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1.
Soft Matter ; 2024 Apr 19.
Artículo en Inglés | MEDLINE | ID: mdl-38639086

RESUMEN

Spontaneous charge separation in drops sliding over a hydrophobized insulator surface is a well-known phenomenon and lots of efforts have been made to utilize this effect for energy harvesting. For maximizing the efficiency of such devices, a comprehensive understanding of the dewetted surface charge would be required to quantitatively predict the electric current signals, in particular for drop sequences. Here, we use a method based on mirror charge detection to locally measure the surface charge density after drops move over a hydrophobic surface. For this purpose, we position a metal electrode beneath the hydrophobic substrate to measure the capacitive current induced by the moving drop. Furthermore, we investigate drop-induced charging on different dielectric surfaces together with the surface neutralization processes. The surface neutralizes over a characteristic time, which is influenced by the substrate and the surrounding environment. We present an analytical model that describes the slide electrification using measurable parameters such as the surface charge density and its neutralization time. Understanding the model parameters and refining them will enable a targeted optimization of the efficiency in solid-liquid charge separation.

2.
Z Med Phys ; 2024 Mar 12.
Artículo en Inglés | MEDLINE | ID: mdl-38480064

RESUMEN

In recent years, access to 3D printers has become increasingly affordable. Alongside industrial and private applications, the significance of 3D printing in the clinical context is also growing. For instance, 3D printing processes enable the production of individual anatomical models that can be used to support patient communication or aid in surgical planning. While filament 3D printing is common, stereolithography (SLA) and selective laser sintering (SLS) printing processes offer higher precision. For the use of 3D printing materials in radiology, understanding their attenuation properties concerning ionizing radiation is crucial. Polymethyl methacrylate (PMMA) serves as an important reference material for radiological applications in this regard. In this research, linear- and mass attenuation coefficients of 38 SLA-/SLS-materials from Formlabs (Somerville, Massachusetts, USA) and PMMA will be determined through intensity measurements in nuclear medicine for the radionuclides technetium-99 m and iodine-131, as well as for X-ray imaging in the range of 60 kVp - 110 kVp tube voltage. Based on the mass attenuation coefficients, correction factors in respect to PMMA will be calculated for each material. A significant number of materials exhibit a deviance within approximately ±5% in respect to PMMA regardless of radiation energy. However, certain materials from the dental and industrial application show deviances up to +500% at the lower end of radiation energy spectrum. In conclusion, most materials can be considered equivalent to PMMA with only minor adjustments required. Materials with high deviances can be utilized as high-contrast materials in custom X-ray phantoms.

3.
J Biol Chem ; 300(5): 107243, 2024 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-38556086

RESUMEN

Sterols are ubiquitous membrane constituents that persist to a large extent in the environment due to their water insolubility and chemical inertness. Recently, an oxygenase-independent sterol degradation pathway was discovered in a cholesterol-grown denitrifying bacterium Sterolibacterium (S.) denitrificans. It achieves hydroxylation of the unactivated primary C26 of the isoprenoid side chain to an allylic alcohol via a phosphorylated intermediate in a four-step ATP-dependent enzyme cascade. However, this pathway is incompatible with the degradation of widely distributed steroids containing a double bond at C22 in the isoprenoid side chain such as the plant sterol stigmasterol. Here, we have enriched a prototypical delta-24 desaturase from S. denitrificans, which catalyzes the electron acceptor-dependent oxidation of the intermediate stigmast-1,4-diene-3-one to a conjugated (22,24)-diene. We suggest an α4ß4 architecture of the 440 kDa enzyme, with each subunit covalently binding an flavin mononucleotide cofactor to a histidyl residue. As isolated, both flavins are present as red semiquinone radicals, which can be reduced by stigmast-1,4-diene-3-one but cannot be oxidized even with strong oxidizing agents. We propose a mechanism involving an allylic radical intermediate in which two flavin semiquinones each abstract one hydrogen atom from the substrate. The conjugated delta-22,24 moiety formed allows for the subsequent hydroxylation of the terminal C26 with water by a heterologously produced molybdenum-dependent steroid C26 dehydrogenase 2. In conclusion, the pathway elucidated for delta-22 steroids achieves oxygen-independent hydroxylation of the isoprenoid side chain by bypassing the ATP-dependent formation of a phosphorylated intermediate.

