Long reach cantilevers for sub-cellular force measurements

Maneuverable, high aspect ratio poly 3-4 ethylene dioxythiophene (PEDOT) fibers are fabricated for use as cellular force probes that can interface with individual pseudopod adhesive contact sites without forming unintentional secondary contacts to the cell. The straight fibers have lengths between 5 and 40 μm and spring constants in the 0.07-23.2 nN μm-1 range. The spring constants of these fibers were measured directly using an atomic force microscope (AFM). These AFM measurements corroborate determinations based on the transverse vibrational resonance frequencies of the fibers, which is a more convenient method. These fibers are employed to characterize the time dependent forces exerted at adhesive contacts between apical pseudopods of highly migratory D. discoideum cells and the PEDOT fibers, finding an average terminal force of 3.1 ± 2.7 nN and lifetime of 23.4 ± 18.5 s to be associated with these contacts

Controlled electrochemical growth of ultra-long gold nanoribbons

Citation: Basnet, G., Panta, K. R., Thapa, P. S., & Flanders, B. N. (2017). Controlled electrochemical growth of ultra-long gold nanoribbons. Applied Physics Letters, 110(7), 5. doi:10.1063/1.4976027This paper describes the electrochemical growth of branchless gold nanoribbons with similar to 40 nm x similar to 300 nm cross sections and >100 mu m lengths (giving length-to-thickness aspect ratios of > 10(3)). These structures are useful for opto-electronic studies and as nanoscale electrodes. The 0.75-1.0V voltage amplitude range is optimal for branchless ribbon growth. Reduced amplitudes induce no growth, possibly due to reversible redox chemistry of gold at reduced amplitudes, whereas elevated amplitudes, or excess electrical noise, induce significant side-branching. The inter-relatedness of voltage-amplitude, noise, and side-branching in electrochemical nanoribbon growth is demonstrated. Published by AIP Publishing

Forces at Individual Pseudopod-Filament Adhesive Contacts

On-chip cellular force sensors are fabricated from cantilever poly(3,4-ethylene dioxythiophene) filaments that visibly deflect under forces exerted at individual pseudopod-filament adhesive contacts. The shape of the deflected filaments and their ∼3 nN/μm spring constants are predicted by cantilever rod theory. Pulling forces exerted by Dictyostelium discoideumcells at these contacts are observed to reach ∼20 nN without breaking the contact

Directional growth of polypyrrole and polythiophene wires

This work establishes an innovative electrochemical approach to the template-free growth of conducting polypyrrole and polythiophene wires along predictable interelectrode paths up to 30 um in length. These wires have knobby structures with diameters as small as 98 nm. The conductivity of the polypyrrole wires is 0.5+/=0.3 S cm-1; that of the polythiophene wires is 7.6+/=0.8 S cm-1. Controlling the growth path enables fabrication of electrode-wire-target assemblies where the target is a biological cell in the interelectrode gap. Such assemblies are of potential use in cell stimulation studies.Peer reviewedPhysicsMicrobiology and Molecular Genetic

Physical characterixation and in vitro biological impact of highly aggregated antibodies separated into size-enriched populations by fluorescence-activated cell sorting

An IgG2 monoclonal antibody (mAb) solution was subjected to stirring, generating high concentrations of nanometer and subvisible particles, which were then successfully size enriched into different size bins by low speed centrifugation or a combination of gravitational sedimentation and Fluorescence-Activated Cell Sorting (FACS). The size-fractionated mAb particles were assessed for their ability to elicit the release of cytokines from a population of donor-derived human peripheral blood mononuclear cells (PBMC) at two phases of the immune response. Fractions enriched in nanometer-sized particles showed a lower response than those enriched in micron-sized particles in this assay. Particles of 5–10 μm in size displayed elevated cytokine release profiles compared to other size ranges. Stir-stressed mAb particles had amorphous morphology, contained protein with partially altered secondary structure, elevated surface hydrophobicity (compared to controls), and trace levels of elemental fluorine. FACS size-enriched the mAb particle samples, yet did not notably alter the overall morphology or composition of particles as measured by Microflow imaging, Transmission Electron Microscopy, and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy. The utility and limitations of FACS for size separation of mAb particles and potential of in-vitro PBMC studies to rank order the immunogenic potential of various types of mAb particles is discussed

Long reach cantilevers for sub-cellular force measurements

Maneuverable, high aspect ratio poly 3-4 ethylene dioxythiophene (PEDOT) fibers are fabricated for use as cellular force probes that can interface with individual pseudopod adhesive contact sites without forming unintentional secondary contacts to the cell. The straight fibers have lengths between 5 and 40 μm and spring constants in the 0.07–23.2 nN μmˉ¹ range. The spring constants of these fibers were measured directly using an atomic force microscope (AFM). These AFM measurements corroborate determinations based on the transverse vibrational resonance frequencies of the fibers, which is a more convenient method. These fibers are employed to characterize the time dependent forces exerted at adhesive contacts between apical pseudopods of highly migratory D. discoideum cells and the PEDOT fibers, finding an average terminal force of 3.1± 2.7 nN and lifetime of 23.4 ± 18.5 s to be associated with these contacts

