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Energetic electron-induced radiolysis constitutes a highly versatile approach for tailored synthesis and modification of nano- and biomaterials. In doing so, one-step protocols are highly desirable, as they allow for efficient synthesis and combinations of these materials classes in hybrid materials. With this motivation, the formation of iron oxide nanoparticles by electron beam radiolysis was investigated in detail. Particles with an average size of ≈6 nm were synthesized by irradiating microemulsions containing Fe3+ions with 10 MeV electrons. The mechanistic and kinetic details of formation were revealed by pulse radiolysis, and the structural–magnetic properties of the resulting nanoparticles were characterized using high-resolution transmission electron microscopy, selective area diffraction, and vibrating sample magnetometry. The formation of nanoparticles with superparamagnetic properties was observed when microemulsions were irradiated with doses of 50 kGy and above. While the particles obtained from irradiation with just 50 kGy are partially characterized by an amorphous nature, the crystallinity in the magnetite/maghemite phases increases with increasing irradiation dose, as observed via a selective area electron diffraction pattern. This is also reflected in an increasing saturation magnetization.

Dynamic restructuring of silver catalysts during the industrial conversion of methanol to formaldehyde leads to surface faceting and pinhole formation. Subsequent sintering under reaction conditions, followed by increased pressure drop and decreased catalyst activity requires catalyst bed replacement after several months of operation. This necessitates a comprehensive understanding of the bulk catalyst restructuring under exposure to different gas environments. In this work, Ag restructuring was studied at elevated temperatures under different reactive and inert gas environments. Bubble formation within catalysts of 5–8 μm thickness was visualized in real-time using in situX-ray ptychography. Stepwise heating up to 650 °C in combination with imaging was used to determine the effect of temperature on silver restructuring. Dynamic changes within the catalyst were further quantified in terms of relative changes in mass on selected regions at a constant temperature of 500 °C. Quantitative assessment of dynamic changes in the catalyst resulting from bubble growth and movement revealed the influence of temperature, time, and gas environment on the degree of restructuring. Post-mortem scanning electron microscopy with energy-dispersive X-ray spectroscopy mapping confirmed the redistribution of material as a consequence of bubble rupture and collapse. The formation of pores and cavities under different gas environments was additionally confirmed using a fixed bed reactor, and subsequent examination using focused-ion beam milling, providing detailed analysis of the surface structure. This study demonstrates the unique advantage of correlative hard X-ray and electron microscopy for quantitative morphological studies of industrial catalysts.

5-Lipoxygenase (5-LO), a fatty acid oxygenase, is the central enzyme in leukotriene (LT) biosynthesis, potent arachidonic acid-derived lipid mediators released by innate immune cells, that control inflammatory and allergic responses. In addition, through interaction with 12- and 15-lipoxgenases, the enzyme is involved in the formation of omega-3 fatty acid-based oxylipins, which are thought to be involved in the resolution of inflammation. The expression of 5-LO is frequently deregulated in solid and liquid tumors, and there is strong evidence that the enzyme plays an important role in carcinogenesis. However, global inhibition of LT formation and signaling has not yet shown the desired success in clinical trials. Curiously, the release of 5-LO-derived lipid mediators from tumor cells is often low, and the exact mechanism by which 5-LO influences tumor cell function is poorly understood. Recent data now show that in addition to releasing oxylipins, 5-LO can also influence gene expression in a lipid mediator-independent manner. These non-canonical functions, including modulation of miRNA processing and transcription factor shuttling, most likely influence cancer cell function and the tumor microenvironment and might explain the low clinical efficacy of pharmacological strategies that previously only targeted oxylipin formation and signaling by 5-LO. This review summarizes the canonical and non-canonical functions of 5-LO with a particular focus on tumorigenesis, highlights unresolved issues, and suggests future research directions.