4.
Chemistry ; 30(21): e202400105, 2024 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-38299788

RESUMEN

Partial ligand substitution at the iron pentacarbonyl radical cation generates novel half-sandwich complexes of the type [Fe(η6-arene)(CO)2]⋅+ (arene=1,3,5-tri-tert-butylbenzene, 1,3,5-trimethylbenzene, benzene and fluorobenzene). Of those, the bulkier 1,3,5-tri-tert-butylbenzene (mes*) derivative [Fe(mes*)(CO)2]⋅+ was fully characterized by XRD analysis, IR, NMR, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry as the [Al(ORF)4]- (RF=C(CF3)3) salt. Chemical electronation, i. e., the single electron reduction, with decamethylferrocene generates neutral [Fe(mes*)(CO)2], whereas further deelectronation under CO-pressure leads to a dicationic three-legged [Fe(mes*)(CO)3]2+ salt with [Al(ORF)4]- counterion. The full substitution of the carbonyl ligands in [Fe(CO)5]⋅+[Al(ORF)4]- mainly resulted in disproportionation reactions, giving solid Fe(0) and the dicationic bis-arene salts [Fe(η6-arene)2]2+([Al(ORF)4]-)2 (arene=1,3,5-trimethylbenzene, benzene and fluorobenzene). Only by employing the very large fluoride bridged anion [F-{Al(ORF)3}2]-, it was possible to isolate an open shell bis-arene cation salt [Fe(C6H6)2]⋅+[F-{Al(ORF)3}2]-. The highly reactive cation was characterized by XRD analysis, cw-EPR, Mössbauer spectroscopy and cyclic voltammetry. The disproportionation of [Fe(C6H6)2]⋅+ salts to give solid Fe(0) and [Fe(C6H6)2]2+ salts was analyzed by a suitable cycle, revealing that the thermodynamic driving force for the disproportionation is a function of the size of the anion used and the polarity of the solvent.

5.
Environ Sci Atmos ; 4(2): 265-274, 2024 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-38371605

RESUMEN

Aerosols formed and grown by gas-to-particle processes are a major contributor to smog and haze in megacities, despite the competition between growth and loss rates. Rapid growth rates from ammonium nitrate formation have the potential to sustain particle number in typical urban polluted conditions. This process requires supersaturation of gas-phase ammonia and nitric acid with respect to ammonium nitrate saturation ratios. Urban environments are inhomogeneous. In the troposphere, vertical mixing is fast, and aerosols may experience rapidly changing temperatures. In areas close to sources of pollution, gas-phase concentrations can also be highly variable. In this work we present results from nucleation experiments at -10 °C and 5 °C in the CLOUD chamber at CERN. We verify, using a kinetic model, how long supersaturation is likely to be sustained under urban conditions with temperature and concentration inhomogeneities, and the impact it may have on the particle size distribution. We show that rapid and strong temperature changes of 1 °C min-1 are needed to cause rapid growth of nanoparticles through ammonium nitrate formation. Furthermore, inhomogeneous emissions of ammonia in cities may also cause rapid growth of particles.

6.
Environ Sci Technol ; 58(3): 1601-1614, 2024 Jan 23.
Artículo en Inglés | MEDLINE | ID: mdl-38185880

RESUMEN

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth's climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.


Asunto(s)
Contaminantes Atmosféricos , Monoterpenos Bicíclicos , Ozono , Compuestos Orgánicos Volátiles , Monoterpenos/química , Nitratos/química , Aerosoles/análisis , Compuestos Orgánicos Volátiles/química
7.
Int J Mol Sci ; 25(2)2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38255921

RESUMEN

5-Deazaflavins are analogs of naturally occurring flavin cofactors. They serve as substitutes for natural flavin cofactors to investigate and modify the reaction pathways of flavoproteins. Demethylated 5-deazaflavins are potential candidates for artificial cofactors, allowing us to fine-tune the reaction kinetics and absorption characteristics of flavoproteins. In this contribution, demethylated 5-deazariboflavin radicals are investigated (1) to assess the influence of the methyl groups on the electronic structure of the 5-deazaflavin radical and (2) to explore their photophysical properties with regard to their potential as artificial cofactors. We determined the proton hyperfine structure of demethylated 5-deazariboflavins using photochemically induced dynamic nuclear polarization (photo-CIDNP) spectroscopy, as well as density functional theory (DFT). To provide context, we compare our findings to a study of flavin mononucleotide (FMN) derivatives. We found a significant influence of the methylation pattern on the absorption properties, as well as on the proton hyperfine coupling ratios of the xylene moiety, which appears to be solvent-dependent. This effect is enhanced by the replacement of N5 by C5-H in 5-deazaflavin derivatives compared to their respective flavin counterparts.


