| 45261. |
- Hao, Xian, et al.
(författare)
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Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex
- 2013
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723 .- 2041-1723. ; 4
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Tidskriftsartikel (refereegranskat)abstract
- Coordination chemistry has been a consistently active branch of chemistry since Werner’s seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal–ligand interactions at the single-molecule level remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold substrate surfaces and gold-coated atomic force microscopy tips. The coordination and bond breaking between terpyridine and osmium are followed in situ by electrochemically controlled atomic force microscopy at the single-molecule level. The redox state of the central metal atom is found to have a significant impact on the metal–ligand interactions. The present approach represents a major advancement in unravelling the nature of metal–ligand interactions and could have broad implications in coordination chemistry.
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| 45262. |
- Hapeta, Piotr, et al.
(författare)
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Nitrogen as the major factor influencing gene expression in Yarrowia lipolytica
- 2020
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Ingår i: Biotechnology Reports. - : Elsevier BV. - 2215-017X. ; 27
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Tidskriftsartikel (refereegranskat)abstract
- Yarrowia lipolytica is an important industrial microorganism used for the production of oleochemicals. The design of effective biotechnological processes with this cell factory requires an in-depth knowledge of its metabolism. Here we present a transcriptomic study of Y. lipolytica grown in the presence of glycerol and glucose, and mixture of both at different carbon to nitrogen ratios. It emerged that the transcriptomic landscape of Y. lipolytica is more sensitive to the nitrogen availability than to the utilized carbon source, as evidenced by more genes being differentially expressed in lower carbon to nitrogen ratio. Specifically, expression of hexokinase (HXK1) is significantly susceptible to changes in nitrogen concentrations. High HXK1 expression in low nitrogen seems to impact other genes which are implicated in tricarboxylic acid cycle and erythritol biosynthesis. We further show that expression of HXK1 and two genes belonging to the sugar porter family might be controlled by GATA-like zinc-finger proteins.
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| 45263. |
- Happel, Markus, 1985, et al.
(författare)
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SOx storage and release kinetics for ceria-supported Pt
- 2009
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Ingår i: Applied Catalysis B: Environmental. - : Elsevier BV. - 0926-3373 .- 1873-3883. ; 91:3-4, s. 679-682
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Tidskriftsartikel (refereegranskat)abstract
- The SOx storage and release kinetics on CeO2 have been studied by lean SOx adsorption and temperature programmed desorption for different pairwise configurations of individual monolith samples, i.e., Pt/CeO2 + SiO2, Pt/SiO2 + CeO2, CeO2 + Pt/SiO2 and CeO2 + SiO2. In the case of sole ceria, SOx adsorption proceeds both via SO2 and SO3 adsorption although the latter channel is kinetically favored. Hence, the rate of SO2 oxidation is crucial for the overall SOx storage kinetics. It is also found that physical contact between Pt and ceria is important for the storage process. This is attributed to efficient transport routes for SOx (surface diffusion and spill-over processes) and/or specific adsorption sites at the platinum–ceria interface. The main route for SOx release is found to be thermal decomposition where the effect of platinum is minor, although an indirect effect cannot be ruled out. Different mechanistic scenarios for SOx adsorption are discussed, which may serve as a guide for future experiments.
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| 45264. |
- Haq, I., et al.
(författare)
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Interaction of Delta- and Lambda-[Ru(phen)2DPPZ]2+ with DNA: A Calorimetric and Equilibrium Binding Study
- 1995
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 117:17, s. 4788-4796
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Tidskriftsartikel (refereegranskat)abstract
- Fluorescence and absorption spectroscopy, isothermal titration calorimetry, and viscosity measurements have been used to characterize the interaction of Delta and Lambda [Ru(phen)(2)DPPZ](2+) with calf thymus DNA. The method of continuous variations revealed two distinct binding stoichiometries for both Delta- and Lambda-DPPZ, corresponding to 0.7 and 3 mol of base pair/mol of ligand. Binding isotherms were obtained for the two enantiomers, both of which show strong binding to DNA, with K = 3.2 x 10(6) M(-1) bp and 1.7 x 10(6) M(-1) bp for the Delta and Lambda isomers, respectively, at 25 degrees C in solutions containing 50 mM NaCl. Titration calorimetry gave Delta H values of +0.3 kcal mol(-1) for Delta-DPPZ and +2.9 kcal mol(-1) for Lambda-DPPZ for their interaction with DNA. These small positive enthalpies, which were confirmed using thermal difference spectroscopy, indicated that the binding of these compounds to DNA is entropically driven. An enthalpy of +2.5 kcal mol(-1) was obtained for the binding of the parent compound, tris(phenanthroline)-Ru(II), to DNA. Titration of all three compounds into buffer gave a nonnegligible heat of dilution. The salt dependence of the binding constant was examined for both isomers. The slope SK = (delta logK/delta log[Na+]) was found to be 1.9 and 2.1 for the Delta and Lambda isomers, respectively. By using polyelectrolyte theory to interpret the observed salt dependence of the equilibrium constant, it can be shown that there is a significant nonelectrostatic contribution to the binding constant. Relative viscosity experiments showed that both Delta- and Lambda-DPPZ increase the length of rod-like DNA, in a manner consistent with binding by classical intercalation. Fluorescence energy transfer experiments provided additional evidence for the intercalation of Delta- and Lambda-[Ru(phen)(2)DPPZ](2+) into DNA.
