Confinement-Driven Photophysics in Hydrazone-Based Hierarchical Materials

Confinement-imposed photophysics was probed for novel stimuli-responsive hydrazone-based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution-like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady-state and time-resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone-based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.     

A simple slurry consolidometer designed for the estimation of the consistency limits of soils

An inexpensive slurry consolidometer design is described that uses porous polyethylene as the permeable barrier for sample dewatering (maximum effective stress of 200 kPa) and permits monitoring of sample pore-water pressures less than 100 kPa with a portable pressure transducer. The instrument is applied in this study to the consolidation-based estimation of the Atterberg soil consistency limits of both agricultural soils and till and glaciolacustrine materials (clay fraction predominantly Ca-saturated illites) sampled from sonic boreholes. All soils originated from southwestern Ontario, Canada. With the normally consolidated (virgin) compression line expressed as a w(logσ') function, the A.S.T.M. liquid and plastic limits of the borehole soils were found to occupy relatively fixed positions on the VCL at mean effective stresses of about 61 kPa and 0.42 MPa, respectively. Marginally plastic and non-plastic soils could be distinguished as having compression line slopes approaching zero. The effective stress at the liquid limit decreased logarithmically from 61 kPa with increasing organic carbon content in the agricultural soils. Consolidated slurries of all soils investigated that were clearly plastic exhibited a mean drop-cone penetration depth of approximately 13 mm at the A.S.T.M. liquid limit, a significant departure from the British Standard of 20 mm. Slurry consolidation can be used as a sample preparation method for measurement of the liquid limit by the drop-cone or one-point A.S.T.M. procedures. It has also shown potential as a procedural alternative for the estimation of both test indices, mostly for geotechnical applications. It is probable that this unified test protocol must be recalibrated for soils where the dominant clay minerals and saturating bases are different from those in this study.     

Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

Derivations and spectral triples on quantum domains II: Quantum annulus

Science China Mathematics - Continuing our study of spectral triples on quantum domains, we look at unbounded invariant and covariant derivations in the quantum annulus. In particular, we...     

Efficient polymer passivation of ligand‐stripped nanocrystal surfaces

Water‐dispersible, polymer‐wrapped nanocrystals are highly sought after for use in biology and chemistry, from nanomedicine to catalysis. The hydrophobicity of their native ligand shell, however, is a significant barrier to their aqueous transfer as single particles. Ligand exchange with hydrophilic small molecules or, alternatively, wrapping over native ligands with amphiphilic polymers is widely employed for aqueous transfer; however, purification can be quite cumbersome. We report here a general two‐step method whereby reactive stripping of native ligands is first carried out using trialkyloxonium salts to reveal a bare nanocrystal surface. This is followed by chemically directed immobilization of a hydrophilic polymer coating. Polyacrylic acids, with side‐chain grafts or functional end groups, were found to be extremely versatile in this regard. The resulting polymer‐wrapped nanocrystal dispersions retained much of the compact size of their bare nanocrystal precursors, highlighting the unique role of monomer side‐chain functionality to serve as effective, conformal ligation motifs. As such, they are well poised for applications where tailored chemical functionality at the nanocrystal's periphery or improved access to their surfaces is desirable. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

D-bar Operators on Quantum Domains

We study the index problem for the d-bar operators subject to Atiyah- Patodi-Singer boundary conditions on noncommutative disk and annulus.     

Geometrically nonlinear continuum thermomechanics with surface energies coupled to diffusion

Surfaces can have a significant influence on the overall response of a continuum body but are often neglected or accounted for in an ad hoc manner. This work is concerned with a nonlinear continuum thermomechanics formulation which accounts for surface structures and includes the effects of diffusion and viscoelasticity. The formulation is presented within a thermodynamically consistent framework and elucidates the nature of the coupling between the various fields, and the surface and the bulk. Conservation principles are used to determine the form of the constitutive relations and the evolution equations. Restrictions on the jump in the temperature and the chemical potential between the surface and the bulk are not a priori assumptions, rather they arise from the reduced dissipation inequality on the surface and are shown to be satisfiable without imposing the standard assumptions of thermal and chemical slavery. The nature of the constitutive relations is made clear via an example wherein the form of the Helmholtz energy is explicitly given.     

Well-posedness of a model of strain gradient plasticity for plastically irrotational materials

The initial boundary value problem corresponding to a model of strain gradient plasticity due to [Gurtin, M., Anand, L., 2005. A theory of strain gradient plasticity for isotropic, plastically irrotational materials. Part I: Small deformations. J. Mech. Phys. Solids 53, 1624–1649] is formulated as a variational inequality, and analysed. The formulation is a primal one, in that the unknown variables are the displacement, plastic strain, and the hardening parameter. The focus of the analysis is on those properties of the problem that would ensure existence of a unique solution. It is shown that this is the case when hardening takes place. A similar property does not hold for the case of softening. The model is therefore extended by adding to it terms involving the divergence of plastic strain. For this extended model the desired property of coercivity holds, albeit only on the boundary of the set of admissible functions.     

Multi-element analysis of bone from the osteogenesis imperfecta model (OIM) mouse using thermal and fast neutron activation analysis

Osteogenesis imperfecta (OI) is a heritable osteoporotic bone disease, due to defects in either type I procollagen genes (COL1A1 or COL1A2), resulting in abnormal and/or reduced levels of type I procollagen and alterations in bone mineralization. Our long term objectives are to evaluate the impact of proα1(I) and proα2(I) collagen mutations and the role of the genetic background on bone mineralization. Tibias from wildtype, heterozygous (oim/+), and homozygous (oim/oim) animals were subjected to instrumental neutron activation analysis (INAA) to measure F, P, Na, Mg, Cl, Ca, K, and Zn using the University of Missouri Research Reactor (MURR) pneumatic-tube irradiation facility.