Additive-Free Green Light-Induced Ligation Using BODIPY Triggers

Photochemical ligation is important in biomaterials engineering for spatiotemporal control of biochemical processes. Such reactions however generally require activation by high energy UV or short wavelength blue light, which can limit their use as a consequence of the potential of these high energy light sources to damage living cells. Herein, we present an additive-free, biocompatible, chemical ligation triggered by mild visible light. BODIPY dyes with a pendant thioether attached at the meso-position undergo photolysis of the [C−S] bond under green light (λ=530 nm) excitation, producing an ion pair intermediate that can react specifically with a propiolate group. The utility of this photochemical ligation in materials science is demonstrated by the fabrication of hydrogels with specific architectures, photo-immobilization of biomacromolecules, and live cell encapsulation within a hydrogel scaffold.     

Development of Amino–Oxazoline and Amino–Thiazoline Organic Catalysts for the Ring‐Opening Polymerisation of Lactide

The ring‐opening polymerisation of lactide by a range of amino–oxazoline and amino–thiazoline catalysts is reported. The more electron‐rich derivatives are demonstrated to be the most highly active and polymerisation is well controlled, as evidenced by the linear relationship between the molecular weight and both the monomer conversion and the monomer‐to‐initiator ratio. Mechanistic studies reveal significant interactions between the monomer, initiator and catalyst and that the polymerisation is first order with respect to each of these components. These observations indicate that the polymerisation operates by a general base/pseudo‐anionic mechanism.     

Block copolymer materials from the organocatalytic ring‐opening polymerization of a pentaerythritol‐derived cyclic carbonate

9‐Phenyl‐2,4,8,10‐tetraoxaspiro[5,5]undecanone (PTO) was synthesized from pentaerythritol via the acid‐catalyzed acetal formation reaction with benzaldehyde and subsequent ring closure with ethyl chloroformate. The cyclic carbonate monomer was subsequently polymerized by ring‐opening polymerization (ROP) initiated from 1,4‐butanediol (1,4‐BDO) using the 1‐(3,5‐bis(trifluoromethyl)phenyl)‐3‐cyclohexylthiourea and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene dual organocatalytic system. It was found that the organocatalyst allowed for the synthesis of well‐defined polymers with minimal adverse side reactions and low dispersities. This system was then employed in the ROP of PTO initiated from an α,ω‐dihydroxy poly(caprolactone) (PCL) macroinitiator, with varying molecular weights, to yield a series of A‐B‐A block copolymers. These materials were characterized by ¹H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis and tensile analysis. It was found that the chain extension from PCL with poly(PTO) (PPTO) blocks yielded a thermoplastic material with superior tensile properties (elongation and Young's modulus) to that of the PCL homopolymer. Furthermore, it was noted that the addition of PPTO could be employed to alter the crystallization properties (crystallization temperature (T_c), and percentage crystallization) of the central PCL block. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2279–2286     

Automatic detection of myocardial contours in cine-computed tomographic images

Quantitative evaluation of cardiac function from cardiac images requires the identification of the myocardial walls. This generally requires the clinician to view the image and interactively trace the contours. This method is susceptible to great variability that depends on the experience and knowledge of the particular operator tracing the contours. The particular imaging modality that is used may also add tracing difficulties. Cine-computed tomography (cine-CT) is an imaging modality capable of providing high quality cross-sectional images of the heart. CT images, however, are cluttered, i.e., objects that are not of interest, such as the chest wall, liver, stomach, are also visible in the image. To decrease this variability, investigators have developed computer-assisted or near-automatic techniques for tracing these contours. All of these techniques, however, require some operator intervention to confidently identify myocardial borders. The authors present a new algorithm that automatically finds the heart within the chest, and then proceeds to outline (detect) the myocardial contours. Information at each tomographic slice is used to estimate the contours at the next tomographic slice, thus allowing the algorithm to work in near-apical cross-sectional images where the myocardial borders are often difficult to identify. The algorithm does not require operator input and can be used in a batch mode to process large quantities of data. An evaluation and correction phase is included to allow an operator to view the results and selectively correct portions of contours. The authors tested the algorithm by automatically identifying the myocardial borders of 27 cardiac images obtained from three human subjects and quantitatively comparing these automatically determined borders with those traced by an experienced cardiologist.     

