High-resolution stereolithography: Negative spaces enabled by control of fluid mechanics.

Stereolithography enables the fabrication of three-dimensional (3D) freeform structures via light-induced polymerization. However, the accumulation of ultraviolet dose within resin trapped in negative spaces, such as microfluidic channels or voids, can result in the unintended closing, referred to as overcuring, of these negative spaces. We report the use of injection continuous liquid interface production to continuously displace resin at risk of overcuring in negative spaces created in previous layers with fresh resin to mitigate the loss of Z-axis resolution.

Liposome-tethered supported lipid bilayer platform for capture and release of heterogeneous populations of circulating tumor cells.

Because of scarcity, vulnerability, and heterogeneity in the population of circulating tumor cells (CTCs), the CTC isolation system relying on immunoaffinity interaction exhibits inconsistent efficiencies for all types of cancers and even CTCs with different phenotypes in individuals. Moreover, releasing viable CTCs from an isolation system is of importance for molecular analysis and drug screening in precision medicine, which remains a challenge for current systems. In this work, a new CTC isolation microfluidic platform was developed and contains a coating of the antibody-conjugated liposome-tethered-supported lipid bilayer in a developed chaotic-mixing microfluidic system, referred to as the "LIPO-SLB" platform.

Orthogonal Photochemistry toward Direct Encryption of a 3D-Printed Hydrogel.

Encryption technologies are essential for information security and product anti-counterfeiting, but they are typically restricted to planar surfaces. Encryption on complex 3D objects offers great potential to further improve security. However, it is rarely achieved owing to the lack of encoding strategies for nonplanar surfaces.

Multiomic characterization and drug testing establish circulating tumor cells as an tool for personalized medicine.

Matching the treatment to an individual patient's tumor state can increase therapeutic efficacy and reduce tumor recurrence. Circulating tumor cells (CTCs) derived from solid tumors are promising subjects for theragnostic analysis. To analyze how CTCs represent tumor states, we established cell lines from CTCs, primary and metastatic tumors from a mouse model and provided phenotypic and multiomic analyses of these cells.

Influence of Mixed Imide Composition and Thermal Annealing on Ionic Liquid Uptake and Conductivity of Polyimide-Poly(ethylene glycol) Segmented Block Copolymer Membranes.

Understanding the impact of different bridging groups in the two-step polymerization of poly(ethylene glycol) (PEG)-incorporated polyimide (PI) materials is significant. It is known that the proton exchange membranes (PEMs) used in industry today can experience performance degradation under rising temperature conditions. Many efforts have been devoted to overcoming this problem by improving the physical and mechanical properties that extend the hygrothermal life of a PEM.

Surface Characteristics of Poly(alkyl methacrylate)s from Molecular Dynamics Simulations Using All-Atom Force Field.

Molecular dynamics (MD) simulations of melt films of poly(alkyl methacrylate)s (PAMAs) with methyl, ethyl, and n-butyl substituents, respectively, have been performed using an all-atom model to investigate their surface and thin film properties. The applied all-atom force fields predict the bulk densities of PAMAs in good agreement with experiments. Moreover, predictions of the surface tensions of PMMA, PEMA, and Pn-BMA melts are in reasonably good agreement with experiments.

Effect of Increased Ionic Liquid Uptake via Thermal Annealing on Mechanical Properties of Polyimide-Poly(ethylene glycol) Segmented Block Copolymer Membranes.

Proton exchange membranes (PEMs) suffer performance degradation under certain conditions-temperatures greater than 80 °C, relative humidity less than 50%, and water retention less than 22%. Novel materials are needed that have improved water retention, stability at higher temperatures, flexibility, conductivity, and the ability to function at low humidity. This work focuses on polyimide-poly(ethylene glycol) (PI-PEG) segmented block copolymer (SBC) membranes with high conductivity and mechanical strength.

A General Approach for Monolayer Adsorption of High Weight Loadings of Uniform Nanocrystals on Oxide Supports.

