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At least 235 records · Page 13

Calcined Polyethyleneimine Coated Optical Fibers for Distributed pH Monitoring at High Pressures and Temperatures

In the oil and gas, CO2 sequestration, H2 subsurface storage, and geothermal energy sectors, subsurface pH measurements are critical for monitoring the geochemical conditions and estimating potential corrosion rates of wellbore systems. Real-time pH measurements in these conditions are vital for detecting and predicting corrosion deterioration of wellbore components that may jeopardize the safety and continued operation of wellbore systems. Building off of earlier TiO2 based pH sensors and the known pH sensitivity of amine-based polymers, a coating based on the secondary amine polymer polyethyleneimine (PEI) was developed. The sensor coating was treated with a high temperature (500 °C) calcination procedure in air to convert it into a more stable oxidized coating capable of withstanding hot aqueous solutions without dissolving while retaining linear pH sensitivity from pH values between 2 and 11. The sensor performance was measured using optical transmission measurements in solutions of various pHs and using optical backscatter reflectometry for distributed pH sensing demonstration in wellbore-relevant pressures (up to 1000 psi) and temperatures (80 °C). A calibration curve with strong differentiation between acidic and alkaline pH was developed for both transmission-based and distributed pH measurements, using fixed wavelength transmission and integrated linear amplitude of backscattered light for distributed measurements.

Shumski, Alexander↗

3D printed water-stable Cd-doped Cs 4 MnBi 2 Cl 12 /polylactic acid perovskite/polymer composites for high-flux X-ray scintillation

Stable and efficient X-ray scintillators are crucial for medical diagnostics, industrial, and defense applications. However, conventional scintillator technologies face a trade-off between stability, optimal performance, and sustainability. Herein, we introduce 3D-printed Cs 4 MnBi 2 Cl 12 (Pero1) and Cs 4 Cd 0.68 Mn 0.32 Bi 2 Cl 12 (Pero2) perovskite microcrystals embedded within a polylactic acid (PLA) polymer composite as X-ray scintillators, combining efficiency, stability, and sustainability. The orange luminescent perovskite powder phosphors exhibited poor water stability, which was successfully addressed through incorporation into PLA via filament extrusion and fused deposition modeling (FDM) 3D printing. The resulting composite films demonstrated remarkable water stability while maintaining uniform orange emission throughout the polymer matrix, as confirmed by 3D topography scanning and X-ray fluorescence mapping. Structural characterization revealed minimal chemical interaction between the perovskite and PLA matrix, with the composites retaining their crystalline properties. The PLA-Pero2 composite exhibited superior optical properties, with a photoluminescence quantum yield of 47%, nearly 17 times higher than that of PLA-Pero1 (2.8%), attributed to the effective suppression of non-radiative decay pathways through Cd 2+ doping. Under hard X-ray irradiation at synchrotron beamlines, both composites exhibited excellent radioluminescence, with emission peaks at 605 nm, a linear response across a wide X-ray flux range, and remarkable radiation stability, showing less than 3% intensity degradation after 600 seconds of continuous high-dose exposure. The PLA-Pero2 composite achieved a spatial resolution of 5 line pairs per millimeter and a contrast ratio of 0.255. These performance metrics, combined with the polymer's biodegradability and scalability through additive manufacturing, position PLA-based composites as a more sustainable alternative to conventional petroleum-based polymer scintillators for next-generation medical imaging, radiation monitoring, and industrial radiography applications.

3D Printing↗

Real-Time Monitoring of Gas-Phase and Dissolved CO 2 Using a Mixed-Matrix Composite Integrated Fiber Optic Sensor for Carbon Storage Application

