Assessment of nanoparticle loading and dispersion in polymeric materials using optical wavefront correlation

Small concentrations (≤5 wt. %) of nanoparticles in polymeric materials can potentially result in improvements in material properties and functionality. However, poor or non-uniform particle dispersion resulting in clustering (agglomeration) in polymer nanocomposites (PNCs) limits the potential for property enhancement. Achieving good dispersion is considered essential for large-scale production and commercialization of PNCs. New and effective measurement techniques capable of quantitatively characterizing particle loading and dispersion would significantly contribute towards understanding and optimizing the material performance of PNCs and, consequently, play a pivotal role in product development. This paper presents the results of a study using a static light scattering technique, optical wavefront correlation (OWC), for discriminating between different particle loadings and levels of dispersion. The technique has been applied to a range of PNCs, including epoxy resins reinforced with nanoclay platelets or silica microspheres, and zinc oxide and lithium aluminate reinforced polypropylene.     

Design of Enzymatically Cleavable Prodrugs of a Potent Platinum‐Containing Anticancer Agent

Using a versatile synthetic approach, a new class of potential ester prodrugs of highly potent, but systemically too toxic, platinum–acridine anticancer agents was generated. The new hybrids contain a hydroxyl group, which has been masked with a cleavable lipophilic acyl moiety. Both butanoic (butyric) and bulkier 2‐propanepentanoic (valproic) esters were introduced. The goals of this design were to improve the drug‐like properties (e.g., logD) and to reduce the systemic toxicity of the pharmacophore. Two distinct pathways by which the target compounds undergo effective ester hydrolysis, the proposed activating step, have been confirmed: platinum‐assisted, self‐immolative ester cleavage in a low‐chloride environment (LC‐ESMS, NMR spectroscopy) and enzymatic cleavage by human carboxylesterase‐2 (hCES‐2) (LC‐ESMS). The valproic acid ester derivatives are the first example of a metal‐containing agent cleavable by the prodrug‐converting enzyme. They show excellent chemical stability and reduced systemic toxicity. Preliminary results from screening in lung adenocarcinoma cell lines (A549, NCI‐H1435) suggest that the mechanism of the valproic esters may involve intracellular deesterification.     

Redesigning the DNA‐Targeted Chromophore in Platinum–Acridine Anticancer Agents: A Structure–Activity Relationship Study

Platinum–acridine hybrid agents show low‐nanomolar potency in chemoresistant non‐small cell lung cancer (NSCLC), but high systemic toxicity in vivo. To reduce the promiscuous genotoxicity of these agents and improve their pharmacological properties, a modular build–click–screen approach was used to evaluate a small library of twenty hybrid agents containing truncated and extended chromophores of varying basicities. Selected derivatives were resynthesized and tested in five NSCLC cell lines representing large cell, squamous cell, and adenocarcinomas. 7‐Aminobenz[c]acridine was identified as a promising scaffold in a hybrid agent ( P1–B1 ) that maintained submicromolar activity in several of the DNA‐repair proficient and p53‐mutant cancer models, while showing improved tolerability in mice by 32‐fold compared to the parent platinum–acridine ( P1–A1 ). The distribution and DNA/RNA adduct levels produced by the acridine‐ and benz[c]acridine‐based analogues in NCI‐H460 cells (confocal microscopy, ICP‐MS), and their ability to bind G‐quadruplex forming DNA sequences (CD spectroscopy, HR‐ESMS) were studied. P1–B1 emerges as a less genotoxic, more tolerable, and potentially more target‐selective hybrid agent than P1–A1 .     

The role of different linear and non-linear channels of relaxation in scintillator non-proportionality

The non-proportional dependence of a scintillator's light yield on primary particle energy is believed to be influenced crucially by the interplay of non-linear kinetic terms in the radiative and non-radiative decay of excitations versus locally deposited excitation density. A calculation of energy deposition, −dE/dx, along the electron track for NaI is presented for an energy range from several electron-volt to 1 MeV. Such results can be used to specify an initial excitation distribution, if diffusion is neglected. An exactly solvable two-channel (exciton and hole(electron)) model containing 1st and 2nd order kinetic terms is constructed and used to illustrate important features seen in non-proportional light-yield curves, including a dependence on pulse shaping (detection gate width).     