Asunto(s)
Dinitrocresoles , Protones , Riboflavina , Análisis Espectral , Flavoproteínas
8.
Soft Matter ; 20(3): 558-565, 2024 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-38126532

RESUMEN

Water drops sliding down inclined hydrophobic, insulating surfaces spontaneously deposit electric charges. However, it is not yet clear how the charges are deposited. The influence of added non-hydrolysable salt, acid, or base in the sliding water drops as well as the surrounding humidity on surface electrification and charge formation is also not yet fully understood. Here, we measure the charging on hydrophobic solid surfaces (coated with PFOTS or PDMS) by sliding drops with varying concentration for different types of solutions. Solutions of NaCl, CaCl2, KNO3, HCl, and NaOH, were studied whose concentrations varied in a range of 0.01 to 100 mM. The charge increased slightly at low concentrations and decreased at higher concentrations. We attribute this decrease to the combined effect of charge screening as the non-hydrolysable salt concentration increases and pH driven charge regulation. The effect of humidity on the measured charge was tested over the range from 10% to 90% of humidity. It was found that the influence of humidity on the charge measurements below 70% humidity is low.

9.
Anal Chem ; 96(1): 102-109, 2024 01 09.
Artículo en Inglés | MEDLINE | ID: mdl-38109875

RESUMEN

The direct and unambiguous detection and identification of individual metabolite molecules present in complex biological mixtures constitute a major challenge in (bio)analytical research. In this context, nuclear magnetic resonance (NMR) spectroscopy has proven to be particularly powerful owing to its ability to provide both qualitative and quantitative atomic-level information on multiple analytes simultaneously in a noninvasive manner. Nevertheless, NMR suffers from a low inherent sensitivity and, moreover, lacks selectivity regarding the number of individual analytes to be studied in a mixture of a myriad of structurally and chemically very different molecules, e.g., metabolites in a biofluid. Here, we describe a method that circumvents these shortcomings via performing selective, photochemically induced dynamic nuclear polarization (photo-CIDNP) enhanced NMR spectroscopy on unmodified complex biological mixtures, i.e., human urine and serum, which yields a single, background-free one-dimensional NMR spectrum. In doing this, we demonstrate that photo-CIDNP experiments on unmodified complex mixtures of biological origin are feasible, can be performed straightforwardly in the native aqueous medium at physiological metabolite concentrations, and act as a spectral filter, facilitating the analysis of NMR spectra of complex biofluids. Due to its noninvasive nature, the method is fully compatible with state-of-the-art metabolomic protocols providing direct spectroscopic information on a small, carefully selected subset of clinically relevant metabolites. We anticipate that this approach, which, in addition, can be combined with existing high-throughput/high-sensitivity NMR methodology, holds great promise for further in-depth studies and development for use in metabolomics and many other areas of analytical research.


Asunto(s)
Imagen por Resonancia Magnética , Metabolómica , Humanos , Espectroscopía de Resonancia Magnética/métodos , Metabolómica/métodos
10.
J Phys Chem Lett ; 14(49): 11110-11116, 2023 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-38052008

RESUMEN

Water drops on insulating hydrophobic substrates can generate electric potentials of kilovolts upon sliding for a few centimeters. We show that the drop saturation voltage corresponds to an amplified value of the solid-liquid surface potential at the substrate. The amplification is given by the substrate geometry, the drop and substrate dielectric properties, and the Debye length within the liquid. Next to enabling an easy and low-cost way to measure surface- and zeta- potentials, the high drop voltages have implications for energy harvesting, droplet microfluidics, and electrostatic discharge protection.