Odor perception is inherently subjective. Previous work has shown that odorous molecules evoke distributed activity patterns in olfactory cortices, but how these patterns map on to subjective odor percepts remains unclear. In the present study, we collected neuroimaging responses to 160 odors from 3 individual subjects (18 h per subject) to probe the neural coding scheme underlying idiosyncratic odor perception. We found that activity in the orbitofrontal cortex (OFC) represents the fine-grained perceptual identity of odors over and above coarsely defined percepts, whereas this difference is less pronounced in the piriform cortex (PirC) and amygdala. Furthermore, the implementation of perceptual encoding models enabled us to predict olfactory functional magnetic resonance imaging responses to new odors, revealing that the dimensionality of the encoded perceptual spaces increases from the PirC to the OFC. Whereas encoding of lower-order dimensions generalizes across subjects, encoding of higher-order dimensions is idiosyncratic. These results provide new insights into cortical mechanisms of odor coding and suggest that subjective olfactory percepts reside in the OFC.

JNJ‐64264681 is an irreversible covalent inhibitor of Bruton's tyrosine kinase. This phase 1, first‐in‐human, 2‐part (single‐ascending dose [SAD]; multiple‐ascending dose [MAD]) study evaluated the safety, tolerability, pharmacokinetics (PK), and pharmacodynamics (PD; Bruton's tyrosine kinase occupancy [BTKO]) of JNJ‐64264681 oral solution in healthy participants. For SAD (N = 78), 6 increasing doses of JNJ‐64264681 (4–400 mg) or placebo were evaluated in fasted males. The effects of sex, food, and a capsule formulation were evaluated in separate cohorts. For MAD (N = 27), sequential cohorts of male and female participants received 36/100/200 mg JNJ‐64264681 once daily for 10 days. JNJ‐64264681 exposure (peak concentration; area under the concentration‐time curve) was less than dose proportional from 4 mg to 36 mg. Dose‐normalized area under the concentration‐time curves following the 36 mg and 100 mg doses were generally similar. The mean terminal half‐life was 1.6–13.2 hours. With multiple doses, steady state was achieved by day 2. A semimechanistic PK/PD model was developed using the first 5 SAD cohorts’ data to predict %BTKO in MAD cohorts. PK/PD model guided dose‐escalation, and all participants in the 200/400 mg single‐dose cohorts achieved ≥90% BTKO at 4 hours after dosing (peak) with prolonged occupancy. As BTKO data became available from MAD cohorts, it was found that observed BTKO data were consistent with model predictions. JNJ‐64264681 showed no safety signals of concern. Overall, safety, tolerability, PK, BTKO, and PK/PD modeling guided the rationale for dose selection for the subsequent first‐in‐patient lymphoma studies.

A series of {V12}-nuclearity polyoxovanadate cages covalently functionalized with one or sandwiched by two phthalocyaninato (Pc) lanthanide (Ln) moieties viaV–O–Ln bonds were prepared and fully characterized for paramagnetic Ln = SmIII–ErIIIand diamagnetic Ln = LuIII, including YIII. The LnPc-functionalized {V12O32} cages with fully oxidized vanadium centers in the ground state were isolated as (nBu4N)3[HV12O32Cl(LnPc)] and (nBu4N)2[HV12O32Cl(LnPc)2] compounds. As corroborated by a combined experimental (EPR, DC and AC SQUID, laser photolysis transient absorption spectroscopy, and electrochemistry) and computational (DFT, MD, and model Hamiltonian approach) methods, the compounds feature intra- and intermolecular electron transfer that is responsible for a partial reduction at V(3d) centers from VVto VIVin the solid state and at high sample concentrations. The effects are generally Ln dependent and are clearly demonstrated for the (nBu4N)3[HV12O32Cl(LnPc)] representative with Ln = LuIIIor DyIII. Intramolecular charge transfer takes place for Ln = LuIIIand occurs from a Pc ligand viathe Ln center to the {V12O32} core of the same molecule, whereas for Ln = DyIII, only intermolecular charge transfer is allowed, which is realized from Pc in one molecule to the {V12O32} core of another molecule usually viathe nBu4N+countercation. For all Ln but DyIII, two of these phenomena may be present in different proportions. Besides, it is demonstrated that (nBu4N)3[HV12O32Cl(DyPc)] is a field-induced single molecule magnet with a maximal relaxation time of the order 10–3s. The obtained results open up the way to further exploration and fine-tuning of these three modular molecular nanocomposites regarding tailoring and control of their Ln-dependent charge-separated states (induced by intramolecular transfer) and relaxation dynamics as well as of electron hopping between molecules. This should enable us to realize ultra-sensitive polyoxometalate powered quasi-superconductors, sensors, and data storage/processing materials for quantum technologies and neuromorphic computing.

