Amphiphilic polymer co-networks: 32 years old and growing stronger – a perspective
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Polymer Science↗
SEARCH · Engineering Papers
Results for “Stimulus responsive”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Structural Manipulation of a Zirconocene-Based Porous Coordination Cage Using External and Host–Guest Stimuli
Porous coordination cages (PCCs) constructed from a zirconocene-based cluster have drawn great attention for their high stability and structural tunability. These features have enabled these cages to be utilized for a wide array of applications. Here this work demonstrates the structural flexibility and stimulus-responsive features of two interconvertible zirconocene-based PCCs. The subjects, PCC-20c (capsular) and PCC-20t (tetrahedral), are constructed from the same cluster and ligand but exhibit different shapes and properties. In the synthetic study of the cages, it is found that higher temperatures of synthesis yield PCC-20c in several different crystalline phases while lower temperatures of synthesis yield pure phase PCC-20t. Thermodynamic studies on the interconversion of the two cages show that the conversion from PCC-20t into PCC-20c is an entropically driven process and can be largely affected by the solvent environment. Additionally, the process of PCC-20t/c conversion can be mediated by the counter anions and light irradiation as evidenced by the change in equilibrium constants under these influences. The current studies are conducted to decipher how the PCC-20t/c phase can be controllably synthesized, interconverted, and their properties can be modified under the use of external stimuli: heat, light, and guest molecules.
36 MATERIALS SCIENCE↗
Local Chain Dynamics in Sequence-Controlled Polymers as a Tunable Handle for Rare Earth Sequestration
Chain dynamics govern the intricate behaviors of proteins, underpinning functions such as catalysis, recognition, and stimulus response, and are an increasingly appreciated aspect of structure–function relationships. Analogously, manipulating chain dynamics and structure in abiotic polymers via sequence control is an exciting, yet underexplored, strategy for improving material functions. In this work, we report a systematic study relating the sequence of polymeric sequestrants to their structure and dynamics, as well as to their binding affinity and selectivity for model substrates, rare earth elements (REEs). A series of sequence-controlled polymers with metal chelating, solubilizing, and structure forming monomers was synthesized via multiblock polymerization, yielding compositionally identical polymers with spectroscopically resolved domains and distinct morphologies. Using a combination of small-angle X-ray scattering and 19 F NMR relaxometry measurements, we connected differences in polymer structure and dynamics to polymer sequence variables such as the patchiness (density) of the structure forming monomer and the location of the chelating monomer. Furthermore, we found that, relative to calcium, all polymers in the series collapse more and have slower dynamics when binding REEs (lanthanum and lutetium) , though the extent of these effects were sequence-dependent and localized to specific domains within the polymer. Notably, sequence-controlled polymers that exhibited the largest conformational and dynamic changes upon binding REEs also bound REEs with the greatest affinity and modest selectivity. Collectively, these results correlate monomer patterning with dynamics, morphology, and REE binding performance en route to the development of efficient and selective macromolecular chelators.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity
Abstract Flexible metal–organic materials that exhibit stimulus-responsive switching between closed (non-porous) and open (porous) structures induced by gas molecules are of potential utility in gas storage and separation. Such behaviour is currently limited to a few dozen physisorbents that typically switch through a breathing mechanism requiring structural contortions. Here we show a clathrate (non-porous) coordination network that undergoes gas-induced switching between multiple non-porous phases through transient porosity, which involves the diffusion of guests between discrete voids through intra-network distortions. This material is synthesized as a clathrate phase with solvent-filled cavities; evacuation affords a single-crystal to single-crystal transformation to a phase with smaller cavities. At 298 K, carbon dioxide, acetylene, ethylene and ethane induce reversible switching between guest-free and gas-loaded clathrate phases. For carbon dioxide and acetylene at cryogenic temperatures, phases showing progressively higher loadings were observed and characterized using in situ X-ray diffraction, and the mechanism of diffusion was computationally elucidated.