Functional Interdependence in Coupled Dissipative Structures: Physical Foundations of Biological Coordination

Coordination within and between organisms is one of the most complex abilities of living systems, requiring the concerted regulation of many physiological constituents, and this complexity can be particularly difficult to explain by appealing to physics. A valuable framework for understanding biological coordination is the coordinative structure, a self-organized assembly of physiological elements that collectively performs a specific function. Coordinative structures are characterized by three properties: (1) multiple coupled components, (2) soft-assembly, and (3) functional organization. Coordinative structures have been hypothesized to be specific instantiations of dissipative structures, non-equilibrium, self-organized, physical systems exhibiting complex pattern formation in structure and behaviors. We pursued this hypothesis by testing for these three properties of coordinative structures in an electrically-driven dissipative structure. Our system demonstrates dynamic reorganization in response to functional perturbation, a behavior of coordinative structures called reciprocal compensation. Reciprocal compensation is corroborated by a dynamical systems model of the underlying physics. This coordinated activity of the system appears to derive from the system’s intrinsic end-directed behavior to maximize the rate of entropy production. The paper includes three primary components: (1) empirical data on emergent coordinated phenomena in a physical system, (2) computational simulations of this physical system, and (3) theoretical evaluation of the empirical and simulated results in the context of physics and the life sciences. This study reveals similarities between an electrically-driven dissipative structure that exhibits end-directed behavior and the goal-oriented behaviors of more complex living systems.     

An Efficient Synthesis of 15N-Hydroxyurea

Treatment of trimethylsilyl isocyanate with ¹⁵N-hydroxylamine hydrochloride produces ¹⁵N-hydroxyurea, a valuable pharmacological tool, in an efficient, one-pot procedure in 74% yield. Recrystallization of the crude product yields analytically pure material in 47% overall yield.     

Host structure dependence of light yield and proportionality in scintillators in terms of hot and thermalized carrier transport

Several outstanding questions, including why complex halide scintillator host structures allow higher light yield and flatter electron energy response than simple monovalent metal halides, have remained unanswered by current models of luminescence in dense ionization tracks. Our measurements of nonlinear quenching kinetic order, recent literature on hot‐electron transport in scintillators, and calculations presented here of hot‐electron velocity from band structure of SrI₂ and NaI, lead us to expand our previously described diffusion and nonlinear quenching model to include hot‐electron transport. Trends in multivalent versus monovalent metal halides, heavier versus lighter halides, and halides versus oxides versus semiconductors can be predicted based on optical phonon frequency, thermalized band edge mobilities, velocity in the upper conduction bands, and hole self‐trapping. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Octadecyltrimethylammonium surfactant-immobilized cation exchange membranes for solid-phase extraction of phenolic compounds

In this study, octadecyltrimethylammonium surfactant was immobilized onto a cation exchange membrane for the application in solid-phase extraction of phenolic compounds. The results indicate that an HCl prewashing step and the use of hydroxide (or methoxide) counter ion could greatly improve the immobilized surfactant capacity. Through elemental and thermogravimetric analyses, the resulted immobilization percentage on the membrane (compared to membrane ion exchange capacity) was about 50, 100, and 150%, respectively, for the feed surfactant amount of 150, 2000, and 5000 μmol (volume = 20 mL). Phenol, 4-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol, 4-chloro-3-methylphenol, and bisphenol A were the tested compounds in a breakthrough volume experiment. The order of the obtained breakthrough volume values is similar to that of K_ow values of the phenolic compounds. In the solid-phase extraction process from a feed mixture of 0.1 ppm for 4-nitrophenol, 2,4-dichlorophenol, and 4-chloro-3-methylphenol, high concentration factors and almost complete recoveries were achieved. Moreover, by increasing the membrane volume, a larger sample volume could be processed without any deterioration in performance.