Oxygen binding to [Pd(L)(L')] (L= NHC, L' = NHC or PR3, NHC = N-heterocyclic carbene). synthesis and structure of a paramagnetic trans-[Pd(NHC)2(η(1)-O2)2] complex

The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR(3)) complexes with O(2) has been examined. Stopped-flow kinetic studies show that O(2) binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))(η(2)-O(2))] occurs in a rapid, second-order process. The enthalpy of O(2) binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(η(2)-O(2))] but to paramagnetic trans-[(Pd(IPr)(2)(η(1)-O(2))(2)], which has been fully characterized. Computational studies addressing the energetics of O(2) binding have been performed and provide insight into reactivity changes as steric pressure is increased.     

Moments of heavy–light current correlators up to three loops

We consider moments of the non-diagonal vector, axial-vector, scalar and pseudo-scalar current correlators involving two different massive quark flavours up to three-loop accuracy. Expansions around the limits where one mass is zero and the equal-mass case are computed. These results are used to construct approximations valid for arbitrary mass values.     

Gas-phase esterification of microfibrillated cellulose (MFC) films

The barrier properties of microfibrillated cellulose (MFC) films were improved by heterogeneous gas-phase esterification using various combinations of trifluoroacetic acid anhydride, acetic acid and acetic anhydride. The temperature, reagent ratio and reaction time were varied in the experimental design. The effects of two different purification procedures on the barrier properties of esterified MFC films were investigated. Washing with water did not affect the barrier properties compared to those of the films that were not washed, while the use of diethyl ether led to improved barrier properties as measured by the contact angle (CA) of water. The chemical composition of the modified films was studied by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Alterations in hydrophobicity and oxygen permeability were evaluated using dynamic CA and oxygen transmission rate measurements, respectively.     

Modeling of micromachined silicon–polymer 2-2 composite matching layers for 15 MHz ultrasound transducers

Silicon–polymer composites fabricated by micromachining technology offer attractive properties for use as matching layers in high frequency ultrasound transducers. Understanding of the acoustic behavior of such composites is essential for using them as one of the layers in a multilayered transducer structure. This paper presents analytical and finite element models of the acoustic properties of silicon–polymer composites in 2-2 connectivity. Analytical calculations based on partial wave solutions are applied to identify the resonance modes and estimate effective acoustic material properties. Finite Element Method (FEM) simulations were used to investigate the interaction between the composite and the surrounding load medium, either a fluid or a solid, with emphasis on the acoustic impedance of the composite. Composites with lateral periods of 20, 40 and 80 μm were fabricated and used as acoustic matching layers for air-backed transducers operating at 15 MHz. These composites were characterized acoustically, and the results were compared with analytical calculations. The analytical model shows that at low to medium silicon volume fraction, the first lateral resonance in the silicon–polymer 2-2 composite is defined by the composite period, and this lateral resonant frequency is at least 1.2 times higher than that of a piezo-composite with the same polymer filler. FEM simulations showed that the effective acoustic impedance of the silicon–polymer composite varies with frequency, and that it also depends on the load material, especially whether this is a fluid or a solid. The estimated longitudinal sound velocities of the 20 and 40 μm period composites match the results from analytical calculations within 2.7% and 2.6%, respectively. The effective acoustic impedances of the 20 and 40 μm period composites were found to be 10% and 26% lower than the values from the analytical calculations. This difference is explained by the shear stiffness in the solid, which tends to even out the surface displacements of the composites.     

Thermodynamic, kinetic, and computational study of heavier chalcogen (S, Se, and Te) terminal multiple bonds to molybdenum, carbon, and phosphorus

Enthalpies of chalcogen atom transfer to Mo(N[t-Bu]Ar)3, where Ar = 3,5-C6H3Me2, and to IPr (defined as bis-(2,6-isopropylphenyl)imidazol-2-ylidene) have been measured by solution calorimetry leading to bond energy estimates (kcal/mol) for EMo(N[t-Bu]Ar)3 (E = S, 115; Se, 87; Te, 64) and EIPr (E = S, 102; Se, 77; Te, 53). The enthalpy of S-atom transfer to PMo(N[ t-Bu]Ar) 3 generating SPMo(N[t-Bu]Ar)3 has been measured, yielding a value of only 78 kcal/mol. The kinetics of combination of Mo(N[t-Bu]Ar)3 with SMo(N[t-Bu]Ar)3 yielding (mu-S)[Mo(N[t-Bu]Ar)3]2 have been studied, and yield activation parameters Delta H (double dagger) = 4.7 +/- 1 kcal/mol and Delta S (double dagger) = -33 +/- 5 eu. Equilibrium studies for the same reaction yielded thermochemical parameters Delta H degrees = -18.6 +/- 3.2 kcal/mol and Delta S degrees = -56.2 +/- 10.5 eu. The large negative entropy of formation of (mu-S)[Mo(N[t-Bu]Ar)3]2 is interpreted in terms of the crowded molecular structure of this complex as revealed by X-ray crystallography. The crystal structure of Te-atom transfer agent TePCy3 is also reported. Quantum chemical calculations were used to make bond energy predictions as well as to probe terminal chalcogen bonding in terms of an energy partitioning analysis.     

Preparation of 3-Bromo-1,2,4,5-tetrazine

In this synthetic procedure, a seven-step protocol for the preparation of monosubstituted 3-bromo-1,2,4,5-tetrazine is presented. The procedure features efficient transformations and purification methods starting from commercially readily available starting materials and affords the title compound on a gram scale with 13 % overall yield in reliable purity (>97 %). Detailed experimental procedures, supported by images and additional notes, allow the preparation of a valuable advanced building block, enabling further applications in bioconjugation, protein labelling, bio-orthogonal chemistry, heterocycle syntheses, high energy materials, and drug release, among others.     

Negishi Cross-Coupling in the Preparation of Benzyl Substituted Pyrrolo[2,3-d]pyrimidine Based CSF1R Inhibitors

The colony-stimulating factor 1 receptor (CSF1R) is a protein kinase emerging as an attractive target with clinical relevance in cancer, CNS and inflammatory diseases. Molecular docking experiments followed by synthesis and structure–activity relationship have been used to identify low molecular weight structures as promising hits for lead optimization. These molecules are synthesized from a 4-chloro-6-iodo-pyrrolo[2,3-d]pyrimidine building block using Negishi and Suzuki–Miyaura cross-coupling reactions in high yields. Several inhibitors possessed excellent enzymatic potency, and the parent compound preferably binds to the autoinhibited form of CSF1R. Cellular and in vivo profiling indicate that further tuning of drug structure is needed prior to efficacy studies.