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Chang, Che-Wei

Publications and source records attributed to Chang, Che-Wei.

17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Strategies for regeneration of Pt-alloy catalysts supported on silica for propane dehydrogenation

Catalyst stability, resistance to deactivation, and regeneration remain a challenge for high temperature reaction processes. For Pt alloys used in propane dehydrogenation (PDH), the primary pathways of catalyst deactivation include coke formation and metal nanoparticle sintering over time. Recent work shows that silica-supported catalysts provide excellent selectivity for this reaction, but the regenerability of silica-supported catalysts has not been established. In this work, we study a series of Pt alloys, including PtMn, PtZn, and PtSn, for the PDH reaction at 550 °C and 600 °C, and we subject the catalysts to regeneration over multiple cycles. While oxidation in air restores the reactivity completely with minimal catalyst sintering, it is surprising to find that these catalysts can also be regenerated in pure hydrogen. Here we explore the types of coke formed on these catalysts using in situ temperature programmed oxidation (TPO). Two types of coke are found: one on the metallic NP surface, and a second on the silica support. Our work shows that treatment in hydrogen causes redistribution of the coke between the metal and support, which can restore most catalytic activity lost during a reaction run. Finally, periodic introduction of H 2 during a reaction cycle may constitute an unexplored strategy for extending the lifetime of PDH catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Comparison of the Forward and Reverse Photocycle Dynamics of Two Highly Similar Canonical Red/Green Cyanobacteriochromes Reveals Unexpected Differences

Cyanobacteriochromes (CBCRs) are cyanobacterial photoreceptors that exhibit photochromism between two states: a thermally stable dark-adapted state and a metastable light-adapted state with bound linear tetrapyrrole (bilin) chromophores possessing 15Z and 15E configurations, respectively. The photodynamics of canonical red/green CBCRs have been extensively studied; however, the time scales of their excited-state lifetimes and subsequent ground-state evolution rates widely differ and, at present, remain difficult to predict. Here, we compare the photodynamics of two closely related red/green CBCRs that have substantial sequence identity (~68%) and similar chromophore environments: AnPixJg2 from Anabaena sp. PCC 7120 and NpR6012g4 from Nostoc punctiforme. Using broadband transient absorption spectroscopy on the primary (125 fs to 7 ns) and secondary (7 ns to 10 ms) time scales together with global analysis modeling, our studies revealed that AnPixJg2 and NpR6012g4 have comparable quantum yields for initiating the forward ( 15Z P r → 15E P g ) and reverse ( 15E P g → 15Z P r ) reactions, which proceed through monotonic and nonmonotonic mechanisms, respectively. In addition to small discrepancies in the kinetics, the secondary reverse dynamics resolved unique features for each domain: intermediate shunts in NpR6012g4 and a Meta-Gf intermediate red-shifted from the 15Z P r photoproduct in AnPixJg2. Altogether, this study supports the conclusion that sequence similarity is a useful criterion for predicting pathways of the light-induced evolution and quantum yield of generating primary intermediate Φ p within subfamilies of CBCRs, but more studies are still needed to develop a comprehensive molecular level understanding of these processes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Conservation and diversity in the secondary forward photodynamics of red/green cyanobacteriochromes

Cyanobacteriochromes (CBCRs) are photosensitive proteins that are distantly related to the phytochrome family of photoreceptors and, like phytochromes, exhibit photoactivity initiated by the excited-state photoisomerization of a covalently bound bilin chromophore. The canonical red/green photoswitching sub-family is the most studied class of CBCRs studied to date. Recently, a comparative study of the ultrafast (100 fs–10 ns) forward photodynamics of nine red/green photoswitching CBCR domains isolated from Nostoc punctiforme were reported (S. M. Gottlieb, P. W. Kim, C.-W. Chang, S. J. Hanke, R. J. Hayer, N. C. Rockwell, S. S. Martin, J. C. Lagarias and D. S. Larsen, Conservation and Diversity in the Primary Forward Photodynamics of Red/Green Cyanobacteriochromes, Biochemistry, 2015, 54, 1028–1042). We extend this study by characterizing the secondary (10 ns–1 ms) forward photodynamics of eight red/green photoswitching CBCRs from N. punctiforme with broadband time-resolved absorption spectroscopy. We demonstrate that the dynamics of these representative red/green CBCRs can be separated into two coexisting pathways involving a photoactive pathway that is successful in generating the terminal light-adapted 15E P g population and an unsuccessful pathway that stalls after generating a meta-stable Lumi-O f intermediate. The photoactive pathway evolves through a similar mechanism from excitation of the dark-adapted 15Z P r state to generate a far-red absorbing Lumi-R f and then via a succession of blue-shifting photointermediates to ultimately generate the 15E P g state. This suggests a steady deviation from planarity of the bilin chromophore during the dynamics. While, the general mechanism for this evolution is conserved among these CBCBs, the timescales of these dynamics deviate significantly. Only half of the characterized CBCRs exhibit the unproductive pathways due to photoexcitation of dark-adapted 15Z P o sub-population that upon photoexcitation generates a meta-stable Lumi-O f intermediate, which eventually decays back to the 15Z P o subpopulation. 15Z P o is ascribed the horizontal Asp657 configuration that disrupts H-bonding with the chromophore in the dark-adapted state; its presence can be identified via enhanced absorption of high-energy tail of the electronic absorption spectrum.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Reverse Photodynamics of the Noncanonical Red/Green NpR3784 Cyanobacteriochrome from Nostoc punctiforme