Monodispersed metal and semiconductor nanocrystals have attracted great attention in fundamental and applied research due to their tunable size, morphology, and well-defined chemical composition. Utilizing these nanocrystals in a controllable way is highly desirable especially when using them as building blocks for the preparation of nanostructured materials. Their deposition onto oxide materials provide them with wide applicability in many areas, including catalysis.

Nanoscale Spatial Distribution of Supported Nanoparticles Controls Activity and Stability in Powder Catalysts for CO Oxidation and Photocatalytic H Evolution.

Supported metal nanoparticles are essential components of high-performing catalysts, and their structures are intensely researched. In comparison, nanoparticle spatial distribution in powder catalysts is conventionally not quantified, and the influence of this collective property on catalyst performance remains poorly investigated. Here, we demonstrate a general colloidal self-assembly method to control uniformity of nanoparticle spatial distribution on common industrial powder supports.

Interface Characteristics of Neat Melts and Binary Mixtures of Polyethylenes from Atomistic Molecular Dynamics Simulations.

Molecular dynamics simulations of free-standing thin films of neat melts of polyethylene (PE) chains up to CH and their binary mixtures with n-CH are performed employing a united atom model. We estimate the surface tension values of PE melts from the atomic virial tensor over a range of temperatures, which are in good agreement with experimental results. Compared with short n-alkane systems, there is an enhanced surface segregation of methyl chain ends in longer PE chains.

General Self-Assembly Method for Deposition of Graphene Oxide into Uniform Close-Packed Monolayer Films.

Depositing a morphologically uniform monolayer film of graphene oxide (GO) single-layer sheets is an important step in the processing of many composites and devices. Conventional Langmuir-Blodgett (LB) deposition is often considered to give the highest degree of morphology control, but film microstructures still vary widely between GO samples. The main challenge is in the sensitive self-assembly of GO samples with different sheet sizes and degrees of oxidation.

Langmuir-Blodgett Deposition of Graphene Oxide-Identifying Marangoni Flow as a Process that Fundamentally Limits Deposition Control.

Langmuir-Blodgett deposition is a popular route to produce thin films of graphene oxide for applications such as transparent conductors and biosensors. Unfortunately, film morphologies vary from sample to sample, often with undesirable characteristics such as folded sheets and patchwise depositions. In conventional Langmuir-Blodgett deposition of graphene oxide, alcohol (typically methanol) is used to spread the graphene oxide sheets onto an air-water interface before deposition onto substrates.

Interfacial and topological effects on the glass transition in free-standing polystyrene films.

United-atom molecular-dynamics computer simulations of atactic polystyrene (PS) were performed for the bulk and free-standing films of 2 nm-20 nm thickness, for both linear and cyclic polymers comprised of 80 monomers. Simulated volumetric glass-transition temperatures (T) show a strong dependence on the film thickness below 10 nm. The glass-transition temperature of linear PS is 13% lower than that of the bulk for 2.

Modular composite hydrogels from cholesterol-functionalized polycarbonates for antimicrobial applications.

Micellar composite hydrogel systems represent a promising class of materials for biomolecule and drug delivery applications. In this work a system combining micellar drug delivery with supramolecular hydrogel assemblies is developed, representing an elegant marriage of aqueous hydrophobic drug delivery and next-generation injectable viscoelastic materials. Novel shear thinning and injectable micellar composite hydrogels were prepared using an amphiphilic ABA-type triblock copolymer consisting of a hydrophilic middle block and cholesterol-functionalized polycarbonates as terminal hydrophobic blocks.

Supramolecular motifs in dynamic covalent PEG-hemiaminal organogels.

Dynamic covalent materials are stable materials that possess reversible behaviour triggered by stimuli such as light, redox conditions or temperature; whereas supramolecular crosslinks depend on the equilibrium constant and relative concentrations of crosslinks as a function of temperature. The combination of these two reversible chemistries can allow access to materials with unique properties. Here, we show that this combination of dynamic covalent and supramolecular chemistry can be used to prepare organogels comprising distinct networks.

