1. |
- Geppert, W.D., et al.
(author)
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Dissociative recombination of protonated methanol
- 2006
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In: Faraday discussions. - Cambridge : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 133, s. 177-190
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Journal article (peer-reviewed)abstract
- The branching ratios of the different reaction pathways and the overall rate coefficients of the dissociative recombination reactions of CH3OH2+ and CD3OD2+ have been measured at the CRYRING storage ring located in Stockholm, Sweden. Analysis of the data yielded the result that formation of methanol or deuterated methanol accounted for only 3 and 6% of the total rate in CH3OH2+ and CD3OD2+, respectively. Dissociative recombination of both isotopomeres mainly involves fragmentation of the C - O bond, the major process being the three-body break-up forming CH3, OH and H (CD3, OD and D). The overall cross sections are best fitted by sigma = 1.2 +/- 0.1 x 10(-15) E-1.15 +/- 0.02 cm(2) and sigma = 9.6 +/- 0.9 x 10(-16) E-1.20 +/- 0.02 cm(2) for CH3OH2+ and CD3OD2+, respectively. From these values thermal reaction rate coefficients of k(T) = 8.9 +/- 0.9 x 10(-7) (T/300) (- 0.59 +/- 0.02) cm(3) s(-1) (CH3OH2+) and k( T) = 9.1 +/- 0.9 x 10(-7) (T/ 300) (- 0.63 +/- 0.02) cm(3) s(-1)(CD3OD2+) can be calculated. A non-negligible formation of interstellar methanol by the previously proposed mechanism via radiative association of CH3+ and H2O and subsequent dissociative recombination of the resulting CH3OH2+ ion to yield methanol and hydrogen atoms is therefore very unlikely.
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2. |
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3. |
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4. |
- Abi Ghaida, Fatima, et al.
(author)
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Enzymatic N2 activation : general discussion
- 2023
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In: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 243, s. 287-295
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Journal article (pop. science, debate, etc.)
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5. |
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6. |
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7. |
- Alonso-Mori, R., et al.
(author)
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Towards characterization of photo-excited electron transfer and catalysis in natural and artificial systems using XFELs
- 2016
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 194, s. 621-638
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Journal article (peer-reviewed)abstract
- The ultra-bright femtosecond X-ray pulses provided by X-ray Free Electron Lasers (XFELs) open capabilities for studying the structure and dynamics of a wide variety of biological and inorganic systems beyond what is possible at synchrotron sources. Although the structure and chemistry at the catalytic sites have been studied intensively in both biological and inorganic systems, a full understanding of the atomic-scale chemistry requires new approaches beyond the steady state X-ray crystallography and X-ray spectroscopy at cryogenic temperatures. Following the dynamic changes in the geometric and electronic structure at ambient conditions, while overcoming X-ray damage to the redox active catalytic center, is key for deriving reaction mechanisms. Such studies become possible by using the intense and ultra-short femtosecond X-ray pulses from an XFEL, where sample is probed before it is damaged. We have developed methodology for simultaneously collecting X-ray diffraction data and X-ray emission spectra, using an energy dispersive spectrometer, at ambient conditions, and used this approach to study the room temperature structure and intermediate states of the photosynthetic water oxidizing metallo-protein, photosystem II. Moreover, we have also used this setup to simultaneously collect the X-ray emission spectra from multiple metals to follow the ultrafast dynamics of light-induced charge transfer between multiple metal sites. A Mn-Ti containing system was studied at an XFEL to demonstrate the efficacy and potential of this method.
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8. |
- An, Junxue, et al.
(author)
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The Ru complexes containing pyridine-dicarboxylate ligand: electronic effect on their catalytic activity toward water oxidation
- 2011
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 155, s. 267-275
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Journal article (peer-reviewed)abstract
- Two series of mononuclear ruthenium complexes [Ru(pdc)L-3] (H(2)pdc = 2,6-pyridinedicarboxylic acid; L = 4-methoxypyridine, 1; pyridine, 2; pyrazine, 3) and [Ru(pdc)L-2(dmso)] (dmso = dimethyl sulfoxide; L = 4-methoxypyridine, 4; pyridine, 5) were synthesized and spectroscopically characterized. Their catalytic activity toward water oxidation has been examined using Ce-IV (Ce(NH4)(2)(NO3)(6)) as the chemical oxidant under acidic conditions. Complexes 1, 2 and 3 are capable of catalyzing Ce-IV-driven water oxidation while 4 and 5 are not active. Electronic effects on their catalytic activity were illustrated: electron donating groups increase the catalytic activity.
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9. |
- Andersson, Johan, et al.
(author)
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New paradigm of transition metal polypyridine complex photochemistry
- 2004
-
In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498. ; 127, s. 295-305
-
Journal article (peer-reviewed)abstract
- Using polarization sensitive ultrafast transient absorption spectroscopy we have studied energy transfer and excited state relaxation pathways in a tetranuclear transition metal [( osmium)( ruthenium)(3)] polypyridine complex. Contrary to the generally accepted picture of transition metal complex photochemistry we find that ultrafast energy transfer ( less than or equal to 60 fs) occurs from the excited singlet MLCT state of the peripheral Ru-chromophores to the central Os-core, in efficient competition with intersystem crossing. Energy transfer between relaxed triplet MLCT states is more than an order of magnitude slower ( 600 fs).
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10. |
- Andersson, Joel, et al.