In the companion paper (10.1021/acs.biochem.8b01274), we examined the forward P r photodynamics of NpR3784 (UniProtKB B2J457), a representative member of a noncanonical red/green (R/G) cyanobacteriochrome (CBCR) subfamily. Here the reverse P g → P r photodynamics of NpR3784 was studied by broadband transient absorption pump–probe spectroscopy. Primary (100 fs to 10 ns) and secondary (10 ns to 1 ms) photodynamics were characterized over nine decades of time, which also were complemented with temperature-jump cryokinetics measurements. In contrast with canonical R/G CBCRs, the NpR3784 reverse photoconversion yielded two spectrally distinct primary photoproducts, Lumi-G o and Lumi-G r , which decay on different time scales. The two primary photoproducts of NpR3784 equilibrate on the 40 ns time scale and subsequently propagate as a single intermediate population into P r . Such heterogeneity could arise from differences in the direction of D-ring rotation, in chromophore protonation or hydrogen bonding, or in the mobility of protein residues or of solvent water nearby the chromophore or some combination therein. Here, we conclude that the atypical photodynamics of NpR3784 reflects chromophore–protein interactions that differ from those present in the canonical R/G CBCR family.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Forward Photodynamics of the Noncanonical Red/Green NpR3784 Cyanobacteriochrome from Nostoc punctiforme

Cyanobacteriochromes (CBCRs) make up a diverse family of cyanobacterial photoreceptors distantly related to the phytochrome photoreceptors of land plants. At least two lineages of CBCRs have reacquired red-absorbing dark states similar to the phytochrome Pr resting state but are coupled to green-absorbing light-adapted states rather than the canonical far-red-absorbing light-adapted state. One such lineage includes the canonical red/green (R/G) CBCRs that includes AnPixJg2 (UniProtKB Q8YXY7) and NpR6012g4 (UniProtKB B2IU14) that have been extensively characterized. Here we examine the forward Pr photodynamics of NpR3784 (UniProtKB B2J457), a representative member of the second R/G CBCR subfamily. Using broadband transient absorption pump–probe spectroscopy, we characterize both primary (100 fs to 10 ns) and secondary (10 ns to 1 ms) forward (P r → P g ) photodynamics and compare the results to temperature-jump cryokinetics measurements. Our studies show that primary isomerization dynamics occur on an ~10 ps timescale, yet remarkably, the red-shifted primary Lumi-Rf photoproduct found in all photoactive canonical R/G CBCRs examined to date is extremely short-lived in NpR3784. Furthermore, these results demonstrate that differences in reaction pathways reflect the evolutionary history of R/G CBCRs despite the convergent evolution of their photocycle end products.

*Light↗
DOE OSTI2018

Emerging investigator series: quantification of multiwall carbon nanotubes in plant tissues with spectroscopic analysis

