio QM/MM calculations combined with MD/umbrella sampling calculations. Free energies of the entire reaction are calculated in the gas phase, in a continuum solvent, and in the enzyme elastase. The calculations show that a concerted mechanism in the gas phase is replaced by a stepwise mechanism when solvent effects or an acetate ion are added to the reference system, with the tetrahedral intermediate being a shallow minimum on the free energy surface. In the enzyme, the tetrahedral intermediate is a relatively stable species ( approximately 7 kcal/mol lower in energy than the transition state), mainly due to the electrostatic effects of the oxyanion hole and Asp102. It is formed in the first step of the reaction, as a result of a proton transfer from the nucleophilic water to His57 and of an attack of the remaining hydroxyl on the ester carbonyl. This is the rate-determining step of the reaction, which requires approximately 22 kcal/mol for activation, approximately 5 kcal/mol less than the reference reaction in water. In the second stage of the reaction, only small energy barriers are detected to facilitate the proton transfer from His57 to Ser195 and the breakdown of the tetrahedral intermediate. Those are attributed mainly to a movement of Ser195 and to a rotation of the His57 side chain. During the rotation, the imidazolium ion is stabilized by a strong H-bond with Asp102, and the C(epsilon)(1)-H...O H-bond with Ser214 is replaced by one with Thr213, suggesting that a "ring-flip mechanism" is not necessary as a driving force for the reaction. The movements of His57 and Ser195 are highly correlated with rearrangements of the binding site, suggesting that product release may be implicated in the deacylation process.     

Direct covalent grafting of conjugated molecules onto Si, GaAs, and Pd surfaces from aryldiazonium salts

Using aryldiazonium salts that are air-stable and easily synthesized, we describe here a one-step, room-temperature route to direct covalent bonds between pi-conjugated organic molecules on three material surfaces: Si, GaAs, and Pd. The Si can be in the form of single crystal Si including heavily doped p-type Si, intrinsic Si, heavily doped n-type Si, on Si(111) and Si(100), and on n-type polycrystalline Si. The formation of the aryl-metal or aryl-semiconductor bond attachments was confirmed by corroborating evidence from ellipsometry, reflectance FTIR, XPS, cyclic voltammetry, and AFM analyses of the surface-grafted monolayers. A data-encompassing explanation for the mechanism suggests a diazonium activation by reduction at the open circuit potential, with aryl radical secondary products bonding to the surface. The synthetic details are included for preparing the surface-grafted monolayers and the precursor diazonium salts. This spontaneous diazonium activation reaction offers an attractive route to highly passivating, robust monolayers and multilayers on many surfaces that allow for strong bonds between carbon and surface atoms with molecular species that are near perpendicular to the surface.     

Synthesis and Molecular Structures of Hydrotris(dimethylpyrazolyl)borate Complexes of the Lanthanides

The reaction of lanthanide triflates with 2 equiv of potassium hydrotris(dimethylpyrazolyl)borate (Tp(Me)()2) gives good yields of complexes of composition Ln(Tp(Me)()2)(2)OTf. For La (2), Ce (3), Pr (4), and Nd (5) the complexes are seven-coordinate in the solid state with the triflate group coordinated to the metal in unidentate fashion. Complex 5 crystallizes in the monoclinic space group P2(1)/c with a = 17.629(3) ?, b = 12.740(2) ?, c = 18.163(3) ?, beta = 107.35(1) degrees, V = 3893(1) ?(3), Z = 4, and R(w) = 0.0458. For the complexes of Y (1), Sm (6), Eu (7), Gd (8), Dy (9), Ho (10), and Yb (11), the smaller size of the metal ion leads to ejection of the triflate from the coordination sphere and the complexes are ionic in the solid state with a six-coordinate metal center. Complex 11 crystallizes in the monoclinic space group C2/m with a = 16.593(7) ?, b = 13.671(5) ?, c = 8.746(2) ?, beta = 91.66(3) degrees, V = 1983(1) ?(3), Z = 2, and R(w) = 0.0416. In solution, however, complex 6 adopts a seven-coordinate molecular structure with the triflate ion within the first coordination sphere.