(author)
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Semi-deterministic chemo-mechanical model of boundary lubrication
- 2012
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 156, s. 343-360
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Journal article (peer-reviewed)abstract
- A model for tribofilm growth is developed. The model is used in combination with numerical contact mechanics tools to enable evaluation of the combined effects of chemistry and contact mechanics. The model is tuned with experimental data and is thereafter applied to rough surfaces. The growth of the tribofilm is evaluated for 3 different contact cases and short-term tribofilm growth behaviour is analyzed. The results show how tribofilms grow in patches. The model is expected to be used as a tool for analysis of the interaction between rough surfaces.
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11. |
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12. |
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13. |
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14. |
- Barreleiro, Paula, et al.
(author)
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Mechanism of formation of DNA-cationic vesicle complexes
- 2003
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498. ; 122, s. 191-201
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Journal article (peer-reviewed)abstract
- Cationic vesicles and DNA form complexes that are promising gene delivery systems. Despite the increasing number of publications on their morphology and structure, the mechanism leading to their formation is not yet understood due to a lack of kinetic data. In the present study the kinetics of the interaction between DNA and cationic vesicles were followed using stopped-flow turbidity and small-angle neutron scattering techniques. The neutron real-time experiments were performed on a high-flux diffractometer, the D22 at the ILL, using a stopped-flow set-up. Extruded mixed vesicles of dimethyldioctadecylammonium bromide (DODAB) with various amounts of dioleoylphosphatidylethanolamine (DOPE) were investigated at 25degreesC. The results show that the transition from unilamellar vesicles to a multilamellar structure upon DNA addition occurs in three steps. The first step, on the millisecond time scale, is currently not accessible to neutron scattering but was observed by stopped-flow turbidity and fluorescence experiments. The second step, on a time scale of seconds, corresponds to the formation of an intermediate with a locally cylindrical structure. As time progresses this unstable intermediate evolves to a multilamellar structure, on a time scale of minutes. An understanding of the mechanisms behind the DNA cationic vesicle complex formation event will allow the production of more homogeneous, efficient delivery systems in pharmaceutically acceptable forms.
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15. |
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16. |
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17. |
- Black, John H, 1949
(author)
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Chemistry and cosmology
- 2006
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 133, s. 27-32
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Journal article (peer-reviewed)abstract
- The simplest elements, hydrogen and helium, offer a remarkably rich chemistry, which has controlled crucial features of the early evolution of the universe. Theoretical models of the origin of structure (stars, galaxies, clusters of galaxies, etc.) now incorporate this chemistry in some detail. In addition to the origin of structure, cosmologists are concerned with observational tests of competing world models. Primordial chemistry may give rise to some of the earliest departures from thermodynamic equilibrium in the universe. These effects may be observable as broad-band spectroscopic distortions of the cosmic background radiation, which otherwise exhibits a nearly perfect blackbody spectrum. The chemical history of the expanding universe is followed through a detailed calculation of the evolution of the abundances of H, H+, H, H2, H+2, H+3, and other minor species. It is shown that continuous absorption by the small concentration of H can produce a distortion in the cosmic background spectrum with a maximum at a frequency near /c = 9 cm1 (wavelength 1.1 mm). The predicted effect lies only a factor of 5 below current limits. Its detection would provide an important test of our understanding of the recombination epoch of the universe.
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18. |
- Blazic, Marija, et al.
(author)
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High-throughput selection of (new) enzymes : phage display-mediated isolation of alkyl halide hydrolases from a library of active-site mutated epoxide hydrolases
- 2024
-
In: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498.
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Journal article (peer-reviewed)abstract
- Epoxide hydrolase StEH1, from potato, is similar in overall structural fold and catalytic mechanism to haloalkane dehalogenase DhlA from Xanthobacter autotrophicus. StEH1 displays low (promiscuous) hydrolytic activity with (2-chloro)- and (2-bromo)ethanebenzene producing 2-phenylethanol. To investigate possibilities to amplify these very low dehalogenase activities, StEH1 was subjected to targeted randomized mutagenesis at five active-site amino acid residues and the resulting protein library was challenged for reactivity towards a bait chloride substrate. Enzymes catalyzing the first half-reaction of a hydrolytic cycle were isolated following monovalent phage display of the mutated proteins. Several StEH1 derived enzymes were identified with enhanced dehalogenase activities.
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19. |
- Boll, Rebecca, et al.
(author)
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Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules
- 2014
-
In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498. ; 171, s. 57-80
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Journal article (peer-reviewed)abstract
- This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laser-aligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.
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20. |
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21. |
- Bressler, C., et al.
(author)
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Solvation dynamics monitored by combined X-ray spectroscopies and scattering: photoinduced spin transition in aqueous [Fe(bpy)(3)](2+)
- 2014
-
In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498. ; 171, s. 169-178
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Journal article (peer-reviewed)abstract
- We have studied the photoinduced low spin (LS) to high spin (HS) conversion of aqueous Fe(bpy)(3) with pulse-limited time resolution. In a combined setup permitting simultaneous X-ray diffuse scattering (XDS) and spectroscopic measurements at a MHz repetition rate we have unraveled the interplay between intramolecular dynamics and the intermolecular caging solvent response with 100 ps time resolution. On this time scale the ultrafast spin transition including intramolecular geometric structure changes as well as the concomitant bulk solvent heating process due to energy dissipation from the excited HS molecule are long completed. The heating is nevertheless observed to further increase due to the excess energy between HS and LS states released on a subnanosecond time scale. The analysis of the spectroscopic data allows precise determination of the excited population which efficiently reduces the number of free parameters in the XDS analysis, and both combined permit extraction of information about the structural dynamics of the first solvation shell.
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22. |
- Buckle, J. V., et al.
