The Unified Protocol (UP) theoretically leads to reductions in emotional disorder symptoms by reducing aversive reactions to emotions. However, aversive reactions can take many forms (e.g., ...non-acceptance, behavioral avoidance). We examined if (1) multiple aspects of aversive reactivity predicted session-to-session changes in anxiety and depression in the UP, (2) these aspects reflected a single latent construct, and (3) changes in this latent construct predicted changes in anxiety and depression. Participants (N = 70, M
age
= 33.74, 67.1% female, 74.3% white) completed six sessions of UP modules and measures of aversive reactivity, anxiety, and depression before each session. We used hierarchical linear modeling and random-intercept cross-lagged panel models to test aspects of aversive reactivity and a latent factor of aversive reactivity, respectively, as predictors of session-to-session changes in anxiety and depression. Within-person improvements in four of five aspects of aversive reactivity predicted decreases in anxiety, and improvements in two aspects predicted decreases in depression. However, within-person improvements in latent aversive reactivity predicted decreases in anxiety at five sessions and in depression across all sessions. These results add to the growing literature highlighting the role of aversive reactivity as a potential transdiagnostic process involved in improvements in emotional disorder symptoms during treatment.
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A methodology for the high yield and facile synthesis of isoquinolones from benzamides and alkynes via the oxidative ortho C−H activation of benzamides has been developed. Ag2CO3 proved to be an ...optimal oxidant when MeCN was used as a solvent, and RhCp*Cl22 was utilized as an efficient catalyst. Both N-alkyl and N-aryl secondary benzamides can be applied as effective substrates. Furthermore, primary benzamides react with two alkyne units, leading to tricyclic products via double C−H activation and oxidative coupling. The reactivity of the structurally related 1-hydroxyisoquinoline was also demonstrated, where both N- and O-containing rhodacyclic intermediates can be generated, leading to the construction of different O- or N-containing heterocycles.
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Nanocatalytic tumor therapy is an emerging antitumor option that employs catalytically‐active inorganic nanostructures to produce tumor‐damaging reactive oxygen species. However, initiation of ...nanocatalytic reactions in the tumor intracellular environment is a challenge due to the reliance on acidic pH. By exploiting the pH‐selective multifaceted catalytic activities of Prussian blue‐based nanomaterials (PBNM) as well as the hyperglycolysis characteristics of tumors, it is demonstrated that blocking the monocarboxylate transporter 4 (MCT4)‐mediated lactate effusion in tumor cells can reverse the pH gradient across the tumor cell membrane and cause rapid intracellular acidification as well as neutralization of the extracellular compartment, thus creating vulnerabilities for PBNM‐based nanocatalytic therapies in situ while suppressing tumor stemness/metastasis in vivo. For this purpose, MCT4‐inhibiting siRNAs are incorporated into reactivity‐switchable PBNM‐based nanocatalysts to initiate hydroxyl radical production. Meanwhile, β‐lapachone, a clinically‐approved drug with H2O2‐generating capabilities, is also integrated to sustain the nanocatalytic process. In contrast, the nanocatalyst shows no apparent toxicity to normal cells due to its catalase‐like activities under neutral pH. This treatment strategy can inhibit tumor growth in mice at optimal safety as well as to suppress the cancer cell stemness and lung metastasis, suggesting the clinical translational potential of the findings.
A tumor metabolism modulation strategy is reported to reverse the pH gradient in tumor intracellular and extracellular environment to facilitate the biocatalytic therapy with iron‐based reactivity‐switchable nanocatalysts, which can efficiently inhibit tumor growth and prevent lung metastasis in vivo with reduced health risks. The authors’ findings demonstrate a new approach to regulate tumor cell functions for therapeutic purposes.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Dissolved organic carbon (DOC) measurements and optical properties were applied to assess the photo- and bio-reactivity of dissolved organic matter (DOM) from different sources, including biomass ...leaching, soil leaching and surface waters in a subtropical wetland ecosystem. Samples were exposed to light and/or dark incubated through controlled laboratory experiments. Changes in DOC, ultraviolet (UV-Vis) visible absorbance, and excitation-emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC) were performed to assess sample degradation. Degradation experiments showed that while significant amounts of DOC were consumed during bio-incubation for biomass leachates, a higher degree of bio-recalcitrance for soil leachate and particularly surface waters was displayed. Photo- and bio-humification transformations were suggested for sawgrass, mangrove, and seagrass leachates, as compared to substantial photo-degradation and very little to almost no change after bio-incubation for the other samples. During photo-degradation in most cases the EEM-PARAFAC components displayed photo-decay as compared to a few cases which featured photo-production. In contrast during bio-incubation most EEM-PARAFAC components proved to be mostly bio-refractory although some increases and decreases in abundance were also observed. Furthermore, the sequential photo- followed by bio-degradation showed, with some exceptions, a “priming effect” of light exposure on the bio-degradation of DOM, and the combination of these two processes resulted in a DOM composition more similar to that of the natural surface water for the different sub-environments. In addition, for leachate samples there was a general enrichment of one of the EEM-PARAFAC humic-like component (Ex/Em: <260(305)/416 nm) during photo-degradation and an enrichment of a microbial humc-like component (Ex/Em: <260(325)/406 nm and of a tryptophan-like component (Ex/Em: 300/342 nm) during the bio-degradation process. This study exemplifies the effectiveness of optical property and EEM-PARAFAC in the assessment of DOM reactivity and highlights the importance of the coupling of photo- and bio-degradation processes in DOM degradation.
