Nanoscale-localized multiplexed biological activation of field effect transistors for biosensing applications.

The rise in antibiotic-resistant pathogens, highly infectious viruses, and chronic diseases has prompted the search for rapid and versatile medical tests that can be performed by the patient. Field-effect transistor (FET)-based electronic biosensing platforms are particularly attractive due to their sensitivity, fast turn-around time, potential for parallel detection of multiple pathogens, and compatibility with semiconductor manufacturing. However, an unmet critical need is a scalable, site-selective multiplexed biofunctionalization method with nanoscale precision for immobilizing different types of pathogen-specific bioreceptors on individual FETs, preventing parallel detection of multiple targets.

Substrate Channeling in Compartmentalized Nanoreactors.

Thermo- and photoresponsive nanoreactors based on shell cross-linked micelles (SCMs) for the rhodium-catalyzed asymmetric transfer hydrogenation (ATH) of ketones have been developed from poly(2-oxazoline) triblock terpolymers. The nanoreactors incorporate thermoresponsive poly(2-isopropyl-2-oxazoline) as the hydrophilic corona and are covalently cross-linked with a photoswitchable spiropyran molecule. UV irradiation or changes in temperature trigger morphology switching of the polymer-based nanoreactors that alters the hydrophobicity in separate layers of the SCMs, resulting in dynamic substrate selectivity of the ATH in water.

Progress in the Synthesis of Colloidal Machines.

For the past decade, the field of colloidal science has expanded the collection of colloidal particles to include an entire library of subunits that can be isotropic or anisotropic in terms of structural morphology or chemical composition. Using anisotropic subunits, the field has assembled a variety of static and dynamic structures. For this Account, we use the umbrella term "dynamic colloids" to describe subunits capable of movement, shape-shifting, or any other type of action in response to a stimulus and "static colloids" to describe those that are unresponsive to such stimuli.

Functionalized [2.2]Paracyclophanedienes as Monomers for Poly(-phenylenevinylene)s.

Poly(-phenylenevinylene)s (PPVs) featuring complex side-chains, to date, have only been synthesized by nonliving polymerization methods which have no control over PPV molecular weights, dispersities, or end groups. [2.2]Paracyclophane-1,9-diene (pCpd) has gained attention as a monomer for its ability to be ring-opened to PPV in a living fashion.

Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor.

Water has emerged as a versatile solvent for organic chemistry in recent years due to its abundance, low cost, and environmental friendliness. However, one of the most important reactions, the aldol reaction, in the presence of excess water exhibits low yields and poor enantioselectivities. In this regard, we have employed a multiscale modeling approach to investigate the aldol addition reaction catalyzed by l-proline in the hydrophobic compartment of multicompartment micelle (MCM) nanoreactor consisting of amphiphilic bottlebrush copolymer, which minimizes the water content at the reactive site.

Bent and Twisted: Synthesis of an Alkoxy-Substituted (1,5)Naphthalene-paracyclophanediene.

This contribution describes the synthesis of [2.2](1,5)naphthalenoparacyclophane-1,13-diene in four steps from 1,5-bis(bromomethyl)naphthalene and 1,4-benzenedimethanethiol. Consisting of 2,6-dioctyloxynaphthalene and benzene moieties, the effects of differing arene size on the structure, strain energy, and chemical reactivity of the cyclophanediene are examined.

3D Printing Type 1 Bovine Collagen Scaffolds for Tissue Engineering Applications-Physicochemical Characterization and In Vitro Evaluation.

Collagen, an abundant extracellular matrix protein, has shown hemostatic, chemotactic, and cell adhesive characteristics, making it an attractive choice for the fabrication of tissue engineering scaffolds. The aim of this study was to synthesize a fibrillar colloidal gel from Type 1 bovine collagen, as well as three dimensionally (3D) print scaffolds with engineered pore architectures. 3D-printed scaffolds were also subjected to post-processing through chemical crosslinking (in N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide) and lyophilization.

Orthogonal Supramolecular Assemblies Using Side-Chain Functionalized Helical Poly(isocyanide)s.

Mimicking the structure of proteins using synthetic polymers requires building blocks with structural similarity and the use of various noncovalent and dynamic covalent interactions. We report the synthesis of helical poly(isocyanide)s bearing diaminopyridine and pyridine side-chains and the multistep functionalization of the polymers' side-chains using hydrogen bonding and metal coordination. The orthogonality of the hydrogen bonding and metal coordination was proved by varying the sequence of the multistep assembly.