(author)
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Observations of chemical differentiation in clumpy molecular clouds
- 2006
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 133, s. 63 - 82
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Journal article (peer-reviewed)abstract
- We have extensively mapped a sample of dense molecular clouds (L1512, TMC-1C, L1262, Per7, L1389, L1251E) in lines of HC 3 N, CH 3 OH, SO and C 18 O. We demonstrate that a high degree of chemical differentiation is present in all of the observed clouds. We analyse the molecular maps for each cloud, demonstrating a systematic chemical differentiation across the sample, which we relate to the evolutionary state of the cloud. We relate our observations to the cloud physical, kinematical and evolutionary properties, and also compare them to the predictions of simple chemical models. The implications of this work for understanding the origin of the clumpy structures and chemical differentiation observed in dense clouds are discussed. © The Royal Society of Chemistry 2006.
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23. |
- Bull, James N., et al.
(author)
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Photodetachment and photoreactions of substituted naphthalene anions in a tandem ion mobility spectrometer
- 2019
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 217, s. 34-46
-
Journal article (peer-reviewed)abstract
- Substituted naphthalene anions (deprotonated 2-naphthol and 6-hydroxy-2-naphthoic acid) are spectroscopically probed in a tandem drift tube ion mobility spectrometer (IMS). Target anions are selected according to their drift speed through nitrogen buffer gas in the first IMS stage before being exposed to a pulse of tunable light that induces either photodissociation or electron photodetachment, which is conveniently monitored by scavenging the detached electrons with trace SF6 in the buffer gas. The photodetachment action spectrum of the 2-naphtholate anion exhibits a band system spanning 380-460 nm with a prominent series of peaks spaced by 440 cm(-1), commencing at 458.5 nm, and a set of weaker peaks near the electron detachment threshold corresponding to transitions to dipole-bound states. The two deprotomers of 6-hydroxy-2-naphthoic acid are separated and spectroscopically probed independently. The molecular anion formed from deprotonation of the hydroxy group gives rise to a photodetachment action spectrum similar to that of the 2-naphtholate anion with an onset at 470 nm and a maximum at 420 nm. Near the threshold, the photoreaction with SF6 is observed with displacement of an OH group by an F atom. In contrast, the anion formed from deprotonation of the carboxylic acid group gives rise to a photodissociation action spectrum, recorded on the CO2 loss channel, lying at much shorter wavelengths with an onset at 360 nm and maximum photoresponse at 325 nm.
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24. |
- Campbell, Charles, et al.
(author)
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Bridging model and real catalysts: general discussion
- 2016
-
In: Faraday Discussions. - 1359-6640 .- 1364-5498. ; 188, s. 565-589
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Journal article (other academic/artistic)abstract
- Charles Campbell opened the discussion of the paper by Hans-JoachimFreund: If you have a 3D gold particle and it spreads out to be a 2D particle whenyou adsorb CO2, it must gain energy stability. Did you estimate the energy changeof the overall process to do that?
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25. |
- Campbell, Charles, et al.
(author)
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Catalyst design from theory to practice: general discussion
- 2016
-
In: Faraday Discussions. - 1359-6640 .- 1364-5498. ; 188, s. 279-307
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Journal article (other academic/artistic)abstract
- Hans-Joachim Freund opened the discussion of the paper by Alberto Roldan:How is the atomic hydrogen produced on the greigite surface? In the paper (DOI:10.1039/C5FD00186B) there is no comment whether you studied dissociatehydrogen adsorption.
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26. |
- Canton, S. E., et al.
(author)
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Watching the dynamics of electrons and atoms at work in solar energy conversion
- 2015
-
In: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 185, s. 51-68
-
Journal article (peer-reviewed)abstract
- The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium-cobalt dyads, which belong to the large family of donor-bridge-acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray
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27. |
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28. |
- Chábera, Pavel, et al.
(author)
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Band-selective dynamics in charge-transfer excited iron carbene complexes
- 2019
-
In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 216:2019, s. 191-210
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Journal article (peer-reviewed)abstract
- Ultrafast dynamics of photoinduced charge transfer processes in light-harvesting systems based on Earth-abundant transition metal complexes are of current interest for the development of molecular devices for solar energy conversion applications. A combination of ultrafast spectroscopy and first principles quantum chemical calculations of a recently synthesized iron carbene complex is used to elucidate the ultrafast excited state evolution processes in these systems with particular emphasis on investigating the underlying reasons why these complexes show promise in terms of significantly extended lifetimes of charge transfer excited states. Together, our results challenge the traditional excited state landscape for iron-based light harvesting transition metal complexes through radically different ground and excited state properties in alternative oxidation states. This includes intriguing indications of rich band-selective excited state dynamics on ultrafast timescales that are interpreted in terms of excitation energy dependence for excitations into a manifold of charge-transfer states. Some implications of the observed excited state properties and photoinduced dynamics for the utilization of iron carbene complexes for solar energy conversion applications are finally discussed.
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29. |
- Cheng, Minglun, et al.