Novel chemical sensors that improve detection and quantification of CO 2 are critical to ensuring safe and cost-effective monitoring of carbon storage sites. Fiber optic (FO) based chemical sensor systems are promising field-deployable systems for real-time monitoring of CO 2 in geological formations for long-range distributed sensing. Here, a mixed-matrix composite integrated FO sensor system was developed with a purely optical readout that reliably operates as a detector for gas-phase and dissolved CO 2 . A mixed-matrix composite sensor coating consisting of plasmonic nanocrystals and hydrophobic zeolite embedded in a polymer matrix was integrated on the FO sensor. The mixed-matrix composite FO sensor showed excellent reversibility/stability in a high humidity environment and sensitivity to gas-phase CO 2 over a large concentration range. This remarkable sensing performance was enabled by using plasmonic nanocrystals to significantly enhance the sensitivity and a hydrophobic zeolite to effectively mitigate interference from water vapor. The sensor exhibited the ability to sense CO 2 in the presence of other geologically relevant gases, which is of importance for applications in geological formations. A prototype FO sensor configuration which possesses a robust sensing capability for monitoring dissolved CO 2 in natural water was demonstrated. Reproducibility was confirmed over many cycles, both in a laboratory setting and in the field. More importantly, we demonstrated on-line monitoring capabilities with a wireless telemetry system, which transferred the data from the field to a website. The combination of outstanding CO 2 sensing properties and facile coating processability makes this mixed-matrix composite FO sensor a good candidate suitable for practical carbon storage applications.

54 ENVIRONMENTAL SCIENCES↗

Room Temperature Lasing from Semiconducting Single-Walled Carbon Nanotubes

Miniaturized near-infrared semiconductor lasers that are able to generate coherent light with low energy consumption have widespread applications in fields such as optical interconnects, neuromorphic computing, and deep-tissue optogenetics. With optical transitions at near-infrared wavelengths, diameter-tunable electronic structures, and superlative optoelectronic properties, semiconducting single-walled carbon nanotubes (SWCNTs) are promising candidates for nanolaser applications. However, despite significant efforts in this direction and recent progress toward enhancing spontaneous emission from SWCNTs through Purcell effects, SWCNT-based excitonic lasers have not yet been demonstrated. Leveraging an optimized cavity-emitter integration scheme enabled by a self-assembly process, here we couple SWCNT emission to the whispering gallery modes supported by polymer microspheres, resulting in room temperature excitonic lasing with an average lasing threshold of 4.5 kW/cm 2 . The high photostability of SWCNTs allows stable lasing for prolonged duration with minimal degradation. Finally, this experimental realization of excitonic lasing from SWCNTs, combined with their versatile electronic and optical properties that can be further controlled by chemical modification, offers far-reaching opportunities for tunable near-infrared nanolasers that are applicable for optical signal processing, in vivo biosensing, and optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Polyphenylsulfone and Polysulfone Incompatibility on the Structure and Performance of Blend Membranes for Ultrafiltration

This study deals with the modification of polyphenylsulfone ultrafiltration membranes by introduction of an incompatible polymer polysulfone to the polyphenylsulfone casting solution to improve the permeability. The correlation between properties of the blend polyphenylsulfone/polysulfone solutions and porous anisotropic membranes for ultrafiltration prepared from these solutions was revealed. The blend polyphenylsulfone/polysulfone solutions were investigated using a turbidity spectrum method, optical microscopy and measurements of dynamic viscosity and turbidity. The structure of the prepared blend flat sheet membranes was studied using scanning electron microscopy. Membrane separation performance was investigated in the process of ultrafiltration of human serum albumin buffered solutions. It was found that with the introduction of polysulfone to the polyphenylsulfone casting solution in N-methyl-2-pyrrolidone the size of supramolecular particles significantly increases with the maximum at (40–60):(60:40) polyphenylsulfone:polysulfone blend ratio from 76 nm to 196–354 nm. It was shown that polyphenylsulfone/polysulfone blend solutions, unlike the solutions of pristine polymers, are two-phase systems (emulsions) with the maximum droplet size and highest degree of polydispersity at polyphenylsulfone/polysulfone blend ratios (30–60):(70–40). Pure water flux of the blend membranes passes through a maximum in the region of the most heterogeneous structure of the casting solution, which is associated with the imposition of a polymer-polymer phase separation on the non-solvent induced phase separation upon membrane preparation. The application of polyphenylsulfone/polysulfone blends as membrane-forming polymers and polyethylene glycol (Mn = 400 g·mol -1 ) as a pore-forming agent to the casting solutions yields the formation of ultrafiltration membranes with high membrane pure water flux (270 L·m -2 ·h -1 at 0.1MPa) and human serum albumin rejection of 85%.