If agricultural plants are exposed to carbon nanotubes (CNTs), they can potentially take up the CNTs from growth media and translocate them to their different tissues. In addition, agricultural application of CNTs recently attracted increasing attention, as they could promote germination, enhance crop yield, and exhibit other benefits. For evaluating the environmental effects of CNTs and optimizing their agricultural application, it is essential to quantify CNTs in plant tissues. In this study, pristine (p-) and carboxyl-functionalized (c-) multiwall CNTs (MWCNTs) were extracted from plant tissues by a sequential digestion with nitric acid (HNO 3 ) and sulfuric acid (H 2 SO 4 ). The extracted MWCNTs were stabilized with nonionic surfactant Triton X-100 and analyzed with ultraviolet-visible (UV-vis) spectroscopic analysis to measure the concentration of the MWCNTs in plant (lettuce) tissues. The MWCNT concentration was linearly correlated with the absorbance at 800 nm. The detection limit for p- and c-MWCNTs was achieved at 0.10–0.12, 0.070–0.081, 0.019–0.18 μg mg -1 for leaf, stem, and root tissues, respectively. The developed method was applied for lettuce (Lactuca sativa, cv. black seeded Simpson) hydroponically grown with 5, 10, 20 mg L -1 of p-MWCNTs and c-MWCNTs in the culture solution. We detected 0.21 ± 0.05–4.57 ± 0.39 μg mg -1 p-MWCNTs and 0.20 ± 0.17–0.75 ± 0.25 μg mg -1 c-MWCNTs in the lettuce roots, positively correlated with the dose of CNTs in solution. We have come up with a method for rapid quantification of CNTs in plant tissues using a widely-accessible technique, which can enable reliable analysis of CNTs in plant tissues and provide critical information for evaluating the environmental implications and managing agricultural application of CNTs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Noncanonical Photodynamics of the Orange/Green Cyanobacteriochrome Power Sensor NpF2164g7 from the PtxD Phototaxis Regulator of Nostoc punctiforme

Forward and reverse primary (<10 ns) and secondary (>10 ns) photodynamics of cyanobacteriochrome (CBCR) NpF2164g7 were characterized by global analysis of ultrafast broadband transient absorption measurements. NpF2164g7 is the most C-terminal bilin-binding GAF domain in the Nostoc punctiforme phototaxis sensor PtxD (locus Npun_F2164). Although a member of the canonical red/green CBCR subfamily phylogenetically, NpF2164g7 exhibits an orange-absorbing 15Z P o dark-adapted state instead of the typical red-absorbing 15Z P r dark-adapted state characteristic of this subfamily. The green-absorbing 15E P g photoproduct of NpF2164g7 is unstable, allowing this CBCR domain to function as a power sensor. Photoexcitation of the 15Z P o state triggers inhomogeneous excited-state dynamics with three spectrally and temporally distinguishable pathways to generate the light-adapted 15E P g state in high yield (estimated at 25–30%). Although observed in other CBCR domains, the inhomogeneity in NpF2164g7 extends far into secondary relaxation dynamics (10 ns –1 ms) through to formation of 15E P g . In the reverse direction, the primary dynamics after photoexcitation of 15E P g are qualitatively similar to those of other red/green CBCRs, but secondary dynamics involve a “pre-equilibrium” step before regenerating 15Z P o . As a result, the anomalous photodynamics of NpF2164g7 may reflect an evolutionary adaptation of CBCR sensors that function as broadband light intensity sensors.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Correlating structural and photochemical heterogeneity in cyanobacteriochrome NpR6012g4

Phytochrome photoreceptors control plant growth, development, and the shade avoidance response that limits crop yield in high-density agricultural plantings. Cyanobacteriochromes (CBCRs) are distantly related photosensory proteins that control cyanobacterial metabolism and behavior in response to light. Photoreceptors in both families reversibly photoconvert between two photostates via photoisomerization of linear tetrapyrrole (bilin) chromophores. Spectroscopic and biochemical reprorts have demonstrated heterogeneity in both photostates, but the structural basis for such heterogeneity remains unclear. We discuss solution NMR structures for both photostates of the red/green CBCR NpR6012g4 from Nostoc punctiforme . In addition to identifying structural changes accompanying photoconversion, these structures reveal structural heterogeneity for residues Trp655 and Asp657 in the red-absorbing NpR6012g4 dark state, yielding two distinct environments for the phycocyanobilin chromophore. We use site-directed mutagenesis and fluorescence and absorbance spectroscopy to assign an orange-absorbing population in the NpR6012g4 dark state to the minority configuration for Asp657. This population does not undergo full, productive photoconversion, as shown by time-resolved spectroscopy and absorption spectroscopy at cryogenic temperature. Our research thus elucidate the spectral and photochemical consequences of structural heterogeneity in a member of the phytochrome superfamily, insights that should inform efforts to improve photochemical or fluorescence quantum yields in the phytochrome superfamily.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Finite element approach for transient analysis of multibody systems

A three-dimensional, finite element based formulation for the transient dynamics of constrained multibody systems with trusslike configurations is presented. A convected coordinate system is used to define the rigid-body motion of individual elements in the system. Deformation of each element is defined relative to its convected coordinate system. The formulation is oriented toward joint-dominated structures. Through a series of sequential transformations, the joint degree of freedom is built into the equations of motion of the element to reduce geometric constraints. Based on the derivation, a general-purpose code has been developed. Two examples are presented to illustrate the application of the code.

