| 1. |
- Englund, Elias, et al.
(författare)
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Expanding Extender Substrate Selection for Unnatural Polyketide Biosynthesis by Acyltransferase Domain Exchange within a Modular Polyketide Synthase
- 2023
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 145:16, s. 8822-8832
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Tidskriftsartikel (refereegranskat)abstract
- Modular polyketide synthases (PKSs) are poly-merases that employ alpha-carboxyacyl-CoAs as extender substrates. This enzyme family contains several catalytic modules, where each module is responsible for a single round of polyketide chain extension. Although PKS modules typically use malonyl-CoA or methylmalonyl-CoA for chain elongation, many other malonyl-CoA analogues are used to diversify polyketide structures in nature. Previously, we developed a method to alter an extension substrate of a given module by exchanging an acyltransferase (AT) domain while maintaining protein folding. Here, we report in vitro polyketide biosynthesis by 13 PKSs (the wild-type PKS and 12 AT-exchanged PKSs with unusual ATs) and 14 extender substrates. Our similar to 200 in vitro reactions resulted in 13 structurally different polyketides, including several polyketides that have not been reported. In some cases, AT-exchanged PKSs produced target polyketides by >100-fold compared to the wild-type PKS. These data also indicate that most unusual AT domains do not incorporate malonyl-CoA and methylmalonyl-CoA but incorporate various rare extender substrates that are equal to in size or slightly larger than natural substrates. We developed a computational workflow to predict the approximate AT substrate range based on active site volumes to support the selection of ATs. These results greatly enhance our understanding of rare AT domains and demonstrate the benefit of using the proposed PKS engineering strategy to produce novel chemicals in vitro.
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| 2. |
- Földváry Ličina, Veronika, et al.
(författare)
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Development of the ASHRAE Global Thermal Comfort Database II
- 2018
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Ingår i: Building and Environment. - : Elsevier BV. - 0360-1323. ; 142, s. 502-512
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Tidskriftsartikel (refereegranskat)abstract
- Recognizing the value of open-source research databases in advancing the art and science of HVAC, in 2014 the ASHRAE Global Thermal Comfort Database II project was launched under the leadership of University of California at Berkeley's Center for the Built Environment and The University of Sydney's Indoor Environmental Quality (IEQ) Laboratory. The exercise began with a systematic collection and harmonization of raw data from the last two decades of thermal comfort field studies around the world. The ASHRAE Global Thermal Comfort Database II (Comfort Database), now an online, open-source database, includes approximately 81,846 complete sets of objective indoor climatic observations with accompanying “right-here-right-now” subjective evaluations by the building occupants who were exposed to them. The database is intended to support diverse inquiries about thermal comfort in field settings. A simple web-based interface to the database enables filtering on multiple criteria, including building typology, occupancy type, subjects' demographic variables, subjective thermal comfort states, indoor thermal environmental criteria, calculated comfort indices, environmental control criteria and outdoor meteorological information. Furthermore, a web-based interactive thermal comfort visualization tool has been developed that allows end-users to quickly and interactively explore the data.
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| 3. |
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| 4. |
- Kapuscinski, Martin, et al.
(författare)
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Temporal Evolution of Superlattice Contraction and Defect-Induced Strain Anisotropy in Mesocrystals during Nanocube Self-Assembly
- 2020
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 14:5, s. 5337-5347
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Tidskriftsartikel (refereegranskat)abstract
- Understanding and controlling defect formation during the assembly of nanoparticles is crucial for fabrication of self-assembled nanostructured materials with predictable properties. Here, time-resolved small-angle X-ray scattering was used to probe the temporal evolution of strain and lattice contraction during evaporation-induced self-assembly of oleate-capped iron oxide nanocubes in a levitating drop. We show that the evolution of the strain and structure of the growing mesocrystals is related to the formation of defects as the solvent evaporated and the assembly process progressed. Superlattice contraction during the mesocrystal growth stage is responsible for the rapidly increasing isotropic strain and the introduction of point defects. The crystal strain, quantified by the Williamson-Hall analysis, became more anisotropic due to the formation of stress-relieving dislocations as the mesocrystal growth was approaching completion. Understanding the formation of the transformation of defects in mesocrystals and superlattices could assist in the development of optimized assembly processes of nanoparticles with multifunctional properties.
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| 5. |
- Liu, Yingxin, et al.
