| 1. |
- Hedin, Niklas, 1969-
(författare)
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NMR studies of complex fluids and solids formed by surfactants
- 2000
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- NMR methods have been designed and employed in studying ofcomplex liquids and solids formed by surfactants. PGSE NMRexperiments are easily biased by convection; this artifact canbe avoided by changing the sample holder and by usingconvection-compensated pulse sequences. The temperaturedistribution within samples was controlled using thetemperature dependent order parameter for CBr2H2dissolved in a thermotropic nematic solvent.Electronic ringing that often spoils accurate NMR experimentsfor broad lines was removed by the using composite pulses andquadrupole echo sequences with appropriate phase cycles.Field-dependent81Br and35Cl NMR relaxation studies in micellar solutions ofC16TAX surfactants showed that the structure ordynamics of the hydration shell is more influenced by thesurfactant cation for bromide than for chloride, in agreementwith their position in the Hoffmeister series. The presence ofa small but significant frequency-dependent relaxation showedthat the lateral self diffusion of the anions may be reduced ascompared to its bulk value in diluted solutions but only with afactor of 1.0 - 2.5. The ions are clearly not "bound" to thesurface. A field-dependent2H NMR relaxation study on the CTABr-α-d2and benzene-d6showed an initial one-dimensional micellargrowth followed by the appearance of microemulsion droplets onaddition of benzene. The local mobility of the benzene wasreduced when solubilized in small amounts, consistent with aninitial average location of benzene at the micellar interface.The surfactant diffusion coefficients fromconvection-compensated PGSE NMR experiments in the C12E8-D2O system showed monotonous growth of the micellesupon increasing temperature. Emulsion droplets in the C12E5-decane-D2O system where shown to coarsen according to theOstwald ripening theory after being brought out of equilibriumby a temperature drop. X-ray scattering and2H NMR line-shape and relaxation experimentssuggested that complex solids formed by a partly-sulfatedpolysaccharide and CnTAB exhibit regular ordering at both microscopicand mesoscopic length scales.Keywords: CTAB, CTAC, C12E8, C12E5, decane, benzene, CBr2H2, polysaccharide, micelle, microemulsion, emulsion,Ostwald ripening, NMR,81Br,35Cl,2H, field- dependent spin relaxation, PGSE, selfdiffusion, convection, ringing, thermometer, generalized Blochequations, EXORCYCLE, quadrupole echo, SAXS, WAXS, cryo-TEM.
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| 2. |
- Huang, Qi, et al.
(författare)
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Effective photocatalytic sterilization based on composites of Ag/InVO4/BiOBr : Factors, mechanism and application
- 2023
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Ingår i: Separation and Purification Technology. - 1383-5866 .- 1873-3794. ; 327
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Tidskriftsartikel (refereegranskat)abstract
- We hypothesized that photocatalysts with a low band gap could be useful in the sterilization of ceramic tiles in the natural environments of toilets using natural light in those settings. Certain photocatalysts can produce reactive oxygen species (ROS) under light illumination, which in turn are bactericidal. The properties of the BiOBr-containing photocatalysts were tuned by creating junctions and heterostructures with Ag and InVO4 and studied with respect to their bactericidal effect in dispersion. The bactericidal mechanism was studied through experiments in which active species were captured and via electron paramagnetic resonance (EPR) spectroscopy. At an optimal dosage of 0.5 g/L, the Ag/InVO4/BiOBr composite had a sterilization efficacy of 99.9999 % in 30 min under visible light illumination of 1000 W. It retained a sterilization efficacy of 99.999 % after four cycles. Anions such as Cl−, SO42−, and NO3− were shown to have no negative impact on sterilization efficacy. It was shown that the holes in the composite photocatalyst and hydroxyl radicals (·OH) were mechanistically critical for the sterilization. The photocatalysts were also studied in the field in the natural environment of a restroom, where they were loaded on ceramic tiles. Samples were collected from the surface of the ceramic tiles and analyzed for bacterial cultures and microbial diversity. The results were compared in the scope of the sterilization ability of various agents at the microbial level. The ceramic tiles loaded with Ag/InVO4/BiOBr showed the least amount of bacteria on their surfaces, and the microbial community richness was also the lowest.