5-Lipoxygenase (5-LO), the central enzyme in the biosynthesis of leukotrienes, is frequently expressed in human solid malignancies even though the enzyme is not present in the corresponding healthy tissues. There is little knowledge on the consequences of this expression for the tumor cells regarding gene expression and cellular function. We established a knockout (KO) of 5-LO in different cancer cell lines (HCT-116, HT-29, U-2 OS) and studied the consequences on global gene expression using next generation sequencing. Furthermore, cell viability, proliferation, migration and multicellular tumor spheroid (MCTS) formation were studied in these cells. Our results show that 5-LO influences the gene expression and cancer cell function in a cell type-dependent manner. The enzyme affected genes involved in cell adhesion, extracellular matrix formation, G protein signaling and cytoskeleton organization. Furthermore, absence of 5-LO elevated TGFβ2expression in HCT-116 cells while MCP-1, fractalkine and platelet-derived growth factor expression was attenuated in U-2 OS cells suggesting that tumor cell-derived 5-LO shapes the tumor microenvironment. In line with the gene expression data, KO of 5-LO had an impact on cell proliferation, motility and MCTS formation. Interestingly, pharmacological inhibition of 5-LO only partly mimicked the KO suggesting that also noncanonical functions are involved.

Graphene liquid cell transmission electron microscopy (TEM) has enabled the observation of a variety of nanoscale transformations. Yet understanding the chemistry of the liquid cell solution and its impact on the observed transformations remains an important step toward translating insights from liquid cell TEM to benchtop chemistry. Gold nanocrystal etching can be used as a model system to probe the reactivity of the solution. FeCl3has been widely used to promote gold oxidation in bulk and liquid cell TEM studies, but the roles of the halide and iron species have not been fully elucidated. In this work, we observed the etching trajectories of gold nanocrystals in different iron halide solutions. We observed an increase in gold nanocrystal etch rate going from Cl–- to Br–- to I–-containing solutions. This is consistent with a mechanism in which the dominant role of halides is as complexation agents for oxidized gold species. Additionally, the mechanism through which FeCl3induces etching in liquid cell TEM remains unclear. Ground-state bleaching of the Fe(III) absorption band observed through pulse radiolysis indicates that iron may react with Cl2·–radicals to form an oxidized transient species under irradiation. Complete active space self-consistent field (CASSCF) calculations indicate that the FeCl3complex is oxidized to an Fe species with an OH radical ligand. Together our data indicate that an oxidized Fe species may be the active oxidant, while halides modulate the etch rate by tuning the reduction potential of gold nanocrystals.