Wu, Shih-Chin↗
NASA NTRS1992

Computing Large-Angle Transients In Structures

LATDYN is computer code for calculating large-angle transient dynamics of flexible articulating structures and mechanisms including joints about which members rotate through large angles. Extends and brings together some of aspects of finite-element analysis of structures, dynamics of multiple bodies, and analysis of control systems. Combines significant portions of their distinct capabilities into one analysis software tool. Software consists of three FORTRAN computer programs: LATDYN program, Preprocessor, and Postprocessor. Written in FORTRAN 77.

Housner, Jerrold M.↗
NASA NTRS1991

Large Angle Transient Dynamics (LATDYN) user's manual

A computer code for modeling the large angle transient dynamics (LATDYN) of structures was developed to investigate techniques for analyzing flexible deformation and control/structure interaction problems associated with large angular motions of spacecraft. This type of analysis is beyond the routine capability of conventional analytical tools without simplifying assumptions. In some instances, the motion may be sufficiently slow and the spacecraft (or component) sufficiently rigid to simplify analyses of dynamics and controls by making pseudo-static and/or rigid body assumptions. The LATDYN introduces a new approach to the problem by combining finite element structural analysis, multi-body dynamics, and control system analysis in a single tool. It includes a type of finite element that can deform and rotate through large angles at the same time, and which can be connected to other finite elements either rigidly or through mechanical joints. The LATDYN also provides symbolic capabilities for modeling control systems which are interfaced directly with the finite element structural model. Thus, the nonlinear equations representing the structural model are integrated along with the equations representing sensors, processing, and controls as a coupled system.

Abrahamson, A. Louis↗
NASA NTRS1991

A finite element approach for the dynamic analysis of joint-dominated structures

A finite element method to model dynamic structural systems undergoing large rotations is presented. The dynamic systems are composed of rigid joint bodies and flexible beam elements. The configurations of these systems are subject to change due to the relative motion in the joints among interconnected elastic beams. A body fixed reference is defined for each joint body to describe the joint body's displacements. Using the finite element method and the kinematic relations between each flexible element and its corotational reference, the total displacement field of an element, which contains gross rigid as well as elastic effects, can be derived in terms of the translational and rotational displacements of the two end nodes. If one end of an element is hinged to a joint body, the joint body's displacements and the hinge degree of freedom at the end are used to represent the nodal displacements. This results in a highly coupled system of differential equations written in terms of hinge degrees of freedom as well as the rotational and translational displacements of joint bodies and element nodes.

Chang, Che-Wei↗
NASA NTRS1989

Dynamic analysis of flexible mechanical systems using LATDYN

A 3-D, finite element based simulation tool for flexible multibody systems is presented. Hinge degrees-of-freedom is built into equations of motion to reduce geometric constraints. The approach avoids the difficulty in selecting deformation modes for flexible components by using assumed mode method. The tool is applied to simulate a practical space structure deployment problem. Results of examples demonstrate the capability of the code and approach.

Wu, Shih-Chin↗
NASA NTRS1989

A finite element approach for large motion dynamic analysis of multibody structures in space

A three-dimensional finite element formulation for modeling the transient dynamics of constrained multibody space sructures with truss-like configurations is presented. Convected coordinate systems are used to define rigid-body motion of individual elements in the system. These systems are located at one end of each element and are oriented such that one axis passes through the other end of the element. Deformation of each element, relative to its convected coordinate system, is defined by cubic flexural shape functions as used in finite element methods of structural analysis. The formulation is oriented toward joint dominated structures and places the generalized coordinates at the joint. A transformation matrix is derived to integrate joint degree-of-freedom into the equations of motion of the element. Based on the derivation, a general-purpose code LATDYN (Large Angle Transient DYNamics) was developed. Two examples are presented to illustrate the application of the code. For the spin-up of a flexible beam, results are compared with existing solutions available in the literature. For the deployment of one bay of a deployable space truss (the Minimast), results are verified by the geometric knowledge of the system and converged solution of a successively refined model.

Chang, Che-Wei↗