(author)
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Photocatalytic H-2 production using a hybrid assembly of an [FeFe]-hydrogenase model and CdSe quantum dot linked through a thiolato-functionalized cyclodextrin
- 2017
-
In: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 198, s. 197-209
-
Journal article (peer-reviewed)abstract
- It is a great challenge to develop iron-based highly-efficient and durable catalytic systems for the hydrogen evolution reaction (HER) by understanding and learning from [FeFe]-hydrogenases. Here we report photocatalytic H-2 production by a hybrid assembly of a sulfonate-functionalized [FeFe]-hydrogenase mimic (1) and CdSe quantum dot (QD), which is denoted as 1/beta-CD-6-S-CdSe (beta-CD-6-SH = 6-mercapto-beta-cyclodextrin). In this assembly, thiolato-functionalized beta-CD acts not only as a stabilizing reagent of CdSe QDs but also as a host compound for the diiron catalyst, so as to confine CdSe QDs to the space near the site of diiron catalyst. In addition, another two reference systems comprising MAA-CdSe QDs (HMAA = mercaptoacetic acid) and 1 in the presence and absence of beta-CD, denoted as 1/beta-CD/MAA-CdSe and 1/MAA-CdSe, were studied for photocatalytic H-2 evolution. The influences of beta-CD and the stabilizing reagent beta-CD-6-S- on the stability of diiron catalyst, the fluorescence lifetime of CdSe QDs, the apparent electron transfer rate, and the photocatalytic H-2-evolving efficiency were explored by comparative studies of the three hybrid systems. The 1/beta-CD-6-SCdSe system displayed a faster apparent rate for electron transfer from CdSe QDs to the diiron catalyst compared to that observed for MAA-CdSe-based systems. The total TON for visible-light driven H-2 evolution by the 1/beta-CD-6-S-CdSe QDs in water at pH 4.5 is about 2370, corresponding to a TOF of 150 h(-1) in the initial 10 h of illumination, which is 2.7- and 6.6-fold more than the amount of H-2 produced from the reference systems 1/beta-CD/MAA-CdSe and 1/MAA-CdSe. Additionally, 1/beta-CD-6-S-CdSe gave 2.4-5.1 fold enhancement in the apparent quantum yield and significantly improved the stability of the system for photocatalytic H-2 evolution.
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30. |
- D’Acunto, Giulio, et al.
(author)
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Oxygen relocation during HfO2 ALD on InAs
- 2022
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 236, s. 71-85
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Journal article (peer-reviewed)abstract
- Atomic layer deposition (ALD) is one of the backbones for today’s electronic device fabrication. A critical property of ALD is the layer-by-layer growth, which gives rise to the atomic-scale accuracy. However, the growth rate - or growth per cycle - can differ significantly depending on the type of system, molecules used, and several other experimental parameters. Typically, ALD growth rates are constant in subsequent ALD cycles, making ALD an outstanding deposition technique. However, contrary to this steady-state - when the ALD process can be entirely decoupled from the substrate on which the material is grown - the deposition’s early stage does not appear to follow the same kinetics, chemistry, and growth rate. Instead, it is to a large extent determined by the surface composition of the substrate. Here, we present evidence of oxygen relocation from the substrate-based oxide, either the thermal or native oxide of InAs, to the overlayer of HfO2 in the initial ALD phase. This phenomenon enables control of the thickness of the initial ALD layer by controlling the surface conditions of the substrate prior to ALD. On the other hand, we observe a complete removal of the native oxide from InAs already during the first ALD half-cycle, even if the thickness of the oxide layer exceeds one monolayer, together with a self-limiting thickness of the ALD layer of a maximum of one monolayer of HfO2. These observations not only highlight several limitations of the widely used ligand exchange model, but they also give promise for a better control of the industrially important self-cleaning effect of III-V semiconductors, which is crucial for future generation high-speed MOS.
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31. |
- Donahue, Neil M., et al.
(author)
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How do organic vapors contribute to new-particle formation?
- 2013
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In: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 165, s. 91-104
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Journal article (peer-reviewed)abstract
- Highly oxidised organic vapors can effectively stabilize sulphuric acid in heteronuclear clusters and drive new-particle formation. We present quantum chemical calculations of cluster stability, showing that multifunctional species can stabilize sulphuric acid and also present additional polar functional groups for subsequent cluster growth. We also model the multi-generation oxidation of vapors associated with secondary organic aerosol formation using a two-dimensional volatility basis set. The steady-state saturation ratios and absolute concentrations of extremely low volatility products are sufficient to drive new-particle formation with sulphuric acid at atmospherically relevant rates.
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32. |
- Eastoe, Julian, et al.
(author)
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Interrogation of a dynamic multi-catalyst ensemble in asymmetric catalysis
- 2010
-
In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640. ; 145, s. 27-47
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Journal article (peer-reviewed)abstract
- The Trost Standard Ligand (2) is a chiral diphosphine ligand that distinguishes itself by the high selectivity it induces in the Pd-catalysed reactions of allylic substrates that generate slim cyclic or small linear intermediates. However, a range of unusual features, including memory effects, inverse dependence of selectivity and rate on catalyst concentration, high sensitivity to counter-ion, particularly chloride, and decreasing enantioselectivities at lower temperatures, are often encountered, thus requiring considerable optimisation of reaction conditions to attain optimum selectivity. These features can be accounted for by a model involving a dynamic multi-catalyst ensemble. To gain evidence for this model, the manner in which diphosphine 2 interacts with Pd–allyl cations, and in particular the higher-order systems it generates, has been investigated by use of NMR, isotopic labelling, polarimetry, UV, neutron scattering, X-ray crystallography and molecular modeling. Ligand 2 coordinates to Pd–allyl cations to generate a mononuclear P,P-chelate. This is found to readily form non-chelate oligomers, present in a range of forms, including rings, for which high homochiral selectivity in oligomerisation is demonstrated by the technique of pseudoenantiomers. All of these species are in relatively rapid equilibrium, with half-lives for interconversion in the range 2–6 s. Higher-order aggregation is also detected, and thus at even moderate concentrations (>50 mM) large rod-like aggregates are formed.
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33. |
- Fucikova, Anna, et al.