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| 45265. |
- Haq, S., et al.
(författare)
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Clean Coupling of Unfunctionalized Porphyrins at Surfaces To Give Highly Oriented Organometallic Oligomers
- 2011
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 133:31, s. 12031-12039
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Tidskriftsartikel (refereegranskat)abstract
- The direct coupling of complex, functional organic molecules at a surface is one of the outstanding challenges in the road map to future molecular devices. Equally demanding is to meet this challenge without recourse to additional functionalization of the molecular building blocks and via clean surface reactions that leave no surface contamination. Here, we demonstrate the directional coupling of unfunctionalized porphyrin molecules-large aromatic multifunctional building blocks-on a single crystal copper surface, which generates highly oriented one-dimensional organometallic macromolecular nanostructures (wires) in a reaction which generates gaseous hydrogen as the only byproduct. In situ scanning tunneling microscopy and temperature programmed desorption, supported by theoretical modeling, reveal that the process is driven by C-H bond scission and the incorporation of copper atoms in between the organic components to form a very stable organocopper oligomer comprising organometallic edge-to-edge porphyrin-Cu-porphyrin connections on the surface that are unprecedented in solution chemistry. The hydrogen generated during the reaction leaves the surface and, therefore, produces no surface contamination. A remarkable feature of the wires is their stability at high temperatures (up to 670 K) and their preference for 1D growth along a prescribed crystallographic direction of the surface. The on-surface formation of directional organometallic wires that link highly functional porphyrin cores via direct C-Cu-C bonds in a single-step synthesis is a new development in surface-based molecular systems and provides a versatile approach to create functional organic nanostructures at surfaces.
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| 45266. |
- Haque, Mohammad Mazharul, 1984
(författare)
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Electrolyte evaluation and engineering for the performance enhancement of electrochemical capacitors
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- As a consequence of a fast-paced technological evolution along with the acknowledgment of utilizing clean and renewable energy resources over fossil fuels, the importance of energy storage devices is widely recognized. The electrochemical capacitor (EC), commonly known as a supercapacitor or ultracapacitor, is an energy storage device that is already being used in portable consumer electronics, electrification of transportation, and grid-level applications. High power density and long cycle life are the two most prominent properties of ECs, thanks to the electrostatic nature of their charge storage mechanism. These properties are well utilized in a system where ECs are used as a backup power-boosting device to rechargeable batteries. By providing the peak power required, they eventually prolong the battery lifetime. However, the relatively low energy density of ECs compared to rechargeable batteries limits their application as a standalone device. In addition, low operating voltage, adverse self-discharge rate, severe leakage current, elevated temperature incompatibility are some of the crucial issues that are preventing the widespread application of ECs. Besides a general discussion about ECs, the main objective of this thesis is to identify and address the above-mentioned critical challenges, and to propose and demonstrate corresponding solutions. Firstly, it is revealed that utilizing a redox-active KBr electrolyte can enhance both operating voltage and capacitance, and hence increases energy density without sacrificing power density or cycle life. Secondly, an evaluation of elevated temperature influence on the capacitive performance of ECs containing ionic liquid (IL) electrolyte demonstrates a high working temperature beyond 120 °C. Thirdly, a systematic investigation of ECs containing IL at elevated temperatures shows a significant increase of the self-discharge rate with temperature and pinpoints the underlying mechanisms; at lower initial voltages the self-discharge rate is dominated by diffusion of electrolyte ions rather than charge redistribution. Fourthly, the addition of a small amount of liquid crystals (LC) in neutral electrolyte shows a reduction of self-discharge and leakage current due to slower diffusion of ions in the device, which is proposed to originate from the anisotropic properties of LC. Finally, by utilizing the thermocapacitive effect, a thermal charging of ECs containing IL is demonstrated, where a high voltage of more than 900 mV could be recovered when two devices in series are exposed to a 60 °C temperature environment.
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| 45267. |
- Haque, Mohammad Mazharul, 1984, et al.