36 MATERIALS SCIENCE↗

Water vapor transmission rate measurement for moisture barriers using infrared imaging

Here, in this work, we demonstrate a spatially resolved imaging methodology for water vapor transmission rate (WVTR) testing that relies on quantified infrared characterization at water absorption bands. This technique is validated using a moisture barrier on a polymer substrate via calibration of the infrared image intensity with moisture content in the polymer substrate from images taken at different times. The method is compared to existing state of the art techniques such as membrane permeation measurement with coulometric phosphorous pentoxide sensor and optical calcium film testing. This fast, non-destructive and in-situ method enables defect visualization and shows the WVTR with a sensitivity limit of 5·10 –5 g/m 2 /day.

47 OTHER INSTRUMENTATION↗

Electronically Coupled 2D Polymer/MoS 2 Heterostructures

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS 2 heterostructures. In this work, control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS 2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Poly(cyclosilane) Postpolymerization Hydrosilylation

Postpolymerization functionalization is a key strategy in the diversification of polymeric materials for the conferral of tailored properties. Poly(cyclosilane)s are structurally complex polymers with an all-silicon backbone, featuring a periodic array of hydrido (Si–H) side chains that are potentially suitable for postpolymerization functionalization via hydrosilylation. At the same time, classical methods for hydrosilylation employing Pt- or Pd-based catalysts can result in Si–Si bond scission. In this work, we demonstrate borane-catalyzed hydrosilylation reactions between α-olefins and small molecules or three distinct poly(cyclosilane) architectures. We investigate chemoselectivity for end group versus internal Si–H groups and find that 29 Si cross-polarization magic angle spinning can provide insight on site-selectivity in the functionalization of a complex poly(cyclosilane). Furthermore, we show that postpolymerization hydrosilylation, converting oxidatively sensitive Si–H groups to Si–alkyl chains, modulates solubility and physical characteristics, optical properties, pyrolytic reactivity, and air sensitivity.

36 MATERIALS SCIENCE↗

Measuring the Electronic Bandgap of Carbon Nanotube Networks in Non-Ideal p-n Diodes

The measurement of the electronic bandgap and exciton binding energy in quasi-one-dimensional materials such as carbon nanotubes is challenging due to many-body effects and strong electron–electron interactions. Unlike bulk semiconductors, where the electronic bandgap is well known, the optical resonance in low-dimensional semiconductors is dominated by excitons, making their electronic bandgap more difficult to measure. In this work, we measure the electronic bandgap of networks of polymer-wrapped semiconducting single-walled carbon nanotubes (s-SWCNTs) using non-ideal p-n diodes. We show that our s-SWCNT networks have a short minority carrier lifetime due to the presence of interface trap states, making the diodes non-ideal. We use the generation and recombination leakage currents from these non-ideal diodes to measure the electronic bandgap and excitonic levels of different polymer-wrapped s-SWCNTs with varying diameters: arc discharge (~1.55 nm), (7,5) (0.83 nm), and (6,5) (0.76 nm). Our values are consistent with theoretical predictions, providing insight into the fundamental properties of networks of s-SWCNTs. The techniques outlined here demonstrate a robust strategy that can be applied to measuring the electronic bandgaps and exciton binding energies of a broad variety of nanoscale and quantum-confined semiconductors, including the most modern nanoscale transistors that rely on nanowire geometries.