Nonorthogonal Cascade Catalysis in Multicompartment Micelles.

Multicompartment micelles (MCMs) containing acid and base sites in discrete domains are prepared from poly(norbornene)-based amphiphilic bottlebrush copolymers in aqueous media. The acid and base sites are localized in different compartments of the micelle, enabling the nonorthogonal reaction sequence: deacetalization - Knoevenagel condensation - Michael addition of acetals to 2-amino chromene derivatives. Computational simulations using dissipative particle dynamics (DPD) elucidated the bottlebrush composition required to effectively site-isolate the nonorthogonal catalysts.

Protrusion growth driven by myosin-generated force.

Actin-based protrusions extend from the surface of all eukaryotic cells, where they support diverse activities essential for life. Models of protrusion growth hypothesize that actin filament assembly exerts force for pushing the plasma membrane outward. However, membrane-associated myosin motors are also abundant in protrusions, although their potential for contributing, growth-promoting force remains unexplored.

A Polymer Canvas with the Stiffness of the Bone Matrix to Study and Control Mesenchymal Stem Cell Response.

Reproducing in vitro the complex multiscale physical features of human tissues creates novel biomedical opportunities and fundamental understanding of cell-environment interfaces and interactions. While stiffness has been recognized as a key driver of cell behavior, systematic studies on the role of stiffness have been limited to values in the KPa-MPa range, significantly below the stiffness of bone. Here, a platform enabling the tuning of the stiffness of a biocompatible polymeric interface up to values characteristic of human bone is reported, which are in the GPa range, by using extremely thin polymer films on glass and cross-linking the films using ultraviolet (UV) light irradiation.

Catalytically Active Multicompartment Micelles.

This article presents the self-assembly behavior of multicompartment micelles (MCMs) in water into morphologies with multiple segregated domains and their use as supports for aqueous catalysis. A library of poly(norbornene)-based amphiphilic bottlebrush copolymers containing covalently attached l-proline in the hydrophobic, styrene, and pentafluorostyrene domains and a poly(ethylene glycol)-containing repeat unit as the hydrophilic block have been synthesized using ring-opening metathesis polymerization. Interaction parameter (χ) values between amphiphilic blocks were determined using a Flory-Huggins-based computational model.

Customized metallodielectric colloids and their behavior in dielectrophoretic fields.

A synthetic strategy for fabricating colloidal particles with spatially segregated amine-functionalized lobes enables regioselective coating with gold to afford metallodielectric particles with a variety of shapes and lobe sizes. This approach can produce either dissymmetric dumbbell-shaped two-lobed Au-TPM particles (Au-T) or dissymmetric or symmetric three-lobed particles with gold coating on one (Au-T-T and T-Au-T) or two lobes (Au-T-Au). Dielectrophoretic (DEP) forces exerted by an AC field confined between two opposing electrodes generate aggregates ranging from 1D chains to 2D close-packed lattices, depending on the particle shape and lobe arrangement.

Synthesis and Polymerization of an --Substituted Tetraalkoxy [2.2]Paracyclophane-1,9-diene.

This contribution describes the synthesis of an unsymmetrical substituted tetraalkoxy[2.2]paracyclophane-1,9-diene comprised of an -substituted and a -substituted dioctyloxybenzene. ()-4,5,12,15-tetraoctyloxy-[2.

Assessment Structure, Culture, and Resources at US AAVMC-Accredited Colleges of Veterinary Medicine.

While outcomes assessment is commonplace in colleges of veterinary medicine, no information is published on how veterinary colleges resource, administer, and view assessment. Consequently, this article has the following objectives: (a) to determine the current level of resources (personnel, committees, software) allocated toward education assessment and program evaluation in colleges of veterinary medicine, (b) to characterize any common organizational structures within colleges of veterinary medicine for assessment, (c) to determine assessment personnel (faculty and staff) perceptions regarding whether existing assessment resources and structures are sufficient, and (d) to examine the perceived strength of the culture of assessment. Our survey found that most assessment professionals had been in their position for 4 years or less and over 50% did not have formal assessment training.

Supramolecular Helical Miktoarm Star Polymers.