(author)
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The shell matters : one step synthesis of core-shell silicon nanoparticles with room temperature ultranarrow emission linewidth
- 2020
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In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 222:0, s. 135-148
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Journal article (peer-reviewed)abstract
- Here we present a one-step synthesis that provides silicon nanocrystals with a thin shell composed of a ceramic-like carbonyl based compound, embedded in a porous organosilicon film. The silicon nanocrystals were synthesised from hydrogen silsesquioxane molecules, modified with organic molecules containing carbonyl groups, which were annealed at 1000 degrees C in a slightly reducing 5% H-2 : 95% Ar atmosphere. The organic character of the shell was preserved after annealing due to trapping of organic molecules inside the HSQ-derived oxide matrix that forms during the annealing. The individual silicon nanocrystals, studied by single dot spectroscopy, exhibited a significantly narrower emission peak at room temperature (lowest linewidth similar to 17 meV) compared to silicon nanocrystals embedded in a silicon oxide shell (150 meV). Their emission linewidths are even significantly narrower than those of single CdSe quantum dots (>50 meV). It is hypothesized that the Si-core-thin shell structure of the nanoparticle is responsible for the unique optical properties. Its formation within one synthesis step opens new opportunities for silicon-based quantum dots. The luminescence from the produced nanocrystals covers a broad spectral range from 530-720 nm (1.7-2.3 eV) suggesting strong application potential for solar cells and LEDs, following the development of a suitable mass-fabrication protocol.
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34. |
- Gagliardi, L., et al.
(author)
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On the reaction of a uranium atom with a nitrogen molecule: a theoretical attempt
- 2003
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498 .- 1359-6640. ; 124, s. 63-68
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Journal article (peer-reviewed)abstract
- An attempt has been made to study the reaction between a uranium atom and a nitrogen molecule theoretically using multiconfigurational wave functions. The C-2v part of the reaction surface has been computed for several electronic states of various spin multiplicities. The system proceeds from a neutral uranium atom in its (5f)(3)(6d)(7s)(2), 5 L ground state to the linear molecule NUN, which has a (1)Sigma(g)(+) ground state and uranium in a formal U(VI) oxidation state. The effect of spin-orbit coupling has been estimated at crucial points along the reaction. These preliminary results shows that the system proceeds from a quintet state for U + N-2, via a triplet transition state to the final closed shell molecule. An eventual energy barrier for the insertion reaction is caused by the spin-orbit coupling energy.
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35. |
- Galkin, Maxim V., et al.
(author)
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Sustainable sources need reliable standards
- 2017
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In: Faraday discussions. - : ROYAL SOC CHEMISTRY. - 1359-6640 .- 1364-5498. ; 202, s. 281-301
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Journal article (peer-reviewed)abstract
- This review discusses the challenges within the research area of modern biomass fractionation and valorization. The current pulping industry focuses on pulp production and the resulting cellulose fiber. Hemicellulose and lignin are handled as low value streams for process heat and the regeneration of process chemicals. The paper and pulp industry have therefore developed analytical techniques to evaluate the cellulose fiber, while the other fractions are given a low priority. In a strive to also use the hemicellulose and lignin fractions of lignocellulosic biomass, moving towards a biorefining concept, there are severe shortcomings with the current pulping techniques and also in the analysis of the biomass. Lately, new fractionation techniques have emerged which valorize a larger extent of the lignocellulosic biomass. This progress has disclosed the shortcomings in the analysis of mainly the hemicellulose and lignin structure and properties. To move the research field forward, analytical tools for both the raw material, targeting all the wood components, and the generated fractions, as well as standardized methods for evaluating and reporting yields are desired. At the end of this review, a discourse on how such standardizations can be implemented is given.
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36. |
- Gao, Yan, et al.
(author)
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Artificial photosynthesis : photosensitizer/catalyst supramolecular assemblies for light driven water oxidation
- 2014
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 176, s. 225-232
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Journal article (peer-reviewed)abstract
- Three new supramolecular assemblies SA1-SA3 with different linkages between the photosensitizer and catalyst have been synthesized for light driven water oxidation. With flexible -CH2-CH2- chains as the linkage, the assembly SA3 displays the best performance for photocatalytic water oxidation compared with the other two assemblies, a turnover number of 34 has been obtained based on the molecular assembly SA3 in a homogeneous system. This type of assembly connected with flexible linkages represents suitable candidates to construct photoanodes for light driven water splitting in dye sensitized photoelectrochemical devices.
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37. |
- Gatchell, Michael, et al.
(author)
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Spectroscopy of corannulene cations in helium nanodroplets
- 2019
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 217, s. 276-289
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Journal article (peer-reviewed)abstract
- Helium tagging in action spectroscopy is an efficient method for measuring the absorption spectra of complex molecular ions with minimal perturbations to the gas phase spectra. We have used superfluid helium nanodroplets doped with corannulene to prepare cations of these molecules complexed with different numbers of He atoms. In total we identify 13 different absorption bands from corannulene cations between 5500 angstrom and 6000 angstrom. The He atoms cause a small, chemically induced redshift of the band positions of the corannulene ion. By studying this effect as a function of the number of solvating atoms we are able to identify the formation of solvation structures that are not visible in the mass spectrum. The solvation features detected using action spectroscopy agree very well with the results of atomistic modeling based on path-integral molecular dynamics simulations. By additionally doping our He droplets with D-2, we produce protonated corannulene ions. The absorption spectrum of these ions differs significantly from the case of the radical cations as the numerous narrow bands are replaced by a broad absorption feature that spans nearly 2000 angstrom in width.