(författare)
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Exploiting low-grade waste heat to produce electricity through supercapacitor containing carbon electrodes and ionic liquid electrolytes
- 2022
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686. ; 403
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Tidskriftsartikel (refereegranskat)abstract
- Low-grade thermal energy harvesting presents great challenges to traditional thermoelectric systems based on the Seebeck effect, the thermogalvanic effect, and the Soret effect due to fixed temperature gradient and low voltage output. In this study, we report an ionic thermoelectric system, essentially a supercapacitor (SC) containing an ionic liquid (IL) electrolyte and activated carbon electrodes, which works on the thermocapacitive effect and does not require any fixed temperature gradient, rather it works in a homogeneously changing temperature. A systematic investigation is carried out on SCs containing two different ILs, 1-Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl), EMIm TFSI, and 1-Ethyl-3-methylimidazolium acetate, EMIm OAc. A high voltage output of 176 mV is achieved for EMIm TFSI containing SC by exposing just to 60 °C environment. Moreover, a large voltage of 502 mV is recovered from the SC upon subjecting to heat after one electrical charge/discharge cycle. A system containing two SCs in series demonstrates a significant voltage of 947 mV. The observed performance difference between the two ILs is rationalized in terms of the extent of asymmetry in the interfaces of the electrical double layer that essentially originates from different diffusivity of individual ions. The mechanism can be applied to a plethora of ILs to exploit low-grade heat to store electricity without a fixed temperature gradient, opening up the possibility to merge different scientific communities and enrich this rising research field.
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| 45268. |
- Haque, Mohammad Mazharul, 1984, et al.
(författare)
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Identification of self-discharge mechanisms of ionic liquid electrolyte based supercapacitor under high-temperature operation
- 2021
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Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 485
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Tidskriftsartikel (refereegranskat)abstract
- Ionic liquids (ILs) are promising electrolytes for supercapacitors (SCs) aimed for high-temperature applications, where increased ionic conductivity results in superior capacitive performance compared to room temperature (RT) performance. However, an increased temperature also accelerates the self-discharge rate that adversely affects energy retention and restricts the usage of SCs in standalone applications. In this study, a detailed electrochemical investigation on the self-discharge behaviour of carbon-based SCs containing an IL, 1-Ethyl-3-methylimidazolium acetate (EMIM Ac), has been carried out in the temperature range RT - 60 °C, and the underlying self-discharge mechanisms are identified. The results reveal that at a high voltage of 1.5 V, the self-discharge is characterized by a combination of charge redistribution and diffusion at both RT and 60 °C. At 60 °C, the diffusion-controlled mechanism dominates at lower voltages over the charge redistribution effect, while at RT both mechanisms contribute to a similar extent. The observed difference in the self-discharge mechanism between RT and 60 °C is explained in terms of a decreased RC time constant (τRC) at elevated temperature, and the same conclusions are potentially applicable to other IL-containing SCs as well.
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| 45269. |
- Haque, Mohammad Mazharul, 1984, et al.
(författare)
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Ionic liquid electrolyte for supercapacitor with high temperature compatibility
- 2017
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Ingår i: Journal of Physics: Conference Series. - : IOP Publishing. - 1742-6588 .- 1742-6596. ; 922:1
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Konferensbidrag (refereegranskat)abstract
- This work describes the electrochemical investigation of two ionic liquids (ILs), 1-ethyl-3-methylimidazolium acetate (EMIM Ac) and 1-butyl-3-methylimidazolium chloride (BMIM Cl), as electrolytes in supercapacitors (SC). A comprehensive study on high temperature (HT) endurance that is required for system integration in microelectronics has also been carried out. It has been found that EMIM Ac containing SC performs better than a BMIM Cl containing SC, and HT treatment improves the capacitive performance.
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| 45270. |
- Haque, Mohammad Mazharul, 1984, et al.
(författare)
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Self-discharge and leakage current mitigation of neutral aqueous-based supercapacitor by means of liquid crystal additive
- 2020
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Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 453
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Tidskriftsartikel (refereegranskat)abstract
- Self-discharge is being recognized as one of the main obstacles to implementing the supercapacitor (SC) in standalone self-powered systems. Strategies for addressing this issue include the modification of electrodes, electrolytes, separators, and diverse device configurations. However, an improved self-discharge behavior is often achieved with a large compromise on other prominent figures of merit such as capacitance, energy density, or cycle life of the device. In this work, a thorough comparative electrochemical investigation of SCs containing a neutral aqueous electrolyte, 1 M Li2SO4, and with a liquid crystal (LC) additive, 2% 4-n-pentyl-4′-cyanobiphenyl (5CB) in 1 M Li2SO4, has been carried out at different states of charge. The results demonstrate that the device containing the LC additive 5CB exhibits a reduced self-discharge and leakage current without compromising the capacitive performance at different nominal voltages compared to the behavior of the device without 5CB. We suggest an explanation of the difference of the self-discharge behavior between the devices through tunability of the effective conductivity of the electrolyte composite upon applied voltages. As a result, in an open circuit condition, the device containing LC shows a slower diffusion of ions that facilitates a decreased self-discharge and leakage current.
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