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Description
Post-combustion carbon capture is a viable option for reducing CO2 greenhouse gas emissions, and one potentially promising technology for this route is adsorption using chemically and physically based sorbents. A number of exceptional CO2 sorbents materials have been prepared including metal organic frameworks, zeolites, and carbon based materials. One particular

Post-combustion carbon capture is a viable option for reducing CO2 greenhouse gas emissions, and one potentially promising technology for this route is adsorption using chemically and physically based sorbents. A number of exceptional CO2 sorbents materials have been prepared including metal organic frameworks, zeolites, and carbon based materials. One particular group of capable materials are amine based solid sorbents that has shown to possess high adsorption capacities and favorable adsorption kinetics. A key variable in the synthesis of an amine based sorbent is the support which acts as the platform for the amine modification. Aerogels, due to their high porosities and surface areas, appear to be a promising support for an amine modified CO2 sorbent. Therefore, in order to develop a commercially viable CO2 sorbent, particulate aerogels manufactured by Cabot Corporation through an economical and proprietary ambient drying process were modified with amines using a variety of functionalization methods. Two methods of physical impregnation of the amino polymer TEPA were performed in order to observe the performance as well as understand the effects of how the TEPA distribution is affected by the method of introduction. Both samples showed excellent adsorption capacities but poor cyclic stability for lack of any covalent attachment. Furthermore the method of TEPA impregnation seems to be independent on how the polymer will be distributed in the pore space of aerogel. The last two methods utilized involved covalently attaching amino silanes to the surface silanols of the aerogel. One method was performed in the liquid phase under anhydrous and hydrous conditions. The materials developed through the hydrous method have much greater adsorption capacities relative to the anhydrous sample as a result of the greater amine content present in the hydrous sample. Water is another source of silylation where additional silanes can attach and polymerize. These samples also possessed stable cyclic stability after 100 adsorption/regeneration cycles. The other method of grafting was performed in the gas phase through ALD. These samples possessed exceptionally high amine efficiencies and levels of N content without damaging the microstructure of the aerogel in contrast to the liquid phase grafted sorbents.
ContributorsLinneen, Nick (Author) / Lin, Jerry (Thesis advisor) / Pfeffer, Robert (Thesis advisor) / Lind, Mary (Committee member) / Rege, Kaushal (Committee member) / Nielsen, David (Committee member) / Anderson, James (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Synthetic gene networks have evolved from simple proof-of-concept circuits to

complex therapy-oriented networks over the past fifteen years. This advancement has

greatly facilitated expansion of the emerging field of synthetic biology. Multistability is a

mechanism that cells use to achieve a discrete number of mutually exclusive states in

response to environmental inputs. However, complex

Synthetic gene networks have evolved from simple proof-of-concept circuits to

complex therapy-oriented networks over the past fifteen years. This advancement has

greatly facilitated expansion of the emerging field of synthetic biology. Multistability is a

mechanism that cells use to achieve a discrete number of mutually exclusive states in

response to environmental inputs. However, complex contextual connections of gene

regulatory networks in natural settings often impede the experimental establishment of

the function and dynamics of each specific gene network.

In this work, diverse synthetic gene networks are rationally designed and

constructed using well-characterized biological components to approach the cell fate

determination and state transition dynamics in multistable systems. Results show that

unimodality and bimodality and trimodality can be achieved through manipulation of the

signal and promoter crosstalk in quorum-sensing systems, which enables bacterial cells to

communicate with each other.

Moreover, a synthetic quadrastable circuit is also built and experimentally

demonstrated to have four stable steady states. Experiments, guided by mathematical

modeling predictions, reveal that sequential inductions generate distinct cell fates by

changing the landscape in sequence and hence navigating cells to different final states.

Circuit function depends on the specific protein expression levels in the circuit.

We then establish a protein expression predictor taking into account adjacent

transcriptional regions’ features through construction of ~120 synthetic gene circuits

(operons) in Escherichia coli. The predictor’s utility is further demonstrated in evaluating genes’ relative expression levels in construction of logic gates and tuning gene expressions and nonlinear dynamics of bistable gene networks.