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38. |
- Ge, Meng, et al.
(author)
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On the completeness of three-dimensional electron diffraction data for structural analysis of metal-organic frameworks
- 2021
-
In: Faraday discussions. - 1359-6640 .- 1364-5498. ; 231
-
Journal article (peer-reviewed)abstract
- Three-dimensional electron diffraction (3DED) has been proven as an effective and accurate method for structure determination of nano-sized crystals. In the past decade, the crystal structures of various new complex metal-organic frameworks (MOFs) have been revealed by 3DED, which has been the key to understand their properties. However, due to the design of transmission electron microscopes (TEMs), one drawback of 3DED experiments is the limited tilt range of goniometers, which often leads to incomplete 3DED data, particularly when the crystal symmetry is low. This drawback can be overcome by high throughput data collection using continuous rotation electron diffraction (cRED), where data from a large number of crystals can be collected and merged. Here, we investigate the effects of improving completeness on structural analysis of MOFs. We use ZIF-EC1, a zeolitic imidazolate framework (ZIF), as an example. ZIF-EC1 crystallizes in a monoclinic system with a plate-like morphology. cRED data of ZIF-EC1 with different completeness and resolution were analyzed. The data completeness increased to 92.0% by merging ten datasets. Although the structures could be solved from individual datasets with a completeness as low as 44.5% and refined to a high precision (better than 0.04 angstrom), we demonstrate that a high data completeness could improve the structural model, especially on the electrostatic potential map. We further discuss the strategy adopted during data merging. We also show that ZIF-EC1 doped with cobalt can act as an efficient electrocatalyst for oxygen reduction reactions.
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39. |
- Geppert, W D, et al.
(author)
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Extraordinary branching ratios in astrophysically important dissociative recombination reactions
- 2004
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In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 127, s. 425-437
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Journal article (peer-reviewed)abstract
- Branching ratios of the dissociative recombination reactions of the astrophysically relevant ions DCO+, N2H+ and DOCO+ ( as substitute for HOCO+) have been measured using the CRYRING storage ring at the Manne Siegbahn Laboratory at the University of Stockholm, Sweden. For DCO+, the channel leading to D and CO was by far the most important one ( branching ratio 0.88), only small contributions of the CD+O and OD+C product pathways ( branching ratios 0.06 each) were recorded. In the case of N2H+ the surprising result of a break-up of the N-N bond to N and NH ( branching ratio 0.64) was found with the branching ratio of the N-2+H product channel therefore displaying a branching ratio of only 0.36. In the case of DOCO+, the three-body break-up into D+O+CO dominated ( branching ratio 0.68), whereas the contribution of the CO2+H channel was only minute (0.05). The remaining share ( branching ratio 0.27) was taken by the pathway leading to OH+CO. For the dissociative recombination of N2H+ and DOCO+ also absolute reaction cross sections were obtained in the collisional energy range between 0 and 1 eV. From these cross sections it was possible to work out the thermal rate constants, which were found to be k(T) = 1.0 +/- 0.1 x 10(-7) (T/300 K)(-0.51 +/- 0.02) cm(3) s(-1) and k(T) = 1.2 +/- 0.1 x 10(-6) (T/300 K)(-0.64 +/- 0.02) cm(3) s(-1) for N2H+ and DOCO+, respectively.
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40. |
- Gibaud, Thomas, et al.
(author)
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New routes to food gels and glasses
- 2012
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498 .- 1359-6640. ; 158, s. 267-284
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Journal article (peer-reviewed)abstract
- We describe the possibility to create solid-like protein samples whose structural and mechanical properties can be varied and tailored over an extremely large range in a very controlled way through an arrested spinodal decomposition process. We use aqueous lysozyme solutions as a model globular protein system. A combination of video microscopy, small-angle neutron and X-ray scattering and reverse Monte Carlo modeling is used to characterize the structure of the bicontinuous network with two coexisting phases of a dilute protein solution and a glassy or arrested dense protein backbone at all relevant length scales. Rheological measurements are then used to determine the complex mechanical response of these protein gels as a function of protein concentration and quench temperature. While in particular the origin of the dependence of the mechanical properties on quench depth and concentration is not well understood currently, it seems ultimately connected to the particular bicontinuous structure of the arrested spinodal network created by the interplay between the early stage of a spinodal decomposition and the position of the glass line. We then generalize this behavior and discuss how this could open up new routes to prepare gel-like food systems with adjustable structural and mechanical properties. We present results from a first feasibility study where we use a depletion interaction caused by the addition of small non-adsorbing polymers to suspensions of casein micelles in order to create food gels with tunable structural and mechanical properties through an arrested spinodal decomposition process.
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41. |
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42. |
- Gotter, M, et al.
(author)
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Fusion and fission of fluid amphiphilic bilayers
- 2005
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1364-5498. ; 129, s. 327-338
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Journal article (peer-reviewed)abstract
- The system water-oil (n-decane)-nonionic surfactant (C12E5) forms bilayer phases in a large concentration region, but, for a given oil-to-surfactant ratio, only in a narrow temperature range. In addition to the anisotropic lamellar phase (L-alpha) there is also, at slightly higher temperature, a sponge or L-3-phase where the bilayers build up an isotropic structure extending macroscopically in three dimensions. In this phase the bilayer mid-surface has a mean curvature close to zero and a negative Euler characteristic. In this paper we study how the bilayers in the lamellar and the sponge phase respond dynamically to sudden temperature changes. The monolayer spontaneous curvature depends sensitively on temperature and a change of temperature thus provides a driving force for a change in bilayer topology. The equilibration therefore involves kinetic steps of fusion/fission of bilayers. Such dynamic processes have previously been monitored by temperature jump experiments using light scattering in the sponge phase. These experiments revealed an extraordinarily strong dependence of the relaxation time on the bilayer volume fraction phi. At phi<0.1 the relaxation times are so slow that experiments using deuterium nuclear magnetic resonance (H-2-NMR) appear feasible. We here report on the first experiments concerned with the dynamics of the macroscopic phase transition sponge-lamellae by H-2-NMR. We find that the sponge-to-lamellae transition occurs through a nucleation process followed by domain growth involving bilayer fission at domain boundaries. In contrast, the lamellae-to-sponge transformation apparently occurs through a succession of uncorrelated bilayer fusion events.