•EEM PARAFAC was successfully applied to study photo- and bio-degradation of DOM.•Reactivity of biomass and soil leachates was higher than surface water DOM.•Some PARAFAC components were identified as photo and bio degradation intermediates.•DOM solar exposure resulted in priming effect for biodegradation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Cellular processes are carried out by many genes, and their study and optimization requires multiple levers by which they can be independently controlled. The most common method is via a genetically ...encoded sensor that responds to a small molecule. However, these sensors are often suboptimal, exhibiting high background expression and low dynamic range. Further, using multiple sensors in one cell is limited by cross-talk and the taxing of cellular resources. Here, we have developed a directed evolution strategy to simultaneously select for lower background, high dynamic range, increased sensitivity, and low cross-talk. This is applied to generate a set of 12 high-performance sensors that exhibit >100-fold induction with low background and cross-reactivity. These are combined to build a single "sensor array" in the genomes of E. coli MG1655 (wild-type), DH10B (cloning), and BL21 (protein expression). These "Marionette" strains allow for the independent control of gene expression using 12 small-molecule inducers.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
The present article reviews the structures and properties of di-, oligo- and polynuclear transition metal complexes of substituted pyrazolate (pz) ligands with ligating side arms (D
n
) in which the ...N
2-unit of the pyrazole ring acts as a bridge between two metal centres. Extensive literature surveys covering the literature until the beginning of 2008 of symmetrical 3,5-disubstituted ligands of the type D-pz-D-, D
2-pz-D
2- and D
3-pz-D
3 with uni-, bi- and terdentate side arms, respectively, as well as of unsymmetrical 3,5-disubstituted ligands of the type D
1
n
-pz-D
2
m
, are presented together with a comprehensive survey of the structurally characterised complexes thereof. Catalytic and/or stoichiometric reactions of the dinuclear systems are discussed where appropriate.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
477.
Single‐Atom Catalysis in Organic Synthesis Saptal, Vitthal B.; Ruta, Vincenzo; Bajada, Mark A. ...
Angewandte Chemie,
August 21, 2023, Volume:
62, Issue:
34
Journal Article
Peer reviewed
Open access
Single‐atom catalysts hold the potential to significantly impact the chemical sector, pushing the boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal ...species ligated on solid supports, can exist in many coordination environments, all of which have shown important functions in specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging the gap between homogeneous and heterogeneous catalysis. This Review outlines the impressive progress made in recent years regarding the use of single‐atom catalysts in organic synthesis. We also illustrate potential knowledge gaps in the search for more sustainable, earth‐abundant single‐atom catalysts for synthetic applications.
Single‐atom catalysts, featuring atomically dispersed metals on solid carriers, offer limitless possibilities for new, sustainable transformations in the chemical sector. These materials bridge the gap between organometallic and nanoparticle catalysis and are opening exciting avenues for mimicking metalloenzymes. This Review summarizes the impressive progress and potential knowledge gaps in the use of single‐atom catalysts in organic synthesis.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Fusion reactivity for the pB11 fuel has been reassessed for magnetic confinement devices. This study is based on two factors: new measurements of the fusion reaction cross-sections and an accounting ...of the kinetic effects that lead to the increase of the number of protons at higher energies (with respect to a pure Maxwellian). The net effect leads to an approximately 30% increase of the fusion yield for the same global plasma parameters compared to the previous assessments.
Emotion suppression may be linked to poor health outcomes through elevated stress-related physiology. The current meta-analyses investigate the magnitude of the association between suppression and ...physiological responses to active psychological stress tasks administered in the laboratory. Relevant articles were identified through Medline, PsychINFO, PubMed, and ProQuest. Studies were eligible if they (a) used a sample of healthy, human subjects; (b) assessed physiology during a resting baseline and active psychological stress task; and (c) measured self-report or experimentally manipulated suppression. Twenty-four studies were identified and grouped within two separate random effects meta-analyses based on study methodology, namely, manipulated suppression (k = 12) and/or self-report (k = 14). Experimentally manipulated suppression was associated with greater physiological stress reactivity compared to controls (H
g
= 0.20, 95% CI 0.08, 0.33), primarily driven by cardiac, hemodynamic, and neuroendocrine parameters. Self-report trait suppression was not associated with overall physiological stress reactivity but was associated with greater neuroendocrine reactivity (r
=
0.08, 95% CI 0.01, 0.14). Significant moderator variables were identified (i.e., type/duration of stress task, nature of control instructions, type of physiology, and gender). This review suggests that suppression may exacerbate stress-induced physiological arousal; however, this may differ based upon the chosen methodological assessment of suppression.
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The prediction of product translational, vibrational, and rotational energy distributions for arbitrary initial conditions for reactive atom + diatom collisions is of considerable practical interest ...in atmospheric re-entry. Because of the large number of accessible states, determination of the necessary information from explicit (quasi-classical or quantum) dynamics studies is impractical. Here, a machine-learned (ML) model based on translational energy and product vibrational states assigned from a spectroscopic, ro-vibrational coupled energy expression based on the Dunham expansion is developed and tested quantitatively. All models considered in this work reproduce final state distributions determined from quasi-classical trajectory (QCT) simulations with R 2 ∼ 0.98. As a further validation, thermal rates determined from the machine-learned models agree with those from explicit QCT simulations and demonstrate that the atomistic details are retained by the machine learning which makes them suitable for applications in more coarse-grained simulations. More generally, it is found that ML is suitable for designing robust and accurate models from mixed computational/experimental data which may also be of interest in other areas of the physical sciences.
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