From Minutes to Years: Predicting Organotrifluoroborate Solvolysis Rates

Organotrifluoroborates solvolyze in water at rates that vary over five orders of magnitude. The negative logarithm of the solvolytic rate constant, pk_(B?F), correlates exceptionally well with the pK_a of the analogous carboxylic acid (R²=0.984). This unforeseen correlation may be of predictive value for several applications including Suzuki–Miyaura cross‐coupling reactions and the design of ¹⁸F‐organotrifluoroborate radioprosthetic groups.     

Direct visualization of the nanoscopic three‐phase structure and stiffness of NBR/PVC blends by AFM nanomechanical mapping

The PeakForce Quantitative Nanomechanical Mapping based on atomic force microscope (AFM) is employed to first visualize and then quantify the elastic properties of a model nitrile rubber/poly(vinyl chloride) (NBR/PVC) blend at the nanoscale. This method allows us to consistently observe the changes in mechanical properties of each phase in polymer blends. Beyond measuring and discriminating elastic modulus and adhesion forces of each phase, we tune the AFM tips and the peak force parameters in order to reliably image samples. In view of viscoelastic difference in each phase, a three‐phase coexistence of an unmixed NBR phase, the mixed phase, and PVC microcrystallites is directly visualized in NBR/PVC blends. The nanomechanical investigation is also capable of recognizing the crosslinked rubber phase in cured rubber. The contribution of the mixed phase was quantified and it was found that the mechanical properties of blends are mainly determined by the homogeneity and stiffness of the mixed phase. This study furthers our understanding the structure–mechanical property relationship of thermoplastic elastomers, which is important for their potential design and applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 662–669     

Existence of multiplicity harmonic and subharmonic solutions for second‐order quasilinear equation via Poincaré‐Birkhoff twist theorem

In this paper, we investigate the existence and multiplicity of harmonic and subharmonic solutions for second‐order quasilinear equation where , g satisfies the superlinear condition at infinity. We prove that the given equation possesses harmonic and subharmonic solutions by using the phase‐plane analysis methods and a generalized version of the Poincaré‐Birkhoff twist theorem.     

Multifunctional Fluorinated Lubricant-Infused Poly(4-Hydroxybutyrate) (P4HB) Membranes for Full-Thickness Abdominal Wall Defect Repair

Abdominal wall defect caused by surgical trauma, congenital rupture, or tumor resection may result in hernia formation or even death. Tension-free abdominal wall defect repair by using patches is the gold standard to solve such problems. However, adhesions following patch implantation remain one of the most challenging issues in surgical practice. The development of new kinds of barriers is key to addressing peritoneal adhesions and repairing abdominal wall defects. It is already well recognized that ideal barrier materials need to have good resistance to nonspecific protein adsorption, cell adhesion, and bacterial colonization for preventing the initial development of adhesion. Herein, electrospun poly(4-hydroxybutyrate) (P4HB) membranes infused with perfluorocarbon oil are used as physical barriers. The oil-infused P4HB membranes can greatly prevent protein attachment and reduce blood cell adhesion in vitro. It is further shown that the perfluorocarbon oil-infused P4HB membranes can reduce bacterial colonization. The in vivo study reveals that perfluoro(decahydronaphthalene)-infused P4HB membranes can significantly prevent peritoneal adhesions in the classic abdominal wall defects’ model and accelerate defect repair, as evidenced by gross examination and histological evaluation. This work provides a safe fluorinated lubricant-impregnated P4HB physical barrier to inhibit the formation of postoperative peritoneal adhesions and efficiently repair soft-tissue defects.     

EXISTENCE OF HOMOCLINIC SOLUTIONS TO NONAUTONOMOUS SECOND-ORDER p-LAPLACIAN SYSTEM WITH A COERCIVE POTENTIA

In this paper, we investigate a non-autonomous second-order p-Laplacian system.Based on critical point theory, we discuss the existence of homoclinic orbits of ...     