Chemistry↗
Multifunctional nanopore electrode array method for characterizing and manipulating single entities in attoliter-volume enclosures
Structurally regular nanopore arrays fabricated to contain independently controllable annular electrodes represent a new kind of architecture capable of electrochemically addressing small collections of matter—down to the single entity (molecule, particle, and biological cell) level. Furthermore, these nanopore electrode arrays (NEAs) can also be interrogated optically to achieve single entity spectroelectrochemistry. Larger entities such as nanoparticles and single bacterial cells are investigated by dark-field scattering and potential-controlled single-cell luminescence experiments, respectively, while NEA-confined molecules are probed by single molecule luminescence. By carrying out these experiments in arrays of identically constructed nanopores, massively parallel collections of single entities can be investigated simultaneously. The multilayer metal–insulator design of the NEAs enables highly efficient redox cycling experiments with large increases in analytical sensitivity for chemical sensing applications. NEAs may also be augmented with an additional orthogonally designed nanopore layer, such as a structured block copolymer, to achieve hierarchically organized multilayer structures with multiple stimulus-responsive transport control mechanisms. Finally, NEAs constructed with a transparent bottom layer permit optical access to the interior of the nanopore, which can result in the cutoff of far-field mode propagation, effectively trapping radiation in an ultrasmall volume inside the nanopore. Furthermore, the bottom metal layer may be used as both a working electrode and an optical cladding layer, thus, producing bifunctional electrochemical zero-mode waveguide architectures capable of carrying out spectroelectrochemical investigations down to the single molecule level.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Massively parallel, computationally guided design of a proenzyme
Proteins have shown promise as therapeutics and diagnostics, but their effectiveness is limited by our inability to spatially target their activity. To overcome this limitation, we developed a computationally guided method to design inactive proenzymes or zymogens, which are activated through cleavage by a protease. Since proteases are differentially expressed in various tissues and disease states, including cancer, these proenzymes could be targeted to the desired microenvironment. We tested our method on the therapeutically relevant protein carboxypeptidase G2 (CPG2). We designed Pro-CPG2s that are inhibited by 80 to 98% and are partially to fully reactivatable following protease treatment. The developed methodology, with further refinements, could pave the way for routinely designing protease-activated protein-based therapeutics and diagnostics that act in a spatially controlled manner. Confining the activity of a designed protein to a specific microenvironment would have broad-ranging applications, such as enabling cell type-specific therapeutic action by enzymes while avoiding off-target effects. While many natural enzymes are synthesized as inactive zymogens that can be activated by proteolysis, it has been challenging to redesign any chosen enzyme to be similarly stimulus responsive. Here, we develop a massively parallel computational design, screening, and next-generation sequencing-based approach for proenzyme design. For a model system, we employ carboxypeptidase G2 (CPG2), a clinically approved enzyme that has applications in both the treatment of cancer and controlling drug toxicity. Detailed kinetic characterization of the most effectively designed variants shows that they are inhibited by ∼80% compared to the unmodified protein, and their activity is fully restored following incubation with site-specific proteases. Introducing disulfide bonds between the pro- and catalytic domains based on the design models increases the degree of inhibition to 98% but decreases the degree of restoration of activity by proteolysis. A selected disulfide-containing proenzyme exhibits significantly lower activity relative to the fully activated enzyme when evaluated in cell culture. Structural and thermodynamic characterization provides detailed insights into the prodomain binding and inhibition mechanisms. The described methodology is general and could enable the design of a variety of proproteins with precise spatial regulation.
59 BASIC BIOLOGICAL SCIENCES↗
Autonomous hydrogel locomotion regulated by light and electric fields
Autonomous robotic functions in materials beyond simple stimulus-response actuation require the development of functional soft matter that can complete well-organized tasks without step-by-step control. We report the design of photo- and electroactivated hydrogels that can capture and deliver cargo, avoid obstacles, and return without external, stepwise control. By incorporating two spiropyran monomers with different chemical substituents in the hydrogel, we created chemically random networks that enabled photoregulated charge reversal and autonomous behaviors under a constant electric field. In addition, using perturbations in the electric field induced by a dielectric inhomogeneity, the hydrogel could be attracted to high dielectric constant materials and autonomously bypasses the low dielectric constant materials under the guidance of the electric field vector. The photo- and electroactive hydrogels investigated here can autonomously perform tasks using constant external stimuli, an encouraging observation for the potential development of molecularly designed intelligent robotic materials.
42 ENGINEERING↗
The technique of linear prediction filters applied to studies of solar wind-magnetosphere coupling
Linear prediction filtering is a powerful empirical technique suitable for the study of stimulus-response behavior. The technique enables one to determine the most general linear relationship between multiple time-varying quantities, assuming that the physical systems relating the quantities are linear and time invariant. Several researchers have applied linear prediction analysis to investigate solar wind-magnetosphere interactions. This short review describes the method of linear prediction analysis, its application to solar wind-magnetosphere coupling studies both in terms of physical processes, and the results of investigations which have used this technique.