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| 3. |
- Iqbal, Muhammad Naeem, et al.
(författare)
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Activity and Stability of Nanoconfined Alpha-Amylase in Mesoporous Silica
- 2023
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Ingår i: ACS Materials Science Au. - 2694-2461. ; 3:6, s. 659-668
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Tidskriftsartikel (refereegranskat)abstract
- Mesoporous silica particles (MSPs) have been studied for their potential therapeutic uses in controlling obesity and diabetes. Previous studies have shown that the level of digestion of starch by α-amylase is considerably reduced in the presence of MSPs, and it has been shown to be caused by the adsorption of α-amylase by MSPs. In this study, we tested a hypothesis of enzymatic deactivation and measured the activity of α-amylase together with MSPs (SBA-15) using comparably small CNP-G3 (2-chloro-4-nitrophenyl alpha-d-maltotrioside) as a substrate. We showed that pore-incorporated α-amylase was active and displayed higher activity and stability compared to amylase in solution (the control). We attribute this to physical effects: the coadsorption of CNP-G3 on the MSPs and the relatively snug fit of the amylase in the pores. Biosorption in this article refers to the process of removal or adsorption of α-amylase from its solution phase into the same solution dispersed in, or adsorbed on, the MSPs. Large quantities of α-amylase were biosorbed (about 21% w/w) on the MSPs, and high values of the maximum reaction rate (Vmax) and the Michaelis–Menten constant (KM) were observed for the enzyme kinetics. These findings show that the reduced enzymatic activity for α-amylase on MSP observed here and in earlier studies was related to the large probe (starch) being too large to adsorb in the pores, and potato starch has indeed a hydrodynamic diameter much larger than the pore sizes of MSPs. Further insights into the interactions and environments of the α-amylase inside the MSPs were provided by 1H fast magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and 13C/15N dynamic nuclear polarization MAS NMR experiments. It could be concluded that the overall fold and solvation of the α-amylase inside the MSPs were nearly identical to those in solution.
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| 4. |
- Liu, Rongying, 1983-, et al.
(författare)
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Chirality Transfer of Glycopeptide across Scales Defined by the Continuity of Hydrogen Bonds
- 2024
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Ingår i: ACS Nano. - 1936-0851 .- 1936-086X. ; 18:22, s. 14367-14376
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Tidskriftsartikel (refereegranskat)abstract
- In nature, chirality transfer refines biomolecules across all size scales, bestowing them with a myriad of sophisticated functions. Despite recent advances in replicating chirality transfer with biotic or abiotic building blocks, a molecular understanding of the underlying mechanism of chirality transfer remains a daunting challenge. In this paper, the coassembly of two types of glycopeptide molecules differing in capability of forming intermolecular hydrogen bonds enabled the involvement of discontinuous hydrogen bond, which allowed for a nanoscale chirality transfer from glycopeptide molecules to chiral micelles, yet inhibited the micrometer scale chirality transfer toward helix formation, leading to an achiral transfer from chiral micelles to planar monolayer. Upon stacking the monolayer into a bilayer, the nonsuperimposable front and back faces of the chiral micelles involved in the monolayer ribbons lead to the opposite rotation of two layers toward increasing the continuity of H-bonds. The resultant continuity triggered the symmetry breaking of stacked bilayers and thus reactivated the micrometer-scale chirality transfer toward the final helix. This work delineates a promising step toward a better understanding and replicating the naturally occurring chirality transfer events and will be instructive to future chiral material design.
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| 5. |
- Maziarka, Przemyslaw, et al.