Ignition and burning behaviors of automobile oil in engine compartment

Accidental leakage of automobile oils is of great inclination to initiate pool fires in engine compartment, with threats to induce the flashover of other components and flame penetration into the passenger compartment. This paper presents experimental results of the ignition and burning behaviors of a kind of automobile oils (automatic transmission oil) using a cone calorimeter. Measurements of oil temperature, ignition time, mass loss and heat release rate are performed at different external heat fluxes and initial fuel depths. The comparison between experimental and numerical oil temperature evolutions shows that the variations of the ignition time at different experimental conditions depend on the heat dissipation process inside the liquid phase. The steady mass burning rate is nearly independent of initial fuel depth and has a linear relation with external heat fluxes. In addition, the results indicate an increase in peak heat release rate by a large margin initially, followed by a relatively small margin under thicker initial fuel depths, while its variations are proportional to external heat fluxes. Correlations are also developed to determine the peak heat release rate as a function of the initial fuel depth.

     

Constructing spin-adiabatic states for the modeling of spin-crossing reactions. I. A shared-orbital implementation

In the modeling of spin-crossing reactions, it has become popular to directly explore the spin-adiabatic surfaces. Specifically, through constructing spin-adiabatic states from a two-state Hamiltonian (with spin-orbit coupling matrix elements) at each geometry, one can readily employ advanced geometry optimization algorithms to acquire a “transition state” structure, where the spin crossing occurs. In this work, we report the implementation of a fully-variational spin-adiabatic approach based on Kohn-Sham density functional theory spin states (sharing the same set of molecular orbitals) and the Breit-Pauli one-electron spin-orbit operator. For three model spin-crossing reactions (predissociation of N₂O, singlet-triplet conversion in CH₂, and CO addition to Fe(CO)₄), the spin-crossing points were obtained. Our results also indicated the Breit-Pauli one-electron spin-orbit coupling can vary significantly along the reaction pathway on the spin-adiabatic energy surface. On the other hand, due to the restriction that low-spin and high-spin states share the same set of molecular orbitals, the acquired spin-adiabatic energy surface shows a cusp (ie, a first-order discontinuity) at the crossing point, which prevents the use of standard geometry optimization algorithms to pinpoint the crossing point. An extension with this restriction removed is being developed to achieve the smoothness of spin-adiabatic surfaces.     

External-Radiation-Induced Local Hydroxylation Enables Remote Release of Functional Molecules in Tumors

Radiation-induced cleavage for controlled release in vivo is yet to be established. We demonstrate the use of 3,5-dihydroxybenzyl carbamate (DHBC) as a masking group that is selectively and efficiently removed by external radiation in vitro and in vivo. DHBC reacts mainly with hydroxyl radicals produced by radiation to afford hydroxylation at para/ortho positions, followed by 1,4- or 1,6-elimination to rescue the functionality of the client molecule. The reaction is rapid and can liberate functional molecules under physiological conditions. This controlled-release platform is compatible with living systems, as demonstrated by the release of a rhodol fluorophore derivative in cells and tumor xenografts. The combined benefits of the robust caging group, the good release yield, and the independence of penetration depth make DHBC derivatives attractive chemical caging moieties for use in chemical biology and prodrug activation.     

An Organotrifluoroborate for Broadly Applicable One‐Step 18F‐Labeling

A new zwitterionic organotrifluoroborate is appended to three radiosynthons that afford undergo facile bioconjugation to several clinically relevant peptides and one enzyme inhibitor. Molecularly complex bioconjugates are ¹⁸F‐labeled in a single aqueous step in rapid time (<15 min) without HPLC purification to afford tracers in good yields (>200 mCi, 20–40 %) at high specific activity (≥3 Ci/μmol) and at >98 % purity. PET imaging shows in vivo stability and tumor uptake.     

基于J-C本构模型的Comp.B炸药落锤冲击数值模拟

为研究Comp.B炸药在惯性冲击下的力学响应特性, 基于Johnson-Cook本构模型, 对 点火前的Comp.B炸药大落锤(400kg)冲击实验进行了数值模拟. 在不同应力加载条件下模 拟计算得到了用状态方程和不用状态方程的$\sigma$-$t$曲线, 对比应力峰值、应 力上升时间等主要力学参数, 结果表明考虑了状态方程的数值模 拟结果与实验吻合最好, 可以很好地模拟炸药惯性冲击下的力学响应.