Substituted 2,6-dicyanoanilines are versatile electron donor–acceptor compounds, which have recently received considerable attention, since they exhibit strong fluorescence and may have utility in the synthesis of fluorescent materials, non-natural photosynthetic systems, and materials with nonlinear optical properties. The majority of known synthetic procedures are, however, “stop-and-go” reaction processes involving time-consuming and waste-producing isolation and purification of product intermediates. Here, we present the synthesis of substituted 2,6-dicyanoanilines via atom-economical and eco-friendly one-pot processes, involving metal-free domino reactions, and their subsequent photochemical and photophysical measurements and theoretical calculations. These studies exhibit the existence of an easily tunable radical ion pair-based charge-transfer (CT) emission in the synthesized 2,6-dicyanoaniline-based electron donor–acceptor systems. The charge-transfer processes were explored by photochemical and radiation chemical measurements, in particular, based on femtosecond laser photolysis transient absorption spectroscopy and time-resolved emission spectroscopy, accompanied by pulse radiolysis and complemented by quantum chemical investigations employing time-dependent density-functional theory. This chromophore class exhibits a broad-wavelength-range fine-tunable charge recombination emission with high photoluminescence quantum yields up to 0.98. Together with its rather simple and cost-effective synthesis (using easily available starting materials) and customizable properties, it renders this class of compounds feasible candidates as potential dyes for future optoelectronic devices like organic light-emitting diodes (OLEDs).

Although it is widely accepted that the orbitofrontal cortex (OFC) is important for decision making, its precise contribution to behavior remains a topic of debate. While many loss of function experiments have been conducted in animals, causal studies of human OFC function are relatively scarce. This review discusses recent causal investigations into the human OFC, with an emphasis on advances in network-based brain stimulation approaches to indirectly perturb OFC function. Findings show that disruption of human OFC impairs decisions that require mental simulation of outcomes. Taken together, these results support the idea that human OFC contributes to decision making by representing a cognitive map of the task environment, facilitating inference of outcomes not yet experienced. Future work may utilize similar non-invasive approaches in clinical settings to mitigate decision making deficits in neuropsychiatric disorders.

Accessibility of the human genome is modulated by the ATP-driven SWI/SNF chromatin remodeling multiprotein complexes BAF (BRG1/BRM-associated factor) and PBAF (polybromo-associated BAF factor), which involves reading of acetylated histone tails by the bromodomain-containing proteins SMARCA2 (BRM), SMARCA4 (BRG1), and polybromo-1. Dysregulation of chromatin remodeling leads to aberrant cell proliferation and differentiation. Here, we have characterized a set of potent and cell-active bromodomain inhibitors with pan-selectivity for canonical family VIII bromodomains. Targeted SWI/SNF bromodomain inhibition blocked the expression of key genes during adipogenesis, including the transcription factors PPARγ and C/EBPα, and impaired the differentiation of 3T3-L1 murine fibroblasts into adipocytes. Our data highlight the role of SWI/SNF bromodomains in adipogenesis and provide a framework for the development of SWI/SNF bromodomain inhibitors for indirect targeting of key transcription factors regulating cell differentiation.

There are notably few literature reports of electron donor–acceptor oligoynes, even though they offer unique opportunities for studying charge transport through “all-carbon” molecular bridges. In this context, the current study focuses on a series of carbazole−(C≡C)n−2,5-diphenyl−1,3,4-oxadiazoles (n= 1–4) as conjugated π-systems in general and explores their photophysical properties in particular. Contrary to the behavior of typical electron donor–acceptor systems, for these oligoynes, the rates of charge recombination after photoexcitation increase with increasing electron donor–acceptor distance. To elucidate this unusual performance, we conducted detailed photophysical and time-dependent density functional theory investigations. Significant delocalization of the molecular orbitals along the bridge indicates that the bridging states come into resonance with either the electron donor or acceptor, thereby accelerating the charge transfer. Moreover, the calculated bond lengths reveal a reduction in bond-length alternation upon photoexcitation, indicating significant cumulenic character of the bridge in the excited state. In short, strong vibronic coupling between the electron-donating N-arylcarbazoles and the electron-accepting 1,3,4-oxadiazoles accelerates the charge recombination as the oligoyne becomes longer.