Clauer, C. Robert↗
Attention theory and training research
This study used elements of attention theory as a methodological basis to decompose a complex training task in order to improve training efficiency. The complex task was a microcomputer flight simulation where subjects were required to control the stability of their own helicopter while acquiring and engaging enemy helicopers in a threat enviroment. Subjects were divided into whole-task, part-task, and part/open loop adaptive task groups in a transfer of training paradigm. The effect of reducing mental workload at the early stages of learning was examined with respect to the degree that subordinate elements of the complex task could be automated through practice of consistent, learnable stimulus-response relationships. Results revealed trends suggesting the benefit of isolating consistently mapped sub-tasks for part-task training and the presence of a time-sharing skill over and above the skill required for the separate subtasks.
Connelly, James G., Jr.↗
Plant health sensing
If plants are to be used as a food source for long term space missions, they must be grown in a stable environment where the health of the crops is continuously monitored. The sensor(s) to be used should detect any diseases or health problems before irreversible damage occurs. The method of analysis must be nondestructive and provide instantaneous information on the condition of the crop. In addition, the sensor(s) must be able to function in microgravity. This first semester, the plant health and disease sensing group concentrated on researching and consulting experts in many fields in attempts to find reliable plant health indicators. Once several indicators were found, technologies that could detect them were investigated. Eventually the three methods chosen to be implemented next semester were stimulus response monitoring, video image processing and chlorophyll level detection. Most of the other technologies investigated this semester are discussed here. They were rejected for various reasons but are included in the report because NASA may wish to consider pursuing them in the future.
Manukian, Ara↗
Elevated central venous pressure: A consequence of exercise training-induced hypervolemia
Resting plasma volumes, and arterial and central venous pressures (CVP) were measured in 16 men before and after exercise training to determine if training-induced hypervolemia could be explained by a change in total vascular capacitance. In addition, resting levels of plasma vasopressin (AVP), atrial natriuretic peptide (ANP), aldosterone (ALD), and norepinephrine (NE) were measured before and after training. The same measurements of vacular volume, pressures, and plasma hormones were measured in 8 subjects who did not undergo exercise and acted as controls. The exercise training program consisted of 10 weeks of controlled cycle exercise for 30 min/d, 4 d/wk at 75 to 80 percent of maximal oxygen uptake (VO2max). A training effect was verified by a 20 percent increase in VO2max, a resting bradycardia, and a 370 ml (9 percent) increase in blood volume. Mean arterial blood pressure was unaltered by exercise training, but resting CVP increased. The percent change in blood volume from before to after training was linearly related to the percent change in CVP. As a consequence of elevations in both blood volume and CVP, the volume-to-pressure ratio was essentially unchanged following exercise training. Plasma AVP, ANP, ALD, and NE were unaltered. Results indicate that elevated CVP is a consequence of training-induced hypervolemia without alteration in total effective venous capacitance. This may represent a resetting of the pressure-volume stimulus-response relation for regulation of blood volume.
Convertino, Victor A.↗
Language Research Center's Computerized Test System (LRC-CTS) - Video-formatted tasks for comparative primate research
Automation of a computerized test system for comparative primate research is shown to improve the results of learning in standard paradigms. A mediational paradigm is used to determine the degree to which criterion in the learning-set testing reflects stimulus-response associative or mediational learning. Rhesus monkeys are shown to exhibit positive transfer as the criterion levels are shifted upwards, and the effectiveness of the computerized testing system is confirmed.
Rumbaugh, Duane M.↗
Operator vision aids for space teleoperation assembly and servicing
This paper investigates concepts for visual operator aids required for effective telerobotic control. Operator visual aids, as defined here, mean any operational enhancement that improves man-machine control through the visual system. These concepts were derived as part of a study of vision issues for space teleoperation. Extensive literature on teleoperation, robotics, and human factors was surveyed to definitively specify appropriate requirements. This paper presents these visual aids in three general categories of camera/lighting functions, display enhancements, and operator cues. In the area of camera/lighting functions concepts are discussed for: (1) automatic end effector or task tracking; (2) novel camera designs; (3) computer-generated virtual camera views; (4) computer assisted camera/lighting placement; and (5) voice control. In the technology area of display aids, concepts are presented for: (1) zone displays, such as imminent collision or indexing limits; (2) predictive displays for temporal and spatial location; (3) stimulus-response reconciliation displays; (4) graphical display of depth cues such as 2-D symbolic depth, virtual views, and perspective depth; and (5) view enhancements through image processing and symbolic representations. Finally, operator visual cues (e.g., targets) that help identify size, distance, shape, orientation and location are discussed.