(författare)
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Part 1─Impact of Pyrolysis Temperature and Wood Particle Length on Vapor Cracking and Char Porous Texture in Relation to the Tailoring of Char Properties
- 2024
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Ingår i: Energy & Fuels. - 0887-0624 .- 1520-5029. ; 38:11, s. 9751-9771
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Tidskriftsartikel (refereegranskat)abstract
- Pore size distribution is a key parameter in the performance of biobased pyrolytic char in novel applications. In industrial-scale production, the size of feedstock particles typically exceeds a few millimeters. For such particle sizes, it is a challenge to tailor the final properties of the char based only on the process conditions (experimental and modeling-wise). Pyrolysis studies of single particles larger than a few millimeters provide data sets useful for modeling and optimization of the process. Part 1 of this research focused on the pyrolysis of single particles of beech wood, secondary cracking, and its effect on the char porous texture. It contains a quantitative assessment of the effects of five conversion temperatures (from 300 to 840 °C) and two particle dimensions (Ø8 × 10 mm and Ø8 × 16 mm) on the composition of the pyrolysis vapors and pore morphology of the char. Results from real-time temperature and mass changes are presented along with release profiles of 15 vapor constituents measured by infrared spectroscopy. Furthermore, characterization of the collected bio-oil (using GC-MS/FID) and the textural hierarchical structured char (through N2 and CO2 adsorption, Hg porosimetry, and scanning electron microscopy (SEM)) was performed. Cracking of vapors above 500 °C was compound-specific. The polyaromatic hydrocarbons (PAHs) yield, between 680 and 840 °C, increased 5 times for 10 mm particles and 9 times for 16 mm ones. Besides temperature, PAH yield was suspected to correlate with particle length and PAHs/soot deposition in the micropores. Results showed that the macropores accounted for over 80% of the total pore volume, regardless of the temperature and particle length. Increasing the particle length by 60% caused a reduction in the specific surface area (ca. 15% at 840 °C) of the resulting char, mainly due to a reduction in microporosity. Based on the findings, the production conditions for a specific char application are suggested. The obtained data will be used in Part 2 of this research, devoted to subsequent CFD modeling of the process.
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| 6. |
- Saadattalab, Vahid, et al.
(författare)
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Adsorption of volatile organic compounds on activated carbon with included iron phosphate
- 2023
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Ingår i: Carbon trends. - : Elsevier BV. - 2667-0569. ; 11
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Tidskriftsartikel (refereegranskat)abstract
- Volatile organic compounds (VOCs) are often hazardous and need commonly to be removed from gas mixtures. Capture on activated carbon (AC) is one approach to achieving this. We hypothesized that the smallest pores on ACs and the inclusion of inorganic phosphates could enhance the low gas pressure uptake of two typical VOCs (acetone and isopropanol). To test this hypothesis, ACs were prepared by chemical activation of hydrochars with H3PO4 or a mixture of FeCl3 and H3PO4. The hydrochars had been prepared by hydrothermal carbonization of glucose. The ACs were characterized by XRD, IR, TGA, and the adsorption of N2, CO2, H2O, acetone, and isopropanol. The results showed that the ACs had comparably high adsorption of acetone and isopropanol at low vapor pressures. The low-pressure uptake (at 0.03 kPa) of isopropanol and acetone had values of up to 3.4 mmol/g and 2.2 mmol/g, respectively. This suggests that ACs containing iron phosphate could be of relevance for adsorption driven removal of VOC. It was also observed that the external surface area of the ACs containing iron phosphates increased upon secondary heat treatment in N2.
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| 7. |
- Shu, Chenhua, et al.