Thyroid hormones (THs) operate numerous physiological processes through modulation of the nuclear thyroid hormone receptors and several other proteins. We report direct activation of the nuclear peroxisome proliferator-activated receptor gamma (PPARγ) and retinoid X receptor (RXR) by classical and nonclassical THs as another molecular activity of THs. The T4 metabolite TETRAC was the most active TH on PPARγ with nanomolar potency and binding affinity. We demonstrate that TETRAC promotes PPARγ/RXR signaling in cell-free, cellular, and in vivosettings. Simultaneous activation of the heterodimer partners PPARγ and RXR resulted in high dimer activation efficacy. Compared to fatty acids as known natural ligands of PPARγ and RXR, TETRAC differs markedly in its molecular structure and the PPARγ-TETRAC complex revealed a distinctive binding mode of the TH. Our observations suggest a potential connection of TH and PPAR signaling through overlapping ligand recognition and may hold implications for TH and PPAR pharmacology.

Computed tomography spans a versatile set of techniques that range several length scales and modalities. It is common to them all that the sample must be prepared in a way which allows for addressing the scientific question(s) posed as well as being suitable for the specific setup of the experiment. We present two lathe-based sample preparation workflows developed to prepare biomineralized samples (here bone) for two very different experiments in terms of setup, types of questions asked, and sample requirements. The first experiment, involving the measurement of high throughput (synchrotron) micro-tomography, required the preparation of many samples with homogeneity in size, shape, and bone site. This was achieved through a particular sequence of cutting and embedding steps finalized by lathe milling. The resulting samples were cylindrical in shape with diameters close to the field of view of the ensuing tomography experiment, which allowed maximizing the investigated sample volumes. The second experiment was a combined ptychography and X-ray fluorescence nano-tomography experiment, which required preparation of a few-micrometer-sized sample. Moreover, the scientific interest was in a specific, localized feature in bone. Thus, the sample had to be extracted from a precise location from within the whole bone. Again, the developed workflow comprised many steps, including both lathe milling and focused ion beam milling. Importantly, localized preparation was enabled by measuring in-house X-ray micro-computed tomography at crucial points in the workflow. The presented workflows provide examples of preparation pathways that can be standardized and strongly increase the throughput, quality, and success rate of tomography experiments.

The hierarchical pore systems of Pt/Al2O3exhaust gas aftertreatment catalysts were analyzed with a collection of correlative imaging techniques to monitor changes induced by hydrothermal aging. Synergistic imaging with laboratory X-ray microtomography, synchrotron radiation ptychographic X-ray computed nanotomography, and electron tomography allowed quantitative observation of the catalyst pore architecture from centimeter to nanometer scale. Thermal aging at 750 °C in air and hydrothermal aging at 1050 °C in 10% H2O/air caused increasing structural degradation, which manifested as widespread sintering of Pt particles, increased volume and quantity of macropores (>20 nm), and reduction in effective surface area coupled with decreasing volume and frequency of mesopores (2–20 nm) and micropores (<2 nm). Electron tomography unraveled the three-dimensional (3D) structure with high resolution allowing visualization of meso- and macropores but with samples of maximum 300 nm thickness. To complement this, hard X-ray ptychographic tomography produced quantitative 3D electron density maps of 5 μm diameter samples with spatial resolution <50 nm, effectively filling the resolution gap between electron tomography and hard X-ray microtomography. The obtained 3D volumes are an essential input for future computational modeling of fluid dynamics, mass transport, or diffusion properties and may readily complement bulk one-dimensional porosimetry measurements or simulated porosity.

In this Letter, we report on the creation of hard x-ray beams carrying orbital angular momentum of topological charge −ℏ and −3ℏ at a photon energy of 8.2 keV via spiral phase plates made out of fused silica by ultrashort-pulsed laser ablation. The phase plates feature a smooth phase ramp with a 0.5 μm nominal step height and a surface roughness of 0.5 μm. The measured vortex beams show submicrometer-sized donut rings and agree well with numerical modeling. Fused silica phase plates are potentially suited to manipulate the electromagnetic field in highly intense x-ray beams at x-ray free-electron laser sources.