(författare)
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Assembly, Gelation, and Helicoidal Consolidation of Nanocellulose Dispersions
- 2019
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 35:10, s. 3600-3606
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Tidskriftsartikel (refereegranskat)abstract
- The ability to probe the assembly, gelation, and helicoidal consolidation of cellulose nanocrystal (CNC) dispersions at high concentrations can provide unique insight into the assembly and can assist optimized manufacturing of CNC-based photonic and structural materials. In this Feature Article, we review and discuss the concentration dependence of the structural features, characterized by the particle separation distance and the helical pitch, at CNC concentrations (c) that range from the isotropic state, over the biphasic range, to the fully liquid crystalline state. The structure evolution of CNC dispersions probed by time resolved small-angle X-ray scattering during evaporation-induced assembly highlighted the importance of gelation and consolidation at high concentrations. We briefly discuss how the homogeneity of helicoidal nanostructures in dry CNC films can be improved and present an outlook for future work.
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| 6. |
- Liu, Yingxin, et al.
(författare)
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Assembly of cellulose nanocrystals in a levitating drop probed by time-resolved small angle X-ray scattering
- 2018
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 10:38, s. 18113-18118
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Tidskriftsartikel (refereegranskat)abstract
- Assembly of bio-based nano-sized particles into complex architectures and morphologies is an area of fundamental interest and technical importance. We have investigated the assembly of sulfonated cellulose nanocrystals (CNC) dispersed in a shrinking levitating aqueous drop using time-resolved small angle X-ray scattering (SAXS). Analysis of the scaling of the particle separation distance (d) with particle concentration (c) was used to follow the transition of CNC dispersions from an isotropic state at 1-2 vol% to a compressed nematic state at particle concentrations above 30 vol%. Comparison with SAXS measurements on CNC dispersions at near equilibrium conditions shows that evaporation-induced assembly of CNC in large levitating drops is comparable to bulk systems. Colloidal states with d vs. c scalings intermediate between isotropic dispersions and unidirectional compression of the nematic structure could be related to the biphasic region and gelation of CNC. Nanoscale structural information of CNC assembly up to very high particle concentrations can help to fabricate nanocellulose-based materials by evaporative methods.
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| 7. |
- Liu, Yingxin, 1988-
(författare)
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Nanocellulose-based materials: from colloidal assembly to functional films
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The assembly of nature-based nanomaterials into complex architectures is both a design principle of biological composites, e.g., wood and nacre with outstanding properties and a promising route for developing functional macroscopic materials. This thesis aims to investigate and understand the colloidal and self-assembly behaviour of nanocellulose in aqueous dispersions. Moreover, composite films of nanocellulose and nanoclay/lignin with diverse functionalities, e.g., mechanical and optical properties, are fabricated by tailoring the electrostatic interactions of these building blocks.The evaporation induced assembly of sulfonated cellulose nanocrystal (CNC) has been followed in either an aqueous droplet on substrates or a levitated droplet by real-time small angle X-ray scattering. The evolution of structural features, e.g., an isotropic phase, biphasic phase, fully liquid crystalline and contracted helical structures of drying CNC dispersions were related to the power-law scaling of the particle separation distance (d) with concentrations (c, from 1 vol% to 38 vol%). Below 2 vol%, CNC dispersions consolidated isotropically with a scaling of d ∝ c-1/3, while the fully cholesteric liquid crystalline phase showed a unidimensional contraction of the nematic structure (d ∝ c-1) with increasing concentrations. Competition between gelation and the ordered assembly of CNC was quantitatively evaluated in nanoscale for the first time, which was reflected by a scaling of d ∝ c-2/3.The rheology of composite dispersions of carboxylated cellulose nanofibril (CNF) and nanoclay was investigated, which was influenced by the surface charge of CNF, the morphology of nanoclays and interactions between CNF and clay particles. Optically transparent films of synthetic aminoclay (50 wt%) and CNF were fabricated, of which tensile strength and strain to failure (205 MPa and 7.5%) were significantly higher than those of nacre and other nacre-mimicking nanocellulose-based materials, e.g., montmorillonite-CNF films, due to the formation of ionic bonding between the cationic clay and anionic CNF.Lignin nanoparticles were testified to enhance the colloidal stability and dispersity of carboxylated CNF in dispersions, and showed a remarkable strengthening and stiffening effect on the matrix of CNF. The mechanical properties of lignin-CNF films were superior to previously reported polymer/nanoparticle-CNF composites, such as polyvinyl alcohol-CNF films and even reduced graphene oxide-CNF films.