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43. |
- Gstir, Thomas, et al.
(author)
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Reaction dynamics of the methoxy anion CH3O− with methyl iodide CH3I
- 2024
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In: Faraday discussions. - 1359-6640 .- 1364-5498.
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Journal article (peer-reviewed)abstract
- Studying larger nucleophiles in bimolecular nucleophilic substitution (SN2) reactions bridges the gap from simple model systems to those relevant to organic chemistry. Therefore, we investigated the reaction dynamics between the methoxy anion (CH3O−) and iodomethane (CH3I) in our crossed-beam setup combined with velocity map imaging at the four collision energies 0.4, 0.7, 1.2, and 1.6 eV. We find the two ionic products I− and CH2I−, which can be attributed to the SN2 and proton transfer channels, respectively. The proton transfer channel progresses in a previously observed fashion from indirect to direct scattering with increasing collision energy. Interestingly, the SN2 channel exhibits direct dynamics already at low collision energies. Both the direct stripping, leading to forward scattering, and the direct rebound mechanism, leading to backward scattering into high angles, are observed.
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44. |
- Hakkert, Sebastiaan B., et al.
(author)
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The N-15 NMR chemical shift in the characterization of weak halogen bonding in solution
- 2017
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In: Faraday Discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 203, s. 333-346
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Journal article (peer-reviewed)abstract
- © The Royal Society of Chemistry. We have studied the applicability of 15 N NMR spectroscopy in the characterization of the very weak halogen bonds of nonfluorinated halogen bond donors with a nitrogenous Lewis base in solution. The ability of the technique to detect the relative strength of iodine-, bromine- and chlorine-centered halogen bonds, as well as solvent and substituent effects was evaluated. Whereas computations on the DFT level indicate that 15 N NMR chemical shifts reflect the diamagnetic deshielding associated with the formation of a weak halogen bond, the experimentally observed chemical shift differences were on the edge of detectability due to the low molar fraction of halogen-bonded complexes in solution. The formation of the analogous yet stronger hydrogen bond of phenols have induced approximately ten times larger chemical shift changes, and could be detected and correlated to the electronic properties of substituents of the hydrogen bond donors. Overall, 15 N NMR is shown to be a suitable tool for the characterization of comparably strong secondary interactions in solution, but not sufficiently accurate for the detection of the formation of thermodynamically labile, weak halogen bonded complexes.
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45. |
- Hammarström, Leif, 1964-
(author)
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Artificial photosynthesis : closing remarks
- 2017
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In: Faraday discussions. - : ROYAL SOC CHEMISTRY. - 1359-6640 .- 1364-5498. ; 198, s. 549-560
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Journal article (peer-reviewed)abstract
- This paper derives from my closing remarks lecture at the 198th Faraday Discussion meeting on Artificial Photosynthesis, Kyoto, Japan, February 28-March 2. The meeting had sessions on biological approaches and fundamental processes, molecular catalysts, inorganic assembly catalysts, and integration of systems for demonstrating realistic devices. The field has had much progress since the previous Faraday Discussion on Artificial Photosynthesis in Edinburgh, UK, in 2011. This paper is a personal account of recent discussions and developments in the field, as reflected in and discussed during the meeting. First it discusses the general directions of artificial photosynthesis and some considerations for a future solar fuels technology. Then it comments on some scientific directions in the area of the meeting.
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46. |
- Hawkes, Jeffrey A., et al.
(author)
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Complexity of dissolved organic matter in the molecular size dimension : insights from coupled size exclusion chromatography electrospray ionisation mass spectrometry
- 2019
-
In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 218, s. 52-71
-
Journal article (peer-reviewed)abstract
- This paper investigates the relationship between apparent size distribution and molecular complexity of dissolved organic matter from the natural environment. We used a high pressure size exclusion chromatography (HPSEC) method coupled to UV-Vis diode array detection (UV-DAD) and electrospray ionisation mass spectrometry (ESI-MS) in order to compare the apparent size of natural organic matter, determined by HPSEC-UV and the molecular mass determined online by ESI-MS. We found that there was a clear discrepancy between the two methods, and found evidence for an important pool of organic matter that has a strong UV absorbance and no ESI-MS signal. Contrary to some previous research, we found no evidence that apparently high molecular weight organic matter is constituted by aggregates of low molecular weight (<1000 Da) material. Furthermore, our results suggest that the majority of apparent size variability within the ESI ionisable pool of organic matter is due to secondary interaction and exclusion effects on the HPSEC column, and not true differences in hydrodynamic size or intermolecular aggregation.
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47. |
- Hu, Lan, et al.
(author)
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Electrode kinetics of the NiO porous electrode for oxygen production in the molten carbonate electrolysis cell (MCEC)
- 2015
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In: Faraday discussions. - : Royal Society of Chemistry. - 1359-6640 .- 1364-5498. ; 182, s. 493-509
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Journal article (peer-reviewed)abstract
- The performance of a molten carbonate electrolysis cell (MCEC) is to a great extent determined by the anode, i.e. the oxygen production reaction at the porous NiO electrode. In this study, stationary polarization curves for the NiO electrode were measured under varying gas compositions and temperatures. The exchange current densities were calculated numerically from the slopes at low overpotential. Positive dependency on the exchange current density was found for the partial pressure of oxygen. When the temperature was increased in the range 600-650 degrees C, the reaction order of oxygen decreased from 0.97 to 0.80. However, there are two different cases for the partial pressure dependency of carbon dioxide within this temperature range: positive values, 0.09-0.30, for the reaction order at lower CO2 concentration, and negative values, -0.26-0.01, with increasing CO2 content. A comparison of theoretically obtained data indicates that the oxygen-producing reaction in MCEC could be reasonably satisfied by the reverse of oxygen reduction by the oxygen mechanism I, an n = 4 electron reaction, assuming a low coverage of oxide ions at high CO2 content and an intermediate coverage for a low CO2 concentration.
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48. |
- Huang, Zhehao, et al.
(author)
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Can 3D electron diffraction provide accurate atomic structures of metal-organic frameworks?
- 2021
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In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 225:0, s. 118-132
-
Journal article (peer-reviewed)abstract
- Many framework materials such as metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are synthesized as polycrystalline powders, which are too small for structure determination by single crystal X-ray diffraction (SCXRD). Here, we show that a three-dimensional (3D) electron diffraction method, namely continuous rotation electron diffraction (cRED), can be used for ab initio structure determination of such materials. As an example, we present the complete structural analysis of a biocomposite, denoted BSA@ZIF-CO3-1, in which Bovine Serum Albumin (BSA) was encapsulated in a zeolitic imidazolate framework (ZIF). Low electron dose was combined with ultrafast cRED data collection to minimize electron beam damage to the sample. We demonstrate that the atomic structure obtained by cRED is as reliable and accurate as that obtained by single crystal X-ray diffraction. The high accuracy and fast data collection open new opportunities for investigation of cooperative phenomena in framework structures at the atomic level.
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49. |
- Ikkala, O., et al.
(author)
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Solid state nanofibers based on self-assemblies : From cleaving from self-assemblies to multilevel hierarchical constructs
- 2009
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In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 143, s. 95-107
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Journal article (peer-reviewed)abstract
- Self-assemblies and their hierarchies are useful to construct soft materials with structures at different length scales and to tune the materials properties for various functions. Here we address routes for solid nanofibers based on different forms of self-assemblies. On the other hand, we discuss rational "bottom-up" routes for multi-level hierarchical self-assembled constructs, with the aim of learning more about design principles for competing interactions and packing frustrations. Here we use the triblock copolypeptide poly(l-lysine)-b-poly(γ-benzyl-l-glutamate)-b-poly(l-lysine) complexed with 2â²-deoxyguanosine 5â²-monophosphate. Supramolecular disks (G-quartets) stabilized by metal cations are formed and their columnar assembly leads to a packing frustration with the cylindrical packing of helical poly(γ-benzyl-l-glutamate), which we suggest is important in controlling the lateral dimensions of the nanofibers. We foresee routes for functionalities by selecting different metal cations within the G-quartets. On the other hand, we discuss nanofibers that are cleaved from bulk self-assemblies in a "top-down" manner. After a short introduction based on cleaving nanofibers from diblock copolymeric self-assemblies, we focus on native cellulose nanofibers, as cleaved from plant cell wall fibers, which are expected to have feasible mechanical properties and to be templates for functional nanomaterials. Long nanofibers with 5-20 nm lateral dimensions can be cleaved within an aqueous medium to allow hydrogels and water can be removed to allow highly porous, lightweight, and flexible aerogels. We further describe inorganic/organic hybrids as prepared by chemical vapour deposition and atomic layer deposition of the different nanofibers. We foresee functional materials by selecting inorganic coatings. Finally we briefly discuss how the organic template can be removed e.g., by thermal treatments to allow completely inorganic hollow nanofibrillar structures.
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50. |
- Kamp, Inga, et al.
(author)
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The chemical inventory of the inner regions of planet-forming disks - the JWST/MINDS program
- 2023
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In: Faraday discussions. - 1359-6640 .- 1364-5498. ; 245, s. 112-137
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Journal article (peer-reviewed)abstract
- The understanding of planet formation has changed recently, embracing the new idea of pebble accretion. This means that the influx of pebbles from the outer regions of planet-forming disks to their inner zones could determine the composition of planets and their atmospheres. The solid and molecular components delivered to the planet-forming region can be best characterized by mid-infrared spectroscopy. With Spitzer low-resolution (R = 100, 600) spectroscopy, this approach was limited to the detection of abundant molecules, such as H2O, C2H2, HCN and CO2. This contribution will present the first results of the MINDS (MIRI mid-INfrared Disk Survey, PI:Th Henning) project. Due do the sensitivity and spectral resolution provided by the James Webb Space Telescope (JWST), we now have a unique tool to obtain the full inventory of chemistry in the inner disks of solar-type stars and brown dwarfs, including also less-abundant hydrocarbons and isotopologues. The Integral Field Unit (IFU) capabilities will enable at the same time spatial studies of the continuum and line emission in extended sources such as debris disks, the flying saucer and also the search for mid-IR signatures of forming planets in systems such as PDS 70. These JWST observations are complementary to ALMA and NOEMA observations of outer-disk chemistry; together these datasets will provide an integral view of the processes occurring during the planet-formation phase.
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