Cells must cope with toxic or reactive intermediates formed during metabolism. One coping strategy is to sequester reactions that produce such intermediates within specialized compartments or tunnels connecting different active sites. Here, we show that propionyl-CoA synthase (PCS), an ∼ 400-kDa homodimer, three-domain fusion protein and the key enzyme of the 3-hydroxypropionate bi-cycle for CO2fixation, sequesters its reactive intermediate acrylyl-CoA. Structural analysis showed that PCS forms a multicatalytic reaction chamber. Kinetic analysis suggested that access to the reaction chamber and catalysis are synchronized by interdomain communication. The reaction chamber of PCS features three active sites and has a volume of only 33 nm3. As one of the smallest multireaction chambers described in biology, PCS may inspire the engineering of a new class of dynamically regulated nanoreactors.

Raman scattering investigations of the diamond peak properties of nanodiamonds with a size of 25 nm were performed in terms of temperature and laser power dependency. A similar trend of a bathochromic shift with increasing temperature and laser power was found, indicating the optical induced heating mechanism to be one of the main influencing factors on the Raman scattering behavior of nanodiamonds. As a direct consequence, nanodiamond particle impurities such as graphite have an indirect influence on the diamond peak properties by means of enhanced optical absorption of the particle, resulting in a higher rate of photoinduced heating. The results presented here are not only supplementing the list of influencing factors on the Raman scattering properties of nanodiamonds, but they also demonstrate that even a low graphite content leads to local particle temperature differences in the range of hundreds of °C already at low laser intensities within the range 105W/cm2with a substantial effect on the Raman spectrum of the nanodiamonds. This effect needs to be considered in numerous potential applications utilizing nanodiamonds as sensors.

Sulfur-containing molecules participate in many essential biological processes. Of utmost importance is the methylthioether moiety, present in the proteinogenic amino acid methionine and installed in tRNA by radical-S-adenosylmethionine methylthiotransferases. Although the thiol–ene reaction for carbon–sulfur bond formation has found widespread applications in materials or medicinal science, a biocompatible chemo- and regioselective hydrothiolation of unactivated alkenes and alkynes remains elusive. Here, we describe the design of a general chemoselective anti-Markovnikov hydroalkyl/aryl thiolation of alkenes and alkynes—also allowing the biologically important hydromethylthiolation—by triplet–triplet energy transfer activation of disulfides. This fast disulfide–ene reaction shows extraordinary functional group tolerance and biocompatibility. Transient absorption spectroscopy was used to study the sensitization process in detail. The hereby gained mechanistic insights were successfully employed for optimization of the catalytic system. This photosensitized transformation should stimulate bioimaging applications and carbon–sulfur bond-forming late-stage functionalization chemistry, especially in the context of metabolic labelling. Triplet–triplet energy transfer activation of disulfides enables the chemoselective anti-Markovnikov hydroalkyl/aryl thiolation of alkenes and alkynes—and can also be used for the biologically important hydromethylthiolation reaction. This fast disulfide–ene reaction is biocompatible and is tolerant of a wide range of functional groups. The triplet–triplet energy transfer sensitization process was studied in detail with transient absorption spectroscopy.

In many insects, mating induces drastic changes in male and female responses to sex pheromones or host-plant odors. In the male moth Agrotis ipsilon, mating induces a transient inhibition of behavioral and neuronal responses to the female sex pheromone. As neuropeptides and peptide hormones regulate most behavioral processes, we hypothesize that they could be involved in this mating-dependent olfactory plasticity. Here we used next-generation RNA sequencing and a combination of liquid chromatography, matrix assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and direct tissue profiling to analyze the transcriptome and peptidome of different brain compartments in virgin and mated males and females of A. ipsilon.We identified 37 transcripts encoding putative neuropeptide precursors and 54 putative bioactive neuropeptides from 23 neuropeptide precursors (70 sequences in total, 25 neuropeptide precursors) in different areas of the central nervous system including the antennal lobes, the gnathal ganglion, and the corpora cardiaca–corpora allata complex. Comparisons between virgin and mated males and females revealed tissue-specific differences in peptide composition between sexes and according to physiological state. Mated males showed postmating differences in neuropeptide occurrence, which could participate in the mating-induced olfactory plasticity.