36 MATERIALS SCIENCE↗

Shock Initiation Microscopy with High Time and Space Resolution

In this paper, we describe studies of shock initiation and shock-to-detonation transitions in energetic materials using a tabletop shock compression microscope with nanosecond time resolution and micrometer spatial resolution. Planar input shocks with durations of 4–20 ns are produced using 0–4.5 km/s laser-launched flyer plates. Emphasis is on measurements of temperature, velocities, pressure, and microstructure using photon Doppler velocimetry (PDV), optical pyrometry and high-speed videography. Techniques are discussed for fabricating disposable shock target arrays of tiny plastic-bonded explosives (PBX), liquid and powder explosives, and single-crystal explosives for high-throughput studies. Optical temperature measurements of shocked triaminotrinitrobenzene (TATB) are discussed. Since TATB is yellow, we developed methods to correct for the blue absorption to obtain more accurate temperatures. Hot spots in shocked polymer-encased HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) crystals are observed in real-time, showing a hot spot produced in a collapsing void that ignites a deflagration. Despite the small dimensions of our explosive charges (typically 1 mm diameter and 250 μm length), we produced reproducible detonation states in solid and liquid explosives using short-duration shocks near the von Neumann spike (VNS) pressure. We show the VNS pressure is associated with a transition to high-efficiency gas production from the explosives. In studies of NM, prior to detonation, we see reaction originating at hot spots which coalesce to form a superdetonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Halide perovskite-polymer composite film for bright and stable light-emitting devices

Stability is the primary hindrance for the application of halide perovskite material in light-emitting devices, solar cells, and other devices. In this work, halide perovskite and polymer composite film have been prepared for stable and bright light-emitting devices. Pure-phase Cs4PbBr6 crystals have been synthesized, and their photoluminescence (PL) properties and fluorescence lifetimes have been investigated. The Cs 4 PbBr 6 crystals exhibited high uniformity but underwent rapid photodegradation under light irradiation. To address this issue, we prepared bright light-emitting devices using composite of Cs 4 PbBr 6 crystals and polyethylene oxide (PEO) as the emission layer. The aim was to improve the optical and physical properties of halide perovskites, such as photodegradation and stability. PEO, with its excellent film-forming ability, created a uniform and dense film on the halide perovskite surface, filling microscopic defects and providing a protective barrier. FTIR, morphology, and PL analyses confirmed the protective role of the halide perovskite and polymer composite film. The composite film light-emitting devices demonstrated improved stability and higher PL brightness, with a peak brightness approaching 3 × 10 8 cd/m 2 , which was approximately 75% higher than the pure halide perovskite devices.

Composite film↗

Final Technical Report Wireless Microsensors System for Monitoring Deep Subsurface Operations

This final technical report describes the main findings of the project Wireless Microsensors System for Monitoring Deep Subsurface Operations (FE0031850). The project was part of the U.S. Department of Energy National Energy Technology Laboratory FOA 1998 program to develop new sensor systems for direct observation of parameters associated with CO2 injection and to provide data collection without being disruptive to operations. The overall DOE program was aimed at developing and validating innovative transformational sensor systems, amenable for integration with autonomous intelligent monitoring systems, that are capable of being deployed within the casing annulus and do not have casing perforation or wires/cables in the annulus for installation, power supply, or data transmission needs. Project accomplishments included 1) design and fabrication of a wireless downhole sensor system to monitor parameters for CO2 storage, 2) field testing of the sensor system in two legacy oil & gas wells, and 3) development of an analysis approach that validates the measurements and demonstrates the application of the technology to depict CO2 movement in the subsurface. The project leveraged new sensor technologies along with specialized wellbore telemetry, deployment, and analysis methods designed to address the challenges and risks related to CO2 storage in the subsurface. Results from field testing were a mixture of successes and challenges. The temperature sensor rings, installation procedures in legacy oil & gas wells, wireless powering demonstration, automated data collection, and material compatibility were successful. The wireless data transfer through cement to the wellhead via the sensor relays was not functional beyond the first relay. Consequently, work in the last year of the project included some additional testing of data transmission through different materials along with modeling and analysis of field data for CO2 monitoring applications. This work suggested there are options like polymer cements and open hole annuli that may allow point-to-point transmission along the borehole. The techno-economic analysis suggests that the sensor system is ~40% less expensive than fiber optic distributed temperature system. Modeling of CO2 storage applications suggests temperature can provide an indicator of CO2 saturation but would be best combined with pressure sensors.