These combined results illustrate applications of synthetic gene networks to

understand the cell fate determination and state transition dynamics in multistable

systems. A protein-expression predictor is also developed to evaluate and tune circuit

dynamics.
ContributorsWu, Fuqing (Author) / Wang, Xiao (Thesis advisor) / Haynes, Karmella (Committee member) / Marshall, Pamela (Committee member) / Nielsen, David (Committee member) / Brafman, David (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A

Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A series of solid sorbents were synthesized by functionalizing amines on the surface of silica aerogels. This was done by three coating methods: physical adsorption, magnetically assisted impact coating (MAIC) and atomic layer deposition (ALD). CO2 adsorption capacity of the sorbents was measured at room temperature in a Cahn microbalance. The sorbents synthesized by physical adsorption show the largest CO2 adsorption capacity (1.43-1.63 mmol CO2/g). An additional sorbent synthesized by ALD on hydrophilic aerogels at atmospheric pressures shows an adsorption capacity of 1.23 mmol CO2/g. Studies on one amine-modified sorbent show that the powder is of agglomerate bubbling fluidization (ABF) type. The powder is difficult to fluidize and has limited bed expansion. The ultimate goal is to configure the amine-modified sorbents in a micro-jet assisted gas fluidized bed to conduct adsorption studies. MOF-5 membranes were synthesized on α-alumina supports by two methods: in situ synthesis and secondary growth synthesis. Characterization by scanning electron microscope (SEM) imaging and X-ray diffraction (XRD) show that the membranes prepared by both methods have a thickness of 14-16 μm, and a MOF-5 crystal size of 15-25 μm with no apparent orientation. Single gas permeation results indicate that the gas transport through both membranes is determined by a combination of Knudsen diffusion and viscous flow. The contribution of viscous flow indicates that the membranes have defects.
ContributorsRosa, Teresa M (Author) / Lin, Jerry (Thesis advisor) / Pfeffer, Robert (Thesis advisor) / Dai, Lenore (Committee member) / Nielsen, David (Committee member) / Arizona State University (Publisher)
Created2010
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Description
The world today needs novel solutions to address current challenges in areas spanning areas from sustainable manufacturing to healthcare, and biotechnology offers the potential to help address some of these issues. One tool that offers opportunities across multiple industries is the use of nonribosomal peptide synthases (NRPSs). These are modular

The world today needs novel solutions to address current challenges in areas spanning areas from sustainable manufacturing to healthcare, and biotechnology offers the potential to help address some of these issues. One tool that offers opportunities across multiple industries is the use of nonribosomal peptide synthases (NRPSs). These are modular biological factories with individualized subunits that function in concert to create novel peptides.One element at the heart of environmental health debates today is plastics. Biodegradable alternatives for petroleum-based plastics is a necessity. One NRPS, cyanophycin synthetase (CphA), can produce cyanophycin grana protein (CGP), a polymer composed of a poly-aspartic acid backbone with arginine side chains. The aspartic backbone has the potential to replace synthetic polyacrylate, although current production costs are prohibitive. In Chapter 2, a CphA variant from Tatumella morbirosei is characterized, that produces up to 3x more CGP than other known variants, and shows high iCGP specificity in both flask and bioreactor trials. Another CphA variant, this one from Acinetobacter baylyi, underwent rational protein design to create novel mutants. One, G217K, is 34% more productive than the wild type, while G163K produces a CGP with shorter chain lengths. The current structure refined from 4.4Å to 3.5Å. Another exciting application of NRPSs is in healthcare. They can be used to generate novel peptides such as complex antibiotics. A recently discovered iterative polyketide synthase (IPTK), dubbed AlnB, produces an antibiotic called allenomycin. One of the modular subunits, a dehydratase named AlnB_DH, was crystallized to 2.45Å. Several mutations were created in multiple active site residues to help understand the functional mechanism of AlnB_DH. A preliminary holoenzyme AlnB structure at 3.8Å was generated although the large disorganized regions demonstrated an incomplete structure. It was found that chain length is the primary factor in driving dehydratase action within AlnB_DH, which helps lend understanding to this module.
ContributorsSwain, Kyle (Author) / Nannenga, Brent (Thesis advisor) / Nielsen, David (Committee member) / Mills, Jeremy (Committee member) / Seo, Eileen (Committee member) / Acharya, Abhinav (Committee member) / Arizona State University (Publisher)
Created2022