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| 8. |
- Liu, Yingxin, et al.
(författare)
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Nanoscale Assembly of Cellulose Nanocrystals during Drying and Redispersion
- 2018
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Ingår i: ACS Macro Letters. - : American Chemical Society (ACS). - 2161-1653. ; 7:2, s. 172-177
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Tidskriftsartikel (refereegranskat)abstract
- We have followed the structural evolution during evaporation-induced self-assembly of sulfonated cellulose nanocrystal (CNC) in the presence of H+ and Li+ counterions by small-angle X-ray scattering. Drying of CNC-H dispersions results in ordered films that could not be readily redispersed, while the CNC-Li films were disordered and prone to reswelling and redispersion. The scaling of the separation distance (d) between CNC particles and the particle concentration (c) shows that the CNC-H dispersions display a unidimensional contraction of the nematic structure (d alpha c(-1)) during drying, while the CNC-Li dispersions consolidate isotropically (d alpha c(-1/3)), which is characteristic for hydrogels with no preferential orientation. Temporal evolution of the structure factor and complementary dynamic light-scattering measurements show that CNC-Li is more aggregated than CNC-H during evaporation-induced assembly. Insights on the structural evolution during CNC assembly and redispersion can promote development of novel and optimized processing routes of nanocellulose-based materials.
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| 9. |
- Liu, Yingxin, et al.
(författare)
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Steady-shear and viscoelastic properties of cellulose nanofibril-nanoclay dispersions
- 2017
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Ingår i: Cellulose. - : Springer Science and Business Media LLC. - 0969-0239 .- 1572-882X. ; 24:4, s. 1815-1824
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Tidskriftsartikel (refereegranskat)abstract
- We have investigated the steady-shear and viscoelastic properties of composite dispersions of cellulose nanofibrils (CNFs) with medium or high charge density and two different nanoclays, viz. rodlike sepiolite or plate-like bentonite. Aqueous dispersions of CNFs with medium charge density displayed significantly lower steady-state viscosity and storage modulus but higher gelation threshold compared with CNFs with high charge density. Dynamic light scattering (DLS) results showed that the apparent hydrodynamic radius of bentonite particles increased when CNFs were added, implying that CNFs adsorbed onto the amphoteric edges of the plate-like bentonite particles. The sepiolite network in CNF-sepiolite dispersions was relatively unaffected by addition of small amounts of CNFs, and DLS showed that the hydrodynamic radius of sepiolite did not change when CNFs were added. Addition of CNFs at concentrations above the gelation threshold resulted in drastic decrease of the steady-shear viscosity of the sepiolite dispersion, suggesting that the sepiolite network disintegrates and the rod-like clay particles are aligned also at low shear rate. The relative change in the rheological properties of the clay-based dispersions was always greater on addition of CNFs with high compared with medium charge density. This study provides insight into how the rheology of CNF-nanoclay dispersions depends on both the nanoclay morphology and the interactions between the nanoclay and nanocellulose particles, being of relevance to processing of nanocellulose-clay composites.
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| 10. |
- Liu, Yingxin
(författare)
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Strong and Flexible Nanocomposites of Carboxylated Cellulose Nanofibril Dispersed by Industrial Lignin
- 2018
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 6:4, s. 5524-5532
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrated that industrial lignin can be facilely processed with carboxylated cellulose nanofibril (CNF) to obtain strong, flexible, and transparent nanocomposites via film casting of dispersions. The tensile strength and strain to failure of lignin–CNF nanocomposites (245 MPa and 15%, respectively at 7.7 wt % of lignin) are superior to previously reported polymer/nanoparticle–CNF composites with polymer contents below 50 wt %, such as poly(vinyl alcohol)–CNF films and even reduced graphene oxide–CNF films. The excellent mechanical properties of lignin–CNF nanocomposite films are related to the lignin-enhanced colloidal stability and dispersity of CNF in aqueous dispersions supported by measurements of rheology and dynamic light scattering, which accordingly suppresses the excess fibril aggregates during film formation. Moreover, lignin in the nanocomposites benefits an efficient functionalization of gold/iron oxide nanoparticles on the surface of nanocomposites. This study illustrates the great potential of industrial lignin in developing nanocellulose-based materials with advanced properties and functionalities.
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