47 OTHER INSTRUMENTATION↗

Distributed Magnetic Field and Temperature Monitoring for Superconducting Radio Frequency Cavities

The overall objective of the proposed Phase I program was to design, construct and demonstrate a fiber optic sensing system capable of providing temperature and magnetic field measurements with an enhanced spatial resolution that can be implemented over a large surface area (cryomodules) to survey superconducting radio frequency cavities and magnets. A magnetic field sensor capable of detecting fluxes on the order of 1 μT is required to detect the distribution of trapped flux on the cavity surface. A unique distributed magnetic field sensor was successfully designed and constructed to demonstrate the detection of magnetic fluxes less than 500 nT. The sensor leveraged the ultra-high sensitivity of Sentek’s picoDAS to measure the magnetostriction induced vibrations in a commercially available Metglas 2605 SC ribbon that was in physical contact with sensing fiber. Static magnetic fields were detected by applying an alternating current a copper wire proximate to the Metglas 2605SC ribbon to create an AC bias magnetic field. In an alternative approach, an AC bias magnetic field was applied to a special magnetic field sensing fiber with Metglas 2605SC cladding successfully detect a magnetic field flux of a 3 μT. Exhaustive testing was performed to characterize the dependency of sensor response on the direction of the applied magnetic field. Although the special sensing fiber based magnetic field sensor did not exhibit an observable dependence on the direction of the magnetic field, the Metglas 2605SC ribbon sensor exhibited a clear directional dependence. A wide variety of polymer materials were evaluated to enhance the temperature response of an FBG based sensor at cryogenic temperatures. The processing and performance challenges provided the motivation to develop a new simple cryogenic temperature sensor that uses a commercially available fiber optic splice protector. The EVA hot melt tube that becomes adhered to the optical fiber and the polyolefin outer tube that shrinks upon heating in the fusion splicer heater provide the high thermal expansion coefficient necessary to impart a significant strain on the FBG when exposed to cryogenic temperatures. The temperature sensitivity (Δ𝜆𝐵𝑟𝑎𝑔𝑔~ 62 𝑝𝑝𝑚/℃) of the FBG-based sensor was on par with the best reported to date. The simple design, use of readily available cost-effective materials, and well-established processing techniques lends this approach to the creation of hundreds to thousands of temperature sensors on one single optical fiber length. The inherently small form factor also allows for co-location with the distributed magnetic field sensor. In preparation for field testing of the prototype sensing system at the Jefferson Labs in potential Phase II program, several different cable designs were evaluated to package the sensors. The preliminary successful demonstration of fully functional sensing cables provides the foundation for subsequent development efforts to advance the Technology Readiness Level of the technology. The technical feasibility of the proposed approach was successfully demonstrated in this Phase I effort.

43 PARTICLE ACCELERATORS↗

Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers

Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.

14 SOLAR ENERGY↗

Nanoscale Ferroelectric Control of Novel Electronic States in Layered Two-Dimensional Materials (Final Report)

In this DOE Early Career project “Nanoscale Ferroelectric Control of Novel Electronic States in Layered Two-Dimensional Materials,” the PI’s group has combined ferroelectric field effect with nanoscale domain imaging and writing to design the electronic and optical properties of two-dimensional (2D) van der Waals materials, including graphene and transition metal dichalcogenides MoS2 and ReS2. The van der Waals materials have been prepared into field effect transistor (FET) devices with ferroelectric gates. Through domain patterning in a ferroelectric polymer PVDF-TrEF top-gate via conductive atomic force microscopy, the team has created programmable Schottky junctions in monolayer MoS 2 , where both barrier height and I-V rectifying polarity can be reconfigured. The transport anisotropy of monolayer to few-layer ReS 2 has been mapped out by defining the entire channel into an insulating state and creating nanoscale conducting paths along different directions through domain writing in the ferroelectric top-gate. The result shows that the conductivity along and perpendicular to the Re-chain can differ by >5.5x10 4 . Theoretical modeling points to the band origin of the transport anomaly and reveals the emergence of a flat band in few-layer ReS 2 . The interfacial epitaxial relation between ReS 2 and PVDF-TrFE further promotes the formation of close-packed, highly ordered PVDF-TrFE nanowires with width of 35 nm and 10 nm. Nonvolatile modulation of quantum Hall effect has been achieved in graphene FETs with a ferroelectric oxide Ba 0.4 Sr 0.6 TiO 3 back-gate. Scattering from the remote surface optical phonon in Ba 0.4 Sr 0.6 TiO 3 limits the room temperature mobility of graphene to be about 3x10 4 cm 2 /Vs. Steep-slope switching has been achieved in MoS 2 FETs back-gated by polycrystalline Pb(Zr,Ti)O 3 , which signals a static-state negative capacitance mode without involving an additional dielectric layer. Piezoresponse force microscopy studies show that the sub-threshold swing can be well correlated with the domain wall density in Pb(Zr,Ti)O 3 . The team also observes an unconventional filtering effect of the second harmonic generation response at the MoS 2 /Pb(Zr,Ti)O 3 heterointerface, which can be accounted for by the alignment between one of the polar axes of MoS 2 and the chiral dipole rotation at the surface of domain wall in Pb(Zr,Ti)O 3 . The research supported by this DOE grant has significantly advanced the fundamental understanding and functional design of ferroelectric/2D van der Waals heterostructures for their implementation towards energy applications.