Kinetic Modeling of Sorbitol Hydrogenolysis over Bimetallic RuRe/C Catalyst

Sorbitol hydrogenolysis kinetics using bimetallic RuRe catalyst is reported based on multiple experiments in parallel batch slurry reactors (H₂ pressure: 1.0–6.5 MPa, temperature: 473–503 K) to obtain concentration–time profiles. It is observed that RuRe/C bimetallic catalysts with Ca­(OH)₂ as a base promoter show significantly higher activity and selectivity toward liquid phase products such as 1,2-propanediol, lactic acid, ethylene glycol, and linear alcohols compared with monometallic Ru/C catalysts and other base promoters. It is further found that sorbitol hydrogenolysis initiates with dehydrogenation and subsequent C–C cleavage via retro-aldolization to form smaller molecules (C₂–C₄). Those smaller intermediates undergo dehydration, reorganization, and C–O cleavage to form C₂–C₃ acids, glycols, and linear alcohols as products, which are very similar to glycerol conversion chemistry. For the kinetic modeling, experimental data on concentration–time profiles were obtained using RuRe/C catalysts with Ca­(OH)₂ promoter in which H₂ pressure, catalyst loading, and temperature were varied. The analysis of kinetic models employed a batch slurry reactor model with which several rate equations based on different complex multistep reaction mechanisms were fit to the experimental data in order to gain insights into the reaction pathways and mechanisms. Activation energies for sorbitol hydrogenolysis to glycols and further conversion of glycols to corresponding alcohols are found to be in the range 38 kJ/mol to 125+ kJ/mol. The kinetic model from this work provides the framework for developing rational multiphase reactor engineering strategies for upgrading polyol mixtures (e.g., glycerol, xylitol, sorbitol, and mannitol) to value-added glycols and alcohols

Formation of Self-Organized Nanoporous Anodic Oxide from Metallic Gallium

This paper reports the formation of self-organized nanoporous gallium oxide by anodization of solid gallium metal. Because of its low melting point (ca. 30 °C), metallic gallium can be shaped into flexible structures, permitting the fabrication of nanoporous anodic oxide monoliths within confined spaces like the inside of a microchannel. Here, solid gallium films prepared on planar substrates were employed to investigate the effects of anodization voltage (1, 5, 10, 15 V) and H₂SO₄ concentration (1, 2, 4, 6 M) on anodic oxide morphology. Self-organized nanopores aligned perpendicular to the film surface were obtained upon anodization of gallium films in ice-cooled 4 and 6 M aqueous H₂SO₄ at 10 and 15 V. Nanopore formation could be recognized by an increase in anodic current after a current decrease reflecting barrier oxide formation. The average pore diameter was in the range of 18–40 nm with a narrow diameter distribution (relative standard deviation ca. 10–20%), and was larger at lower H₂SO₄ concentration and higher applied voltage. The maximum thickness of nanoporous anodic oxide was ca. 2 μm. In addition, anodic formation of self-organized nanopores was demonstrated for a solid gallium monolith incorporated at the end of a glass capillary. Nanoporous anodic oxide monoliths formed from a fusible metal will lead to future development of unique devices for chemical sensing and catalysis

Atom Economical Aqueous-Phase Conversion (APC) of Biopolyols to Lactic Acid, Glycols, and Linear Alcohols Using Supported Metal Catalysts

Conversion of renewable biopolyols to value-added chemicals such as lactic acid and glycols usually demands excess hydrogen/oxygen or harsh reaction conditions in strong alkaline medium (220–350 °C). This unfortunately promotes significant side reactions resulting in low carbon selectivity to liquid products, posing significant challenges for the development of sustainable technologies. We report here a new atom economical catalytic conversion of various biopolyols (glycerol, xylitol, mannitol, and sorbitol) to lactic acid with glycols and linear alcohols as co-products at much lower temperatures (115–160 °C) without external addition of either hydrogen or oxygen. Among various metal-based catalysts (Pt, Pd, Rh, Ru, Raney Ni, Raney Co, and Cu) evaluated, Pt/C catalyst gives the highest chemoselectivity (S > 95%) for lactic acid, glycols, and linear alcohols at 115–160 °C. An important finding is that approximately two-thirds of the hydrogen generated in situ via dehydrogenation of polyols over Pt/C catalyst is efficiently utilized for the conversion of the remaining polyols and intermediates to useful products (e.g., glycols and linear alcohols instead of gaseous products) with the remaining available hydrogen for use elsewhere in a biorefinery. The Pt/C catalyst is thus multifunctional facilitating tandem dehydrogenation/hydrogenolysis of polyols. Furthermore, it is observed that Ba²⁺ alkali ion promotes the activity of the Pt/C catalyst by almost 12-fold compared to other alkali promoters such as NaOH, KOH, and Ca­(OH)₂. In addition to being the first reported study on the conversion of C₅∼C₆ polyols (e.g., xylitol and sorbitol) to lactic acid at relatively low temperatures, the results also provide new insights into the mechanism of tandem catalysis of biopolyols conversion to value-added commodity chemicals