11.
Eur Radiol Exp ; 7(1): 67, 2023 11 07.
Artículo en Inglés | MEDLINE | ID: mdl-37932631

RESUMEN

BACKGROUND: Malignant tumors routinely present with irregular shapes and complex configurations. The lack of customization to individual tumor shapes and standardization of procedures limits the success and application of thermal ablation. METHODS: We introduced an automated treatment model consisting of (i) trajectory and ablation profile planning, (ii) ablation probe insertion, (iii) dynamic energy delivery (including robotically driven control of the energy source power and location over time, according to a treatment plan bespoke to the tumor shape), and (iv) quantitative ablation margin verification. We used a microwave ablation system and a liver phantom (acrylamide polymer with a thermochromic ink) to mimic coagulation and measure the ablation volume. We estimated the ablation width as a function of power and velocity following a probabilistic model. Four representative shapes of liver tumors < 5 cm were selected from two publicly available databases. The ablated specimens were cut along the ablation probe axis and photographed. The shape of the ablated volume was extracted using a color-based segmentation method. RESULTS: The uncertainty (standard deviation) of the ablation width increased with increasing power by ± 0.03 mm (95% credible interval [0.02, 0.043]) per watt increase in power and by ± 0.85 mm (95% credible interval [0, 2.5]) per mm/s increase in velocity. Continuous ablation along a straight-line trajectory resulted in elongated rotationally symmetric ablation shapes. Simultaneous regulation of the power and/or translation velocity allowed to modulate the ablation width at specific locations. CONCLUSIONS: This study offers the proof-of-principle of the dynamic energy delivery system using ablation shapes from clinical cases of malignant liver tumors. RELEVANCE STATEMENT: The proposed automated treatment model could favor the customization and standardization of thermal ablation for complex tumor shapes. KEY POINTS: • Current thermal ablation systems are limited to ellipsoidal or spherical shapes. • Dynamic energy delivery produces elongated rotationally symmetric ablation shapes with varying widths. • For complex tumor shapes, multiple customized ablation shapes could be combined.


Asunto(s)
Técnicas de Ablación , Neoplasias Hepáticas , Humanos , Microondas/uso terapéutico , Técnicas de Ablación/métodos , Modelos Teóricos
12.
Phys Chem Chem Phys ; 25(39): 26894-26905, 2023 Oct 11.
Artículo en Inglés | MEDLINE | ID: mdl-37782629

RESUMEN

Heliobacteria are anoxygenic phototrophs that have a Type I homodimeric reaction center containing bacteriochlorophyll g (BChl g). Previous experimental studies have shown that in the presence of light and dioxygen, BChl g is converted into 81-OH-chlorophyll aF (hereafter Chl aF), with an accompanying loss of light-driven charge separation. These studies suggest that the reaction center only loses the ability to transfer electrons once both BChl g' molecules of the P800 special pair have been converted to Chl aF'. The present work confirms that the partially converted BChl g'/Chl aF' special pair remains functional in samples exposed to dioxygen by demonstrating its presence using hyperfine couplings obtained from Q-band 1H ENDOR, 2D 14N HYSCORE and DFT methods. The DFT calculations of the BChl g'/BChl g' homodimeric primary donor, which are based on the recently published X-ray crystal structure, predict that the unpaired electron spin is equally delocalized over both BChl g' molecules and provide an excellent match to the experimental hyperfine couplings of the anaerobic samples. Exposure to dioxygen leads to substantial changes in the hyperfine interactions, indicative of greater localization of the unpaired electron spin. The measured hyperfine couplings are reproduced in the DFT calculations by replacing one of the BChl g' molecules of the primary donor with a Chl aF' molecule. The calculations reveal that the spin density becomes localized on BChl g' in the heterodimeric primary donor. Time-dependent DFT calculations demonstrate that conversion of either or both of the accessory BChl g molecules and/or one of the BChl g' molecules of P800 to Chl aF' results in minor effects on the energy of the charge-separated states. In contrast, if both of the BChl g' molecules of P800 are converted a large increase in the energy of the charge-separated state occurs. This suggests that the reaction center remains functional when only one half of the dimer is converted, however, conversion of both halves of the P800 dimer leads to loss of function.


