Rhodamine 101 Conjugates of Triterpenoic Amides Are of Comparable Cytotoxicity as Their Rhodamine B Analogs

Pentacyclic triterpenoic acids (betulinic, oleanolic, ursolic, and platanic acid) were selected and subjected to acetylation followed by the formation of amides derived from either piperazine or homopiperazine. These amides were coupled with either rhodamine B or rhodamine 101. All of these compounds were screened for their cytotoxic activity in SRB assays. As a result, the cytotoxicity of the parent acids was low but increased slightly upon their acetylation while a significant increase in cytotoxicity was observed for piperazinyl and homopiperazinyl amides. A tremendous improvement in cytotoxicity was observed; however, for the rhodamine B and rhodamine 101 conjugates, and compound 27, an ursolic acid derived homopiperazinyl amide holding a rhodamine 101 residue showed an EC₅₀ = 0.05 µM for A2780 ovarian cancer cells while being less cytotoxic for non-malignant fibroblasts. To date, the rhodamine 101 derivatives presented here are the first examples of triterpene derivatives holding a rhodamine residue different from rhodamine B.     

Multi-component self-assembled molecular-electronic films: towards new high-performance thermoelectric systems

The thermoelectric properties of parallel arrays of organic molecules on a surface offer the potential for large-area, flexible, solution processed, energy harvesting thin-films, whose room-temperature transport properties are controlled by quantum interference (QI). Recently, it has been demonstrated that constructive QI (CQI) can be translated from single molecules to self-assembled monolayers (SAMs), boosting both electrical conductivities and Seebeck coefficients. However, these CQI-enhanced systems are limited by rigid coupling of the component molecules to metallic electrodes, preventing the introduction of additional layers which would be advantageous for their further development. These rigid couplings also limit our ability to suppress the transport of phonons through these systems, which could act to boost their thermoelectric output, without comprising on their impressive electronic features. Here, through a combined experimental and theoretical study, we show that cross-plane thermoelectricity in SAMs can be enhanced by incorporating extra molecular layers. We utilize a bottom-up approach to assemble multi-component thin-films that combine a rigid, highly conductive ‘sticky’-linker, formed from alkynyl-functionalised anthracenes, and a ‘slippery’-linker consisting of a functionalized metalloporphyrin. Starting from an anthracene-based SAM, we demonstrate that subsequent addition of either a porphyrin layer or a graphene layer increases the Seebeck coefficient, and addition of both porphyrin and graphene leads to a further boost in their Seebeck coefficients. This demonstration of Seebeck-enhanced multi-component SAMs is the first of its kind and presents a new strategy towards the design of thin-film thermoelectric materials.

Through an experimental and theoretical study, cross-plane thermoelectricity in Self-Assembled Monolayers (SAMs) was enhanced by adding extra molecular layers, presenting a new strategy towards the design of high thermoelectric materials.     

Functional polysiloxanes. II. Neighboring effect in the hydrosilylation of poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s by allylglycidylether

Polysiloxanes bearing epoxy groups as lateral substituents were prepared by the hydrosilylation of 1‐allyloxy‐2,3‐epoxypropane (allylglycidylether) with poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s (D^H‐D copolymers) of various compositions. To determine the optimal conditions of the hydrosilylation catalyzed by hexachloroplatinic acid, the kinetics of the reaction were investigated for the poly(hydrogenmethylsiloxane) homopolymer. The reaction was first order in platinum, first order in double bonds, and 0.5 in SiH. This kinetic law was consistent with the hypothesis that hydrogenmethylsiloxane dyads are much more reactive than isolated units, which may be explained by the simultaneous insertion of two vicinal SiH's in a binuclear complex of platinum. This peculiar type of neighboring effect was investigated further by comparison of the kinetics of the hydrosilylation of D‐D^H copolymers of various compositions and D^H block lengths and was confirmed by the microstructure of a D‐D^H copolymer (50/50) before and after partial hydrosilylation. Triad analysis by ²⁹Si NMR showed that the resulting copolymer was not statistical but contained a high proportion of isolated SiH. This explains why hydrosilylation proceeded in two steps: a fast reaction of D^H‐D^H dyads and a slow reaction of the remaining isolated D^H units. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 837–845, 2000     

A new theoretical approach for the determination of molecular orientation persistence length of adsorbed nanofilms by FTIR reflectance spectroscopy

FTIR-Reflectance experiments have proved to be a powerful tool for the determination of molecular orientation in thin films adsorbed onto highly reflecting metals. We propose an original method for determination of the persistence length of molecular orientation in the film. This approach is based on the fact that molecular orientation persists only over a given distance from the geometrical interface. This distance is called the “persistence length of molecular orientation”. We then suppose that the nanofilm adsorbed is stratified and consists of an oriented layer (in the near-interface region) plus an isotropic one. Correlation between infrared reflection absorption band intensities and simulated band intensities allows experimentators to determine accurate molecular orientation and persistence length of orientation of a considered functional group. This is accomplished by using various IR reflection angles and p-polarization state of the incident IR wave. Film thickness and complex refractive index spectra, n(v) − i · k(v), are only needed to deduce calculated specular reflectance intensities.     