Fluctuations and some strain related interaction mechanisms in structural phase transitions

Materials which undergo structural phase transitions with bilinear coupling between the spontaneous strain (e ^sp _i ) and the thermodynamic order parameter (Q) of the type λ_i e ^sp _i Q show characteristic fluctuation pattern at T > T _c. Snapshots of such pattern show tweedlike structures with butterfly shaped structure factors. Some experimental fluctuation patterns are reviewed and compared with the theoretical predictions.

At T ≤ T_c , characteristic microstructures often include structural twinning. The relevant energy expressions for order/disorder systems are recalled and their contribution to thermodynamic fluctuations are described. It is anticipated that some of the physical mechanisms may play a role also in improper ferroelastics with coupling of the type λ_i e ^sp _i Q ² _k where Qk is a component of a degenerate order parameter Q = {Qk}.     

Modelling in relation to cation ordering

We review the methodology of using computer models to obtain quantitative information about cation ordering. Empirical interatomic potentials or ab initio electronic structure calculations are used to generate the energies for many configurations containing disordered arrangements of cations, and the parameters in model Hamiltonians can be determined from these energies. Monte Carlo simulations are then used to generate ensemble averages as functions of temperature or chemical composition. Analysis of the Monte Carlo ensembles directly yields the temperature dependence of long-range and short-range order, and thermodynamic quantities such as energy and heat capacity. Use of thermodynamic integration allows for the calculation of entropy and free energy. The methods are illustrated by examples showing long-range order/disorder phase transitions (feldspars), short-range order in solid solutions (pyrope-grossular), and non-convergent ordering (magnesium aluminate spinel); where comparisons with experimental data are possible, the model calculations are seen to give results that are reasonably accurate. The example in which ab initio electronic structure calculations are used show that it is now possible to extract accurate thermodynamic data for ordering processes using models that require no prior experimental data.     

Use of electrical-resistance strain elements in three-dimensional stress analysis

A method for constructing resistance-wire strain gages which may be imbedded in a plastic model without materially altering the stress pattern in the model is presented. The methods used to calibrate the gages and the photoelastic tests made to investigate the effect of the gages on the stress pattern are described. The application of this new three-dimensional technique to evaluate the stress distribution in a thick-walled cylindrical pressure vessel is discussed. Correlation between experimental data and calculated values is given.     

Electron diffraction RDF analysis of amorphous As2Se3,AAs2Se2Te,As2SeTe2 and As2Te3 films

The local order in amorphous films of As₂Se₃, As₂Se₂Te, As₂SeTe₂, and As₂Te₃ has been examined by scanning electron diffraction with direct recording of the intensity of the elastically scattered electrons. The radial distribution functions indicate that there is a systematic increase in mean nearest neighbor distance as the Te concentration is increased, butthe mean coordination number increases slightly around 2.4. Pair function calculation of models shows that the 3-aand 2-fold coordinations of arsenic and chalcogens are retained in these glasses and the interatomic distances are close to those predicted from the Pauling covalent atomic radii of the constituent atomic species. The short range order appears to be similar in amorphous and crystalline As₂Se₃, but different in the case of As₂Te₃ as found by previous workers on bulk materials.     

Electron traps in AℓPO4 substituted zinc silicate phosphors

Recently it has been shown that the incorporation of AℓPO₄ in a Zn₂SiO₄ phosphor results in an improved cathodoluminescent efficiency¹. We report here on electron trap distributions in the substituted phosphors derived from UV excited thermoluminescent glow curve measurements. It has been found that the glow curve peaks are modified appreciably with AℓPO₄ addition, but new peaks do not appear to be introduced. This shift, however is largely due to a considerable change in the absolute value of the detrapping rate, while there is only a relatively small change in the activation energies for detrapping. The phosphors were prepared in a silica rich environment and for the present study were not subjected to post preparation annealing treatments.