A dinuclear ruthenium complex bridged by 2,3,5,6-pyrazinetetracarboxylic acid (μ-LH22–) was synthesized and characterized by X-ray crystallography, cyclic voltammetry under ambient and elevated pressures, electron paramagnetic resonance (EPR) and UV/vis-NIR (NIR = near-infrared) spectroelectrochemistry, pulse radiolysis, and computational methods. We probed for the first time in the field of mixed-valency the use of high-pressure electrochemical methods. The investigations were directed toward the influence of the protonation state of the bridging ligand on the electronic communication between the ruthenium ions, since such behavior is interesting in terms of modulating redox chemistry by pH. Starting from the [RuII(μ-LH22–)RuII]0configuration, which shows an intense metal-to-ligand charge transfer absorption band at 600 nm, cyclic voltammetry revealed a pH-independent, reversible one-electron reduction and a protonation-state-dependent (proton coupled electron transfer, PCET) reversible oxidation. Deeper insight into the electrode reactions was provided by pressure-dependent cyclic voltammetry up to 150 MPa, providing insight into the conformational changes, the protonation state, and the environment of the molecule during the redox processes. Spectroelectrochemical investigations (EPR, UV/vis-NIR) of the respective redox reactions suggest a ligand-centered radical anion [RuII(μ-LH2•3–)RuII]−upon reduction (EPR Δg= 0.042) and an ambiguous, EPR-silent one-electron oxidized state. In both cases, the absence of the otherwise typical broad intervalence charge transfer bands in the NIR region for mixed-valent complexes support the formulation as radical anionic bridged compound. However, on the basis of high-pressure electrochemical data and density functional theory calculations the one-electron oxidized form could be assigned as a charge-delocalized [RuII.5(μ-LH22–)RuII.5]+valence tautomer rather than [RuIII(μ-LH2•3–)RuIII]+. Deprotonation of the bridging ligand causes a severe shift of the redox potential for the metal-based oxidation toward lower potentials, yielding the charge-localized [RuIII(μ-LH3–)RuII]0complex. This PCET process is accompanied by large intrinsic volume changes. All findings are supported by computational methods (geometry optimization, spin population analysis). For all redox processes, valence alternatives are discussed.

In this study, a new modified C60derivative with an oPE/oPPV conjugated bridge bearing two pyridyl groups has been used in combination with a flexible porphyrin dimer (ZnP2) to construct an electron donor/acceptor hybrid (C60-dipyr·ZnP2). This hybrid is based on metal to ligand coordination between the zinc centers of the porphyrin dimer and the two pyridyl groups that oPE/oPPV linker bears. In order to investigate the interactions between the electron donor and acceptor entities, both in the ground state and in the excited states, comprehensive photophysical assays have been carried out. In particular, both absorption and fluorescence titrations provided evidence for strong interactions between the electron donor and the electron acceptor within the hybrid. A binding constant (Kass) in the order of 5.0 × 105M–1has been derived. Furthermore, transient absorption measurements revealed intramolecular electron-transfer from the photoexcited porphyrin dimer (ZnP2) to the fullerene derivative (C60-dipyr), leading to a long-lived charge-separated state with a lifetime of up to 1525 ps.

We consider a non-isothermal multi-phase field model. We subsequently discretize implicitly in time and with linear finite elements. The arising algebraic problem is formulated in two variables where one is the multi-phase field, and the other contains the inverse temperature field. We solve this saddle point problem numerically by a non-smooth Schur–Newton approach using truncated non-smooth Newton multigrid methods. An application in grain growth as occurring in liquid phase crystallization of silicon is considered.