Article
Chemistry, Physical
Xue-Lian Zheng, Jiu Chen, Qizheng Zheng, Cui-Cui Yang, Xin Zhou, Ling Yang, Wei Quan Tian
Summary: This study reveals the mechanism of enhanced NLO properties in CNTs filled with head-to-tail dipolar molecules, which is mainly attributed to the geometric deformation of the outer nanotube and charge transfer between the nanotube and dipolar molecules. The length of the molecular chain also affects the second-order NLO properties.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Daniel C. A. Valente, Mariana T. do Casal, Mario Barbatti, Thomas A. Niehaus, Adelia J. A. Aquino, Hans Lischka, Thiago M. Cardozo
Summary: Extended quantum chemical calculations were conducted for the tetracene dimer, comparing different methods for predicting ground- and excited-state geometries. While good agreement was observed between methods in spectral shape and state character, DFT/MRCI predicted a doubly excited-state character for the S-1 state.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Austen Moss, Youngwoo Jang, Jacob Arvidson, Hong Wang, Francis D'Souza
Summary: In this study, bisbenzimidazole-fused porphyrin dimers and their derivatives were synthesized and characterized. It was found that these dimers exhibit a split Soret band due to excitonic coupling, regardless of the metal ion in the porphyrin cavity. The study also revealed the importance of the rigid pi-spacer connecting porphyrin dimers in governing energy and electron transfer when coupled with an electron acceptor.
Article
Chemistry, Multidisciplinary
Fakhar Hussain, Riaz Hussain, Muhammad Adnan, Shabbir Muhammad, Zobia Irshad, Muhammad Usman Khan, Junaid Yaqoob, Khurshid Ayub
Summary: This study evaluated small pure Au-m (2 >= m <= 7) and copper-doped Aum-xCux clusters using density functional theory. It found that Cu doping significantly improved the nonlinear optical properties of the clusters, enhancing their NLO response and offering potential applications in optoelectronics and electronics.
Article
Physics, Multidisciplinary
Fulin Deng, Xing-Yan Chen, Xin-Yu Luo, Wenxian Zhang, Su Yi, Tao Shi
Summary: We show analytically that the interaction potential between microwave-shielded polar molecules consists of a shielding core and a modified dipolar interaction. The validity of this effective potential is confirmed by comparing its scattering cross sections with those calculated using the full intermolecular potential. Our results demonstrate the possibility of inducing a scattering resonance under current microwave field conditions. Using the effective potential, we also study the Bardeen-Cooper-Schrieffer pairing in microwave-shielded NaK gas and find a significant enhancement in the superfluid critical temperature near the resonance. These findings open up new paths for exploring the many-body physics of ultracold gases with microwave-shielded molecular gases.
PHYSICAL REVIEW LETTERS
(2023)
Article
Chemistry, Physical
Linke Yu, Fengyu Li
Summary: A highly symmetric structure of metal dimers embedded in defect-graphene was designed and found to be stable. The capability of these structures as gas sensors was investigated and certain structures showed promising sensing properties.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Anna Leo, Andrea Peluso
Summary: A multistep kinetic model, in which solvent motion is treated in the framework of Marcus theory and the rates of the elementary electron transfer step are evaluated at full quantum mechanical level, is proposed and applied to calculate the rates of intramolecular electron transfer reactions in rigidly spaced D-Br-A compounds. The calculated rates agree well with experimental results and accurately reproduce their temperature dependence.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Anna Leo, Andrea Peluso
Summary: A multistep kinetic model, which considers solvent motion within the framework of Marcus theory and evaluates the rates of elementary electron transfer at a quantum mechanical level, is proposed. This model is applied to the calculation of intramolecular electron transfer rates in rigidly spaced compounds with different solvents. The calculated rates agree well with experimental results, and their temperature dependence is accurately reproduced.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Lijing Gong, Cheng Ma, Jinkai Lv, Huan Guo, Guobin Zhao
Summary: This study utilizes density functional theory to investigate multiple new substituted compounds, proposing a method for designing nonlinear optical materials by analyzing the effects of different substituents. The results show that inserting different functional groups at specific positions can effectively reduce the band gap, broaden the absorption spectrum, increase the hyperpolarizability, and potentially become candidates for second-order NLO materials.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Physical
Shirui Xue, Zhaoling Huang, Minghui Yun, Dongjing Liu, Zhiliang Pan, Daoguo Yang
Summary: In this paper, the electronic property and adsorption characteristics of a MoS2-CuO heterojunction on CO, NO, and NO2 gas molecules were calculated. The results showed that the heterojunction is more sensitive to NO polar molecules and has the highest adsorption energy and charge transfer. The hybridization of N-2p, Cu-3d, and O-2p orbits and the charge transfer in the adsorption process were revealed, explaining the high sensitivity to NO molecules. Therefore, the MoS2-CuO heterojunction is a promising gas sensor material for the adsorption and detection of polar molecules.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
M. Negri, L. Francaviglia, D. Kaplan, V Swaminathan, G. Salviati, A. Fontcuberta i Morral, F. Fabbri
Summary: This study demonstrates the excitonic absorption and cathodoluminescence emission of MoS2 micro-pyramids grown on SiO2 substrates by CVD. By utilizing CL emission, defect intra-gap states related to the pyramid edges were detected, with enhanced intensity observed at the pyramid basal vertices. Analysis of photoluminescence and absorption provided insights into the optical functionality of MoS2 pyramids, suggesting potential applications for other 3D structures within the 2D materials family.
Article
Chemistry, Multidisciplinary
Ewan Cruickshank, Grant J. Strachan, Magdalena M. Majewska, Damian Pociecha, Ewa Gorecka, John M. D. Storey, Corrie T. Imrie
Summary: The synthesis and characterization of symmetric liquid crystal dimers containing different terminal chains are reported. The nematogenic behavior is observed in the dimers with short alkylthio or alkyloxy terminal chains, while the higher homologues show the smectic A phase. The dimers with alkylthio chains have lower clearing temperatures compared to those with alkyloxy chains, except for the dimers with the shortest terminal chains. The steric and electronic interactions are discussed to explain the observed behavior.
NEW JOURNAL OF CHEMISTRY
(2023)
Review
Environmental Sciences
V. Yamini, Venkatkumar Shanmugam, M. Rameshpathy, Ganesh Venkatraman, Gnanasambandan Ramanathan, Hakim AL Garalleh, Ahmed Hashmi, Kathirvel Brindhadevi, V. Devi Rajeswari
Summary: The increasing production volume of nanoparticles indicates their widespread applications in industries and homes. However, their presence in the environment can have adverse effects on natural systems. The biological activities and effects of nanoparticles depend on factors such as their entry method, size, shape, charge, area, and chemical composition. Research on nanoparticles' sources, synthesis, fate, and toxicity has significantly advanced in the past decade. This research summarizes the pathways and interactions of nanoparticles in ecosystems, as well as their effects on beneficial microorganisms and methods to reduce their toxicity.
ENVIRONMENTAL RESEARCH
(2023)
Article
Physics, Multidisciplinary
Mohaddeseh Norouzi Azizabad, Hosein