Brooks, Thurston L.↗
Toward a New Outlook on Primate Learning and Behavior: Complex Learning and Emergent Processes in Comparative Perspective
Primate research of the 20th century has established the validity of Darwin's postulation of psychological as well as biological continuity between humans and other primates, notably the great apes. Its data make clear that Descartes' view of animals as unfeeling 'beast-machines' is invalid and should be discarded. Traditional behavioristic frameworks, that emphasize the concepts of stimulus, response, and reinforcement and an 'empty-organism' psychology, are in need of major revisions. Revised frameworks should incorporate the fact that, in contrast to the lifeless databases of the 'hard' sciences, the database of psychology entails properties novel to life and its attendant phenomena. The contributions of research this century, achieved by field and laboratory researchers from around the world, have been substantial, indeed revolutionary. It is time to celebrate the progress of our field, to anticipate its significance, and to emphasize conservation of primates in their natural habitats.
Rumbaugh, Duane M.↗
Tensile Properties of Hydrogels and of Snake Skin
Stimulus-responsive or 'smart' gels are of potential interest as sensors and actuators, in industrial separations, and as permeable delivery systems. In most applications, a certain degree of mechanical strength and toughness will be required, yet the large-strain behavior of gels has not been widely reported. Some exceptions include work on gelatin and other food gels, some characterization of soft gels applicable for in-vitro cell growth studies, and toughness determinations on commercial contact lens materials. In general, it can be anticipated that the gel stiffness will increase with increasing degree of crosslinking, but the tensile strength may go through a maximum. Gel properties can be tailored by varying not only the degree of crosslinking, but also the polymer concentration and the nature of the polymer backbone (e.g. its stiffness or solubility). Polypeptides provide an especially interesting case, where secondary structure affects trends in moduli and conformational transitions may accompany phase changes. A few papers on the tensile properties of responsive gels have begun to appear. The responsive hydrogel chosen for the present study, crosslinked hydroxypropylcellulose, shrinks over a rather narrow temperature range near 44 C. Some vertebrate skin is also subject to substantial strain. Among reptiles, the morphologies of the skin and scales show wide variations. Bauer et al. described the mechanical properties and histology of gecko skin; longitudinal tensile properties of snake skin were examined by Jayne with reference to locomotion. The present measurements focus on adaptations related to feeding, including the response of the skin to circumferential tension. Tensile properties will be related to interspecific and regional variation in skin structure and folding.
Hinkley, Jeffrey A.↗
Modelling the firing pattern of bullfrog vestibular neurons responding to naturalistic stimuli
We have developed a neural system identification method for fitting models to stimulus-response data, where the response is a spike train. The method involves using a general nonlinear optimisation procedure to fit models in the time domain. We have applied the method to model bullfrog semicircular canal afferent neuron responses during naturalistic, broad-band head rotations. These neurons respond in diverse ways, but a simple four parameter class of models elegantly accounts for the various types of responses observed. c1999 Elsevier Science B.V. All rights reserved.
Non-NASA Center↗
Signal transduction mechanisms in plants: an overview
This article provides an overview on recent advances in some of the basic signalling mechanisms that participate in a wide variety of stimulus-response pathways. The mechanisms include calcium-based signalling, G-protein-mediated-signalling and signalling involving inositol phospholipids, with discussion on the role of protein kinases and phosphatases interspersed. As a further defining feature, the article highlights recent exciting findings on three extracellular components that have not been given coverage in previous reviews of signal transduction in plants, extracellular calmodulin, extracellular ATP, and integrin-like receptors, all of which affect plant growth and development.
Non-NASA Center↗
Calcium messenger system in plants
The purpose of this review is to delineate the ubiquitous and pivotal role of Ca2+ in diverse physiological processes. Emphasis will be given to the role of Ca2+ in stimulus-response coupling. In addition to reviewing the present status of research, our intention is to critically evaluate the existing data and describe the newly developing areas of Ca2+ research in plants.
NASA Discipline Number 40-30↗