A semi-interpenetrating network approach for dimensionally stabilizing highly-charged anion exchange membranes for alkaline fuel cells.

There is a delicate balance between ion exchange capacity (IEC), conductivity, and dimensional stability in anion exchange membranes as higher charge content can lead to increased water uptake, causing excessive swelling and charge dilution. Using highly-charged benzyltrimethylammonium polysulfone (IEC=2.99 mEq g(-1) ) as a benchmark (which ruptured in water even at room temperature), we report the ability to dramatically decrease water uptake using a semi-interpenetrating network wherein we reinforced the linear polyelectrolyte with a crosslinked poly(styrene-co-divinylbenzene) network.

Biocompatibility of poly(ethylene glycol) and poly(acrylic acid) interpenetrating network hydrogel by intrastromal implantation in rabbit cornea.

We evaluated the biocompatibility of a poly(ethylene glycol) and poly(acrylic acid) (PEG/PAA) interpenetrating network hydrogel designed for artificial cornea in a rabbit model. PEG/PAA hydrogel measuring 6 mm in diameter was implanted in the corneal stroma of twelve rabbits. Stromal flaps were created with a microkeratome.

A simple method for encapsulating single cells in alginate microspheres allows for direct PCR and whole genome amplification.

Microdroplets are an effective platform for segregating individual cells and amplifying DNA. However, a key challenge is to recover the contents of individual droplets for downstream analysis. This paper offers a method for embedding cells in alginate microspheres and performing multiple serial operations on the isolated cells.

Interpenetrating polymer network hydrogel scaffolds for artificial cornea periphery.

Three-dimensional scaffolds based on inverted colloidal crystals (ICCs) were fabricated from sequentially polymerized interpenetrating polymer network (IPN) hydrogels of poly(ethyleneglycol) and poly(acrylic acid). This high-strength, high-water-content IPN hydrogel may be suitable for use in an artificial cornea application. Development of a highly porous, biointegrable region at the periphery of the artificial cornea device is critical to long-term retention of the implant.

Phosphatidylinositol 4,5-bisphosphate is an HCV NS5A ligand and mediates replication of the viral genome.

Background & Aims: Phosphoinositides (PIs) bind and regulate localization of proteins via a variety of structural motifs. PI 4,5-bisphosphate (PI[4,5]P2) interacts with and modulates the function of several proteins involved in intracellular vesicular membrane trafficking. We investigated interactions between PI(4,5)P2 and hepatitis C virus (HCV) nonstructural protein 5A (NS5A) and effects on the viral life cycle.

Directed axonal outgrowth using a propagating gradient of IGF-1.

The temporospatial regulation of axon outgrowth is useful for guiding de novo connectivity or re-connectivity of neurons in neurological injury or disease. Here we report the successful construction of a biocompatible guidance device, in which a linear propagation of IGF-1 gradient sequentially directs axon outgrowth. We observe the extensive in vitro axonal extension over 5 mm with a desired growth rate of ∼ 1 mm/day.

Vesicle adhesion and rupture on silicon oxide: influence of freeze-thaw pretreatment.

We have investigated the effect of freeze-thaw (FT) pretreatment on the adhesion and rupture of extruded vesicles over a wide range of vesicle sizes. To characterize the size distributions of vesicles obtained with and without FT pretreatment, dynamic light scattering (DLS) experiments were performed. The interaction between extruded vesicles and a silicon oxide substrate was investigated by quartz crystal microbalance with dissipation (QCM-D) monitoring, with a focus on comparative analysis of similar-sized vesicles with and without FT pretreatment.

Grafting of cross-linked hydrogel networks to titanium surfaces.

The performance of medical implants and devices is dependent on the biocompatibility of the interfacial region between tissue and the implant material. Polymeric hydrogels are attractive materials for use as biocompatible surface coatings for metal implants. In such systems, a factor that is critically important for the longevity of an implant is the formation of a robust bond between the hydrogel layer and the implant metal surface and the ability for this assembly to withstand physiological conditions.