Helium, the lightest and most weakly interacting noble gas, is well-known for its unsurpassed chemical inertness. In many applications of helium in experimental techniques, such as tagging, messenger, or nanodroplet isolation action spectroscopy of molecules or complexes, it is assumed that the interaction of helium with the respective species, and thus the resulting interaction-induced perturbation, is small enough not to affect their structure and dynamics. Here, we probe the impact of one up to many attached helium atoms on protonated acetylene─an important nonclassical carbocation subject to three-center two-electron bonding in its ground state structure─using highly accurate interaction potentials in conjunction with entropy-based higher-order nonlinear correlation analysis. In particular, using neural network potentials at CCSD(T) accuracy, we disclose the specific structural perturbations due to the tagging of CH with up to 20 He atoms at a temperature of 1 K. Analysis reveals that microsolvation by helium influences the structure of CH noticeably, while our investigation of the quantum configurational information entropy additionally shows that correlations between individual orientational degrees of freedom are affected as a function of cluster size. In particular, it is found that the most probable bridge-like structure of the ro-vibrational quantum ground state of CH, which is nonplanar and trans-bent in contrast to the perfectly planar equilibrium structure, becomes increasingly more localized upon adding helium atoms. The remarkably nonlinear behavior of the angular correlations as a function of cluster size is traced back to the buildup of the quantum microsolvation shell that enhances anisotropy up to = 6 while more and more isotropic solvation takes over beyond six. Our approach is general and thus sets the stage to investigate the salient effects on the structure of flexible molecules due to tagging beyond the specific case.
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http://dx.doi.org/10.1021/acs.jpca.2c08967 | DOI Listing |
Nanoscale
January 2025
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China.
Photocatalytic detoxification of sulfur mustards (, bis (2-chloroethyl) sulfide, SM) is an effective approach for protecting the ecological environment and human health. In order to fabricate COFs with high performance for the selective transformation of the SM simulant 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO), three porphyrin-based COFs with different donor groups (R = H, OH, and OMe) were synthesized. Among these COFs, COF-OMe, which possesses the strongest electron-donating ability, demonstrated a faster and higher detoxification rate of CEES at various concentrations, achieving selective oxidation of CEES to non-toxic CEESO with 99.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
January 2025
Center for Materials Science and Nanotechnology (SMN), Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, Oslo N-0315, Norway.
The flexibility of the H-ZSM-5 zeolite upon adsorption of selected coke precursors was investigated using both theoretical and experimental approaches. Four structural models with varying active site locations were analyzed through density functional theory (DFT) simulations to determine their responses to different types and quantities of aromatic molecules. Complementary experimental analysis was performed, allowing for a direct comparison with the theoretical findings, using thermogravimetric analysis (TGA), nitrogen adsorption (N adsorption), solid-state NMR, and X-ray diffraction (XRD).
View Article and Find Full Text PDFSmall Methods
January 2025
NEST, Istituto Nanoscienze - CNR and Scuola Normale Superiore, Pisa, I-56127, Italy.
A ground-breaking graphene-based biosensor designed for label-free detection of immunoglobulin M (IgM) achieving a remarkable concentration of 100 zeptomolar (10 m), is reported. The sensor is a two-terminal device and incorporates a millimeter-wide gold interface, bio-functionalized with ≈10 anti-IgM antibodies and capacitively coupled to a bare graphene electrode through a water-soaked paper strip. In this configuration, few affinity binding events trigger a collective electrostatic reorganization of the protein layer, leading to an extended surface potential (SP) shift of the biofunctionalized Au surface.
View Article and Find Full Text PDFInt Clin Psychopharmacol
January 2025
Department of Neuroscience, Rehabilitation, Ophthalmology, Genetics, Maternal and Child Health (DINOGMI), Section of Psychiatry, University of Genoa.
Schizophrenia is a serious psychiatric condition requiring continuous treatment with antipsychotic medications available in different formulations, including oral antipsychotics (OAPs) and long-acting injectables (LAIs). This narrative review aims to comprehensively outline the advantages and disadvantages of OAPs and LAIs to support clinicians in choosing different formulations based on the presentation of clinical symptoms. An electronic search of the PubMed database was performed in June 2024, and additional articles were retrieved from the references or personal knowledge of the authors.
View Article and Find Full Text PDFBioact Mater
April 2025
Wellman Center for Photomedicine and Department of Dermatology, Massachusetts General Hospital, Harvard Medical School, Boston, MA, USA.
Cancer nanovaccines hold the promise for personalization, precision, and pliability by integrating all the elements essential for effective immune stimulation. An effective immune response requires communication and interplay between antigen-presenting cells (APCs), tumor cells, and immune cells to stimulate, extend, and differentiate antigen-specific and non-specific anti-tumor immune cells. The versatility of nanomedicine can be adapted to deliver both immunoadjuvant payloads and antigens from the key players in immunity (i.
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