We report a hydrogen-bonded supramolecular miktoarm star polymer containing three distinct helical arms. Our design involves two helical poly(methacrylamide) arms connected by a barbituric acid (Ba) at the center, prepared through the reversible addition-fragmentation chain-transfer polymerization with a bifunctional agent. Together with a telechelic helical poly(isocyanide) end-functionalized with a Hamilton Wedge (HW) that is complementary to Ba, the two components assemble into an AB-type star copolymer.

Photoresponsive Azobenzene-Functionalized Shell Cross-Linked Micelles for Selective Asymmetric Transfer Hydrogenation.

We describe the substrate-selective asymmetric transfer hydrogenation of aromatic ketones using rhodium complexes immobilized on a photoresponsive nanoreactor. The nanoreactor switches its morphology upon light irradiation in a wavelength-selective manner. Kinetic studies show that the gated behavior in the cross-linking layer is key to discriminating among substrates and reagents during catalysis.

Role of the radiologist in the diagnosis and management of the two forms of hepatic echinococcosis.

Echinococcosis is a parasitic disease caused by two zoonotic tapeworms (cestodes) of the Echinocococcus genus. It can be classified as either alveolar or cystic echinococcosis. Although the two forms differ significantly in terms of imaging findings, they share similarities in terms of management and treatment.

Hearing Someone Laugh and Seeing Someone Yawn: Modality-Specific Contagion of Laughter and Yawning in the Absence of Others.

Laughter and yawning can both occur spontaneously and are highly contagious forms of social behavior. When occurring contagiously, laughter and yawning are usually confounded with a social situation and it is difficult to determine to which degree the social situation or stimulus itself contribute to its contagion. While contagious yawning can be reliably elicited in lab when no other individuals are present, such studies are more sparse for laughter.

Compartmentalisation of molecular catalysts for nonorthogonal tandem catalysis.

The development of nonorthogonal tandem catalysis enables the use of a combination of arbitrary catalysts to rapidly synthesize complex products in a substainable, efficient, and timely manner. The key is to compartmentalise the molecular catalysts, thereby overcoming inherent incompatibilities between individual catalysts or reaction conditions. This tutorial review analyses the development of the past two decades in the field of nonorthogonal tandem catalysis with an emphasis on compartmentalisation strategies.

Near-Infrared Fluorescent Micelles from Poly(norbornene) Brush Triblock Copolymers for Nanotheranostics.

This contribution describes the design and synthesis of multifunctional micelles based on amphiphilic brush block copolymers (BBCPs) for imaging and selective drug delivery of natural anticancer compounds. Well-defined BBCPs were synthesized via one-pot multi-step sequential grafting-through ring-opening metathesis polymerization (ROMP) of norbornene-based macroinitiators. The norbornenes employed contain a poly(ethylene glycol) methyl ether chain, an alkyl bromide chain, and/or a near-infrared (NIR) fluorescent cyanine dye.

Intramolecular Folding of Coil-Helix Block Copolymers Induced by Quadrupole Interactions.

True tertiary architectures with defined local secondary structures are rare in synthetic systems. Adapting well-developed synthetic building blocks and controlling their folding through diverse interactions can be a general approach toward this goal. In this contribution, the synthesis of 3D hierarchical assemblies with distinct secondary domains formed through the intramolecular folding of a block copolymer containing a coil-like poly(styrene) (PS) block with a helical poly(isocyanide) block induced by phenyl-pentafluorophenyl quadrupole interactions is reported.

Engineering of Janus-Like Dendrimers with Peptides Derived from Glycoproteins of Herpes Simplex Virus Type 1: Toward a Versatile and Novel Antiviral Platform.

Novel antiviral nanotherapeutics, which may inactivate the virus and block it from entering host cells, represent an important challenge to face viral global health emergencies around the world. Using a combination of bioorthogonal copper-catalyzed 1,3-dipolar alkyne/azide cycloaddition (CuAAC) and photoinitiated thiol-ene coupling, monofunctional and bifunctional peptidodendrimer conjugates were obtained. The conjugates are biocompatible and demonstrate no toxicity to cells at biologically relevant concentrations.

Secondary Structure in Nonpeptidic Supramolecular Block Copolymers.

Proteins contain a level of complexity-secondary and tertiary structures-that polymer chemists aim to imitate. The bottom-up synthesis of protein-mimicking polymers mastering sequence variability and dispersity remains challenging. Incorporating polymers with predefined secondary structures, such as helices and π-π stacking sheets, into block copolymers circumvents the issue of designing and predicting one facet of their 3D architecture.