36 MATERIALS SCIENCE↗

Calcined Polyethyleneimine-Coated Optical Fibers for Distributed pH Monitoring at High Pressures and Temperatures

In the oil and gas, CO2 sequestration, H2 subsurface storage, and geothermal energy sectors, subsurface pH measurements are critical for monitoring the geochemical conditions and estimating potential corrosion rates of wellbore systems. Real-time pH measurements in these conditions are vital for detecting and predicting corrosion deterioration of wellbore components that may jeopardize the safety and continued operation of wellbore systems. Previous tests using metal oxide-based coatings (TiO2) provided strong responses at elevated temperatures and moderate pressure stability but provided poor differentiation between acidic and alkaline solutions. Building off the pH responsiveness of the TiO2 surface and known pH sensitivity of amine-based polymers, a coating based on the secondary amine polymer polyethyleneimine (PEI) was developed. As the polymer itself is highly water soluble and easily removed by aqueous solutions, the sensor coating was treated with a high temperature (500 °C) calcination procedure in air to convert it into a more stable oxidized coating capable of withstanding hot aqueous solutions without dissolving while retaining linear pH sensitivity from pH values between 2 and 11. The sensor performance was measured using optical transmission measurements in solutions of various pHs and using optical backscatter reflectometry for distributed pH sensing demonstration in wellbore-relevant pressures (up to 1,000 psi) and temperatures (80 °C).

Shumski, Alexander↗

Polymer compositions

Compositions including one or more polymers are provided. Exemplary polymers include polymeric carbon monoxides. The compositions can be prepared by subjecting a source material to x-rays, optionally at increased pressures. The compositions can be used in a variety of applications, such as fuels, optics, and electronics.

Pravica, Michael↗

Single-molecule investigations of single-chain cellulose biosynthesis

Cellulose biosynthesis in sessile bacterial colonies originates in the membrane-integrated bacterial cellulose synthase (Bcs) AB complex. We utilize optical tweezers to measure single-strand cellulose biosynthesis by BcsAB from Rhodobacter sphaeroides . Synthesis depends on uridine diphosphate glucose, Mg 2+ , and cyclic diguanosine monophosphate, with the last displaying a retention time of ∼80 min. Below a stall force of 12.7 pN, biosynthesis is relatively insensitive to force and proceeds at a rate of one glucose addition every 2.5 s at room temperature, increasing to two additions per second at 37°. At low forces, conformational hopping is observed. Single-strand cellulose stretching unveiled a persistence length of 6.2 nm, an axial stiffness of 40.7 pN, and an ability for complexes to maintain a tight grip, with forces nearing 100 pN. Stretching experiments exhibited hysteresis, suggesting that cellulose microstructure underpinning robust biofilms begins to form during synthesis. Cellohexaose spontaneously binds to nascent single cellulose strands, impacting polymer mechanical properties and increasing BcsAB activity.

59 BASIC BIOLOGICAL SCIENCES↗