Designing Microgels for Cell Culture and Controlled Assembly of Tissue Microenvironments

Micrometer‐sized hydrogels, termed microgels, are emerging as multifunctional platforms that can recapitulate tissue heterogeneity in engineered cell microenvironments. The microgels can function as either individual cell culture units or can be assembled into larger scaffolds. In this manner, individual microgels can be customized for single or multicell coculture applications, or heterogeneous populations can be used as building blocks to create microporous assembled scaffolds that more closely mimic tissue heterogeneities. The inherent versatility of these materials allows user‐defined control of the microenvironments, from the order of singly encapsulated cells to entire 3D cell scaffolds. These hydrogel scaffolds are promising for moving towards personalized medicine approaches and recapitulating the multifaceted microenvironments that exist in vivo.     

INCREASE IN REFRACTORINESS IN CERAMIC BODIES IN INTERRUPTED HEAT TREATMENT1

The increase in refractoriness referred to here is usually termed freezing. The study was undertaken to overcome the tendency of pyrometric cones to set or freeze when subjected to prolonged heat treatment when the temperature is more or less fluctuating. The work includes a study of the freezing tendency of some natural clays, of several pottery bodies, and of pyrometric cones. A body was developed that does not freeze under the treatment that produces the phenomenon in the other materials tested but the cause is not established.     

Chlorination of polyesters

By photochemical chlorination chlorine was substituted on the gem-dimethyl groups of the polyterephthalate and polycarbonate of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, the polyterephthalate of 2,2-dimethyl-1,3-propanediol, and the polycarbonate of 4,4′-isopropylidenediphenol (bisphenol A). The factors affecting polyester degradation, the efficiency of chlorination, and the degree of chlorination were investigated, and the effects of chlorine content on the solubility, flammability, density, hydrolytic stability, thermal stability, tensile properties, electrical properties, and heat-distortion temperatures of cast films were determined. The chlorinated polyesters of particular interest, because of their properties, are the polycarbonates of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and bisphenol A.     

Particulate platform for bioluminescent immunosensing

The present study examines pyruvate kinase-conjugated antibodies for potential use in ELISA applications. The conjugates had an acceptable stability, and the coupling inflicted only minor impairment on the kinase activity. To mimic the setup of an immunoassay under development, a test antigen (BSA) was attached to polystyrene nanoparticles. This arrangement was found to be suitable as solid support for presentation of antigens in sensitive bioluminescence assays. The nanoparticles were well characterized in terms of protein surface load and were used to establish the number of conjugate complexes needed to generate a detectable signal. Under the biochemical conditions employed here, the detection limit of the pyruvate kinase conjugate lies in the femtomole range.     

Aliphatic polyamides prepared by ester-amine polycondensation as potential drug carrier polymers

Aliphatic polyamides of interest as macromolecular drug carriers are synthesized by base-catalyzed polycondensation of aliphatic diesters with diamines. The reactions are conducted in the presence of anhydrous sodium carbonate at temperatures ranging from ambient to 65°C, initially in the undilute state. The addition of aprotic solvent at a later stage serves to maintain sufficiently low viscosity for proper homogenization. The comonomers, diethyl 3,6,9-trioxaundecanedioate and 4,7,10-trioxa-1,13-tridecanediamine, copolymerize to form polymer 1, a straight-chain polyamide devoid of specific functionality. Use of diethyl tartrate in lieu of the aforementioned diester leads to polyamide 2 possessing hydroxyl side groups. Other experiments in which diamines incorporating additional (secondary) amino groups are employed afford polyamides 3–8 containing such secondary amine functions as main-chain constituents. The water-soluble target polymers are crudely fractionated by aqueous dialysis (12000–14000 molecular mass cut-off) and collected by freeze-drying in yields of 20 to 40%. The low-yield range has been accepted in this investigation as the price to be paid for the realization of linear polyamide structures in accordance with compositional expectations, a requirement vital for the proper functioning of the polymers as drug carriers. The practicability of drug binding (conjugating) is exemplified by the coupling of ferrocene as a drug model to polyamide 5 via amide linkage. The water-soluble conjugate 5-Fc features an iron content corresponding to one ferrocene group in the repeat unit. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2143–2150, 1999     

Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly

Near‐field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle‐based cluster assemblies have exhibited signal enhancements in surface‐enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low‐cost fabrication methods. Here an innovative method is developed for fabricating self‐organized clusters of metal nanoparticles on diblock copolymer thin films as SERS‐active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self‐organized chemically functionalized poly(methyl methacrylate) domains on polystyrene‐block‐poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub‐10‐nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 10⁹ while simultaneously producing uniform signal enhancements in point‐to‐point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full‐wave electromagnetic simulations. Reusability for small‐molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non‐lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.