(författare)
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Desulfurization of diesel via joint adsorption and extraction using a porous liquid derived from ZIF-8 and a phosphonium-type ionic liquid
- 2023
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Ingår i: Reaction Chemistry & Engineering. - 2058-9883. ; :12, s. 3124-3132
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Tidskriftsartikel (refereegranskat)abstract
- A type-III porous liquid based on zeolitic imidazolate framework-8 (ZIF-8) and an ionic liquid trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([THTDP][BTI]) was synthesized and used for the desulfurization of model diesel. The desulfurization effect by ZIF-8/[THTDP][BTI] combined both the adsorptive desulfurization by ZIF-8 and the extraction desulfurization by [THTDP][BTI]. The removal of the three chosen aromatic organic sulfides by the ZIF-8/[THTDP][BTI] porous liquid followed the order of dibenzothiophene (73.1%) > benzothiophene (70.0%) > thiophene (61.5%). It was further found that deep desulfurization could be realized by ZIF-8/[THTDP][BTI] through triple desulfurization cycles and ZIF-8/[THTDP][BTI] can be regenerated readily. The desulfurization mechanism was explored further in detail by conformation search and density functional theory calculations. Calculations supported that the large molecular volume of [THTDP][BTI] excluded itself from the cavities of ZIF-8, making the pores of ZIF-8 in the porous liquid unoccupied and accessible by other guest species, here the studied organic sulfides. These calculations indicate that the van der Waals interactions were the main interactions between ZIF-8/[THTDP][BTI] and specifically benzothiophene. This work supports that the porous liquid ZIF-8/[THTDP][BTI] could potentially be used for desulfurization of diesel in industry.
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| 8. |
- Szego, Anthony E., et al.
(författare)
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Precapture of CO2 and Hydrogenation into Methanol on Heterogenized Ruthenium and Amine-Rich Catalytic Systems
- 2023
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Ingår i: ChemistryOpen. - 2191-1363. ; 12:6
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Tidskriftsartikel (refereegranskat)abstract
- A heterogenized alternative to the homogeneous precapture of CO2 with amines and subsequent hydrogenation to MeOH was developed using aminated silica and a Ru-MACHOTM catalyst. Commercial mesoporous silica was modified with three different amino-silane monomers and used as support for the Ru catalyst. These composites were studied by TEM and solid-state NMR spectroscopy before and after the catalytic reaction. These catalytic reactions were conducted at 155 degrees C at a H-2 and CO2 pressures of 75 and 2 bar, respectively, with the heterogeneous system (gas-solid) being probed with gas-phase infrared spectroscopy used to quantify the resulting products. High turnover number (TON) values were observed for the samples aminated with secondary amines.
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| 9. |
- Zhou, Xiaofeng, 1989-, et al.
(författare)
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Enhanced Generation of Reactive Oxygen Species via Piezoelectrics based on p–n Heterojunctions with Built-In Electric Field
- 2024
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Ingår i: ACS Applied Materials and Interfaces. - 1944-8244 .- 1944-8252. ; 16:16, s. 20472-20484
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Tidskriftsartikel (refereegranskat)abstract
- Tuning the charge transfer processes through a built-in electric field is an effective way to accelerate the dynamics of electro- and photocatalytic reactions. However, the coupling of the built-in electric field of p–n heterojunctions and the microstrain-induced polarization on the impact of piezocatalysis has not been fully explored. Herein, we demonstrate the role of the built-in electric field of p-type BiOI/n-type BiVO4 heterojunctions in enhancing their piezocatalytic behaviors. The highly crystalline p–n heterojunction is synthesized by using a coprecipitation method under ambient aqueous conditions. Under ultrasonic irradiation in water exposed to air, the p–n heterojunctions exhibit significantly higher production rates of reactive species (·OH, ·O2–, and 1O2) as compared to isolated BiVO4 and BiOI. Also, the piezocatalytic rate of H2O2 production with the BiOI/BiVO4 heterojunction reaches 480 μmol g–1 h–1, which is 1.6- and 12-fold higher than those of BiVO4 and BiOI, respectively. Furthermore, the p–n heterojunction maintains a highly stable H2O2 production rate under ultrasonic irradiation for up to 5 h. The results from the experiments and equation-driven simulations of the strain and piezoelectric potential distributions indicate that the piezocatalytic reactivity of the p–n heterojunction resulted from the polarization intensity induced by periodic ultrasound, which is enhanced by the built-in electric field of the p–n heterojunctions. This study provides new insights into the design of piezocatalysts and opens up new prospects for applications in medicine, environmental remediation, and sonochemical sensors.
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