Micro/macro viability analysis of individual‐based models: Investigation into the viability of a stylized agricultural cooperative

The mathematical viability theory proposes methods and tools to study at a global level how controlled dynamical systems can be confined in a desirable subset of the state space. Multilevel viability problems are rarely studied since they induce combinatorial explosion (the set of N agents each evolving in a p‐dimensional state space, can evolve in a Np dimensional state space). In this article, we propose an original approach which consists in solving first local viability problems and then studying the real viability of the combination of the local strategies, by simulation where necessary. In this article, we consider as multilevel viability problem a stylized agricultural cooperative which has to keep a minimum of members. Members have an economical constraint and some members have a simple model of the functioning of the cooperative and make assumptions on other members' behavior, especially proviable agents which are concerned about their own viability. In this framework, the model assumptions allow us to solve the local viability problem at the agent level. At the cooperative level, considering mixture of agents, simulation results indicate if and when including proviable agents increases the viability of the whole cooperative. © 2014 Wiley Periodicals, Inc. Complexity 21: 276–296, 2015     

A multi-criteria large neighbourhood search for the transportation of disabled people

This paper addresses the problem of optimizing the transportation of disabled persons from home to specialized centres or schools. It is modelled as a Dial-a-ride problem (DARP), where several people share the same destination. Particular emphasis is placed on the objective function in order to consider several potentially conflicting interests. We propose a multi-criteria model from Multi-attribute Utility Theory based on the Choquet integral. The resulting multi-criteria DARP is then solved with a large neighbourhood search algorithm. This method includes classical destroy and repair heuristics as well as new operators exploiting the shared destination feature and criterion-specific operators. The algorithm is evaluated on a set of 14 real-world instances in the field of health care logistics, with up to 200 requests and 51 destination points.     

All-in-one disulfide bridging enables the generation of antibody conjugates with modular cargo loading

Antibody–drug conjugates (ADCs) are valuable therapeutic entities which leverage the specificity of antibodies to selectively deliver cytotoxins to antigen-expressing targets such as cancer cells. However, current methods for their construction still suffer from a number of shortcomings. For instance, using a single modification technology to modulate the drug-to-antibody ratio (DAR) in integer increments while maintaining homogeneity and stability remains exceptionally challenging. Herein, we report a novel method for the generation of antibody conjugates with modular cargo loading from native antibodies. Our approach relies on a new class of disulfide rebridging linkers, which can react with eight cysteine residues, thereby effecting all-in-one bridging of all four interchain disulfides in an IgG1 antibody with a single linker molecule. Modification of the antibody with the linker in a 1 : 1 ratio enabled the modulation of cargo loading in a quick and selective manner through derivatization of the linker with varying numbers of payload attachment handles to allow for attachment of either 1, 2, 3 or 4 payloads (fluorescent dyes or cytotoxins). Assessment of the biological activity of these conjugates demonstrated their exceptional stability in human plasma and utility for cell-selective cytotoxin delivery or imaging/diagnostic applications.

Tetra-divinylpyrimidine (TetraDVP) linkers offer a method for the generation of antibody conjugates with modular cargo loading and excellent stability via all-in-one disulfide bridging.     

Brookite TiO2 Nanoparticle Films for Dye‐Sensitized Solar Cells

Brookite TiO₂ nanoparticles have been synthesized at low temperature by a soft solution growth method and have been used as building blocks to prepare pure brookite nanoparticle porous films. The film brookite structure was confirmed by XRD and Raman spectroscopy. By spectrophotometry, it was shown that the films had a direct band gap of 3.4 eV. After sensitization by the N719 dye, efficient cells have been produced. A best overall conversion efficiency of 5.97 %, without a scattering layer, was found for the larger TiO₂ starting nanoparticles. The cell open‐circuit voltage was improved compared with that of anatase cells and a lower electron diffusion coefficient was found in the photoanodes made of smaller brookite particles. Lanthanum‐doped brookite nanoparticle films were also studied. They showed a marked decreased in the amount of dye loading, and hence, the solar cells had a reduced current density that was not compensated for by the increased open‐circuit voltage of the cells.