Softening by charging: how collective modes of ionic association in concentrated redoxmer/electrolyte solutions define the structural and dynamic properties in different states of charge.

Understanding the physical and chemical processes occurring in concentrated electrolyte solutions is required to achieve redox flow batteries with high energy density. Highly concentrated electrolyte solutions are often studied in which collective crowded interactions between molecules and ions become predominant. Herein, experimental and computational methods were used to examine non-aqueous electrolyte solutions in two different states of charge as a function of redoxmer concentration. As the latter increases and the ionic association strengthens, the electric conductivity passes through a maximum and the solution increasingly gels, which is seen through a rapid non-linear increase in viscosity. We establish that the structural rigidity of ionic networks is closely connected with this loss of fluidity and show that charging generally yields softer ionic assemblies with weaker attractive forces and improved dynamical properties.

Cell Death Persists in Rapid Extrusion of Lysis-Resistant Coated Cardiac Myoblasts.

As the demand for organ transplants continues to grow faster than the supply of available donor organs, a new source of functional organs is needed. High resolution high throughput 3D bioprinting is one approach towards generating functional organs for transplantation. For high throughput printing, the need for increased print resolutions (by decreasing printing nozzle diameter) has a consequence: it increases the forces that cause cell damage during the printing process. Here, a novel cell encapsulation method provides mechanical protection from complete lysis of individual living cells during extrusion-based bioprinting. Cells coated in polymers possessing the mechanical properties finely-tuned to maintain size and shape following extrusion, and these encapsulated cells are protected from mechanical lysis. However, the shear forces imposed on the cells during extrusion still cause sufficient damage to compromise the cell membrane integrity and adversely impact normal cellular function. Cellular damage occurred during the extrusion process independent of the rapid depressurization.

The fate of phenothiazine-based redox shuttles in lithium-ion batteries.

The stability and reactivity of the multiple oxidation states of aromatic compounds are critical to the performance of these species as additives and electrolytes in energy-storage applications. Both for the overcharge mitigation in ion-intercalation batteries and as electroactive species in redox flow batteries, neutral, radical-cation, and radical-anion species may be present during charging and discharging processes. Despite the wide range of compounds evaluated for both applications, the progress identifying stable materials has been slow, limited perhaps by the overall lack of analysis of the failure mechanism when a material is utilized in an energy-storage device. In this study, we examined the reactivity of phenothiazine derivatives, which have found interest as redox shuttles in lithium-ion battery applications. We explored the products of the reactions of neutral compounds in battery electrolytes and the products of radical cation formation using bulk electrolysis and coin cell cycling. Following the failure of each cell, the electrolytes were characterized to identify redox shuttle decomposition products. Based on these results, a set of decomposition mechanisms is proposed and further explored using experimental and theoretical approaches. The results highlight the necessity to fully characterize and understand the chemical degradation mechanisms of the redox species in order to develop new generations of electroactive materials.

Overcharge performance of 3,7-disubstituted N-ethylphenothiazine derivatives in lithium-ion batteries.

3,7-Disubstituted N-ethylphenothiazine derivatives were synthesized as redox shuttle candidates for lithium-ion batteries. Battery cycling results show that three derivatives prevent overcharge.

Early human prostate adenocarcinomas harbor androgen-independent cancer cells.

Although blockade of androgen receptor (AR) signaling represents the main treatment for advanced prostate cancer (PrCa), many patients progress to a lethal phenotype of "Castration-Resistant" prostate cancer (CR-PrCa). With the hypothesis that early PrCa may harbor a population of androgen-unresponsive cancer cells as precursors to CR-recurrent disease, we undertook the propagation of androgen-independent cells from PrCa-prostatectomy samples of early, localized (Stage-I) cases. A collection of 120 surgical specimens from prostatectomy cases was established, among which 54 were adenocarcinomas. Hormone-free cell culture conditions were developed allowing routine propagation of cells expressing prostate basal cell markers and stem/progenitor cell markers, and which proliferated as spheres/spheroids in suspension cultures. Colonies of androgen-independent epithelial cells grew out from 30/43 (70%) of the adenocarcinoma cases studied in detail. Fluorescence microscopy and flow cytometry showed that CR-PrCa cells were positive for CD44, CD133, CK5/14, c-kit, integrin α2ß1, SSEA4, E-Cadherin and Aldehyde Dehydrogenase (ALDH). All 30 CR-PrCa cell cultures were also TERT-positive, but negative for TMPRSS2-ERG. Additionally, a subset of 22 of these CR-PrCa cell cultures was examined by orthotopic xenografting in intact and castrated SCID mice, generating histologically typical locally-invasive human PrCa or undifferentiated cancers, respectively, in 6-8 weeks. Cultured PrCa cells and orthotopically-induced in vivo cancers lacked PSA expression. We report here the propagation of Cancer Initiating Cells (CIC) directly from Stage I human PrCa tissue without selection or genetic manipulation. The propagation of stem/progenitor-like CR-PrCa cells derived from early human prostate carcinomas suggests the existence of a subpopulation of cells resistant to androgen-deprivation therapy and which may drive the subsequent emergence of disseminated CR-PrCa.

Linear and spiral forms of longitudinal cuts in graphitized N-doped multiwalled carbon nanotubes (g-N-MWCNTs).

Nitrogen-containing multiwalled nanotubes (N-MWCNTs), formed by CVD from a nitrogen-containing feedstock have a 'bamboo' structure in which the axes of the graphene planes are not parallel to the axis of the nanotube and the core is periodically bridged. We find that thermal and chemical treatment of these materials can produce nanotubes that have been cut longitudinally in either a linear or in a spiral manner. In addition, these longitudinally cut nanotubes can be partially or fully unrolled by sonication in an aqueous surfactant, producing graphite platelets as well as narrow structures that could be thin graphite ribbons or very narrow, intact N-MWCNTs. These different morphologies of graphite, available from one source, suggest that there are multiple structures of N-MWCNTs present, few as simple as stacked cups or nested scrolls.