Asunto(s)
Bacterioclorofila A , Bacterioclorofilas , Clorofila A , Bacterioclorofilas/química , Espectroscopía de Resonancia por Spin del Electrón
13.
Ann Transl Med ; 11(10): 346, 2023 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-37675318

RESUMEN

Background: Liver surgery is the standard of care for primary and many secondary liver tumors. Due to variability and complexity in liver anatomy preoperative imaging is necessary to determine resectability and for planning the surgical strategy. In the last few years, computer-assisted resection planning has been introduced in liver surgery. Aim of this trial was the evaluation of computer-assisted three-dimensional (3D)-navigation for liver surgery. Methods: This study was a prospective randomized-controlled pilot trial and patients were randomized in navigated or non-navigated group. Primary end point was the quotient of intraoperative resected volume and planned resection volume. Secondary end points included operation time, resection margin and postoperative complications. 3D reconstructions were performed with MeVis Distant Services (MeVis AG, Bremen, Germany). The navigation system CAS-One Liver (CAScination AG, Bern, Switzerland) was used for intraoperative computer-assisted 3D-navigation. Results: The data of 16 patients with 20 liver tumors were used in this analysis. Of these, 8 liver tumors were resected with the utilization of intraoperative navigation. Two postoperative complications were classified grade IIIa or higher. There was no difference in duration of operation (189 vs. 180 min, P=0.970), rate of postoperative complications (n=1 vs. n=1, P=0.696) and length of hospital stay (9 vs. 7 days, P=0.368) between the two groups. Minimal resection margin (0.15 vs. 0.40 cm, P=0.384) and quotient of planned to intraoperative resection volume (0.94 vs. 1.11, P=0.305) were also similar. Conclusions: Intraoperative navigation is a technology that can be safely used during liver resection. Surgical accuracy is not yet superior to the current standard of intraoperative orientation. Further technological advances with suitable deformation algorithms and augmented reality systems will enable a further improvement of the technical feasibility.

14.
Angew Chem Int Ed Engl ; 62(43): e202309334, 2023 Oct 23.
Artículo en Inglés | MEDLINE | ID: mdl-37571931

RESUMEN

Deazaflavins are important analogues of the naturally occurring flavins: riboflavin, flavin mononucleotide (FMN), and flavin adenine dinucleotide (FAD). The use of 5-deazaflavin as a replacement coenzyme in a number of flavoproteins has proven particularly valuable in unraveling and manipulating their reaction mechanisms. It was frequently reported that one-electron-transfer reactions in flavoproteins are impeded with 5-deazaflavin as the cofactor. Based on these findings, it was concluded that the 5-deazaflavin radical is significantly less stable compared to the respective flavin semiquinone and quickly re-oxidizes or undergoes disproportionation. The long-standing paradigm of 5-deazaflavin being solely a two-electron/hydride acceptor/donor-"a nicotinamide in flavin clothing"-needs to be re-evaluated now with the indirect observation of a one-electron-reduced (paramagnetic) species using photochemically induced dynamic nuclear polarization (photo-CIDNP) 1 H nuclear magnetic resonance (NMR) under biologically relevant conditions.

15.
J Pers Oriented Res ; 9(1): 17-28, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37389031

RESUMEN

In this article, we demonstrate that latent variable analysis can be of great use in person-oriented research. Starting with exploratory factor analysis of metric variables, we present an example of the problems that come with generalization of aggregate-level results to subpopulations. Oftentimes, results that are valid for populations do not represent subpopulations at all. This applies to confirmatory factor analysis as well. When variables are categorical, latent class analysis can be used to create latent variables that explain the covariation of observed variables. In an example, we demonstrate that latent class analysis can be applied to data from individuals, when the number of observation points is sufficiently large. In each case of latent variables analysis, the latent variables can be considered moderators of the structure of covariation among observed variables.

16.
Chemistry ; 29(42): e202300909, 2023 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-37194623

RESUMEN

The unsubstituted acenium radical cations (ARCs) are extremely sensitive and were hitherto only studied in situ, i. e. in the gas phase, as dilute solutions in strong acids or by matrix isolation spectroscopy at about 10 K. In this study, room temperature stable ARC salts with the weakly coordinating anion [F{Al(ORF )3 }2 ]- (ORF =-OC(CF3 )3 ) supported by the weakly coordinating solvent 1,2,3,4-tetrafluorobenzene (TFB) were prepared and structurally, electrochemically and spectroscopically characterized. Reaction of the neutral acenes with Ag+ [F{Al(ORF )3 }2 ]- led, non-innocent,[54] to intermediate [Ag2 (acene)2 ]2+ complexes, which decompose over time to Ag0 and the corresponding (impure) ARC salts. By contrast, direct deelectronation with the recently developed innocent[54] deelectronator radical cation salt [anthraceneHal ]+⋅ [F{Al(ORF )3 }2 ]- led to phase-pure products [acene]+⋅ [F{Al(ORF )3 }2 ]- (anthraceneHal =9,10-dichlorooctafluoroanthracene; acene=anthra-, tetra-, pentacene). For the first time, a homogenous set of spectroscopic data on analytically pure ARC salts was obtained. In addition, cyclovoltammetric measurements of the acenes connected the potentials in solution with those in the gas-phase. Hence, the data complement the existing isolated gas-phase, strong acid or matrix isolation studies. A first entry to follow-up chemistry of the acenium radical cations as ligand forming oxidizers was demonstrated by reaction with 1 / 2 ${{ 1/2 }}$ Co2 (CO)8 giving [Co(anthracene)(CO)2 ]+ .

17.
J Vasc Access ; : 11297298231175526, 2023 May 17.
Artículo en Inglés | MEDLINE | ID: mdl-37198871

RESUMEN

Central venous cannulation is usually performed via the internal jugular vein (IJV) or subclavian vein (SclV) using the Seldinger technique. The puncture of the SclV can be achieved supraclavicular which was described by Yoffa in 1965. The original approach by Yoffa is based on anatomical landmarks. Ventriculoatrial (VA) shunts in patients suffering from hydrocephalus are becoming more common. It is the procedure of choice in patients with ventriculoperitoneal (VP) shunt complications. We present a case of a female patient with a complex cervical venous anatomy and an obscure inaccessible right internal jugular vein (IJV). Subsequently, we decided to use an ultrasound guided supraclavicular approach to the right subclavian vein for implantation of a VA shunt.

18.
ACS Catal ; 13(8): 5236-5244, 2023 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-37123593

RESUMEN

Well-defined, bench stable Mn(I) non-pincer-type complexes were tested as earth-abundant transition metal catalysts for the selective reduction of CO2 to boryl-protected MeOH in the presence of pinacolborane (HBpin). Essentially, quantitative yields were obtained under mild reaction conditions (1 bar CO2, 60 °C), without the need of any base or additives, in the presence of the alkylcarbonyl Mn(I) bis(phosphine) complexes fac-[Mn(CH2CH2CH3)(dippe)(CO)3] [Mn1, dippe = 1,2-bis(diisopropylphosphino)ethane] and [Mn(dippe)(CO)2{(µ-H)2(Bpin)}] (Mn4), that is obtained by reaction of the bench-stable precatalyst Mn1 with HBpin via elimination of butanal. Preliminary mechanistic details were obtained by a combination of NMR experiments and monitoring of the catalytic reactions.

19.
Nat Commun ; 14(1): 1300, 2023 Mar 09.
Artículo en Inglés | MEDLINE | ID: mdl-36894536

RESUMEN

The growth of lithium dendrites in inorganic solid electrolytes is an essential drawback that hinders the development of reliable all-solid-state lithium metal batteries. Generally, ex situ post mortem measurements of battery components show the presence of lithium dendrites at the grain boundaries of the solid electrolyte. However, the role of grain boundaries in the nucleation and dendritic growth of metallic lithium is not yet fully understood. Here, to shed light on these crucial aspects, we report the use of operando Kelvin probe force microscopy measurements to map locally time-dependent electric potential changes in the Li6.25Al0.25La3Zr2O12 garnet-type solid electrolyte. We find that the Galvani potential drops at grain boundaries near the lithium metal electrode during plating as a response to the preferential accumulation of electrons. Time-resolved electrostatic force microscopy measurements and quantitative analyses of lithium metal formed at the grain boundaries under electron beam irradiation support this finding. Based on these results, we propose a mechanistic model to explain the preferential growth of lithium dendrites at grain boundaries and their penetration in inorganic solid electrolytes.

20.
Chemistry ; 29(29): e202300094, 2023 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-36866600

RESUMEN

The synthesis of imines denotes a cornerstone in organic chemistry. The use of alcohols as renewable substituents for carbonyl-functionality represents an attractive opportunity. Consequently, carbonyl moieties can be in situ generated from alcohols upon transition-metal catalysis under inert atmosphere. Alternatively, bases can be utilized under aerobic conditions. In this context, we report the synthesis of imines from benzyl alcohols and anilines, promoted by KOt Bu under aerobic conditions at room temperature, in the absence of any transition-metal catalyst. A detailed investigation of the radical mechanism of the underlying reaction is presented. This reveals a complex reaction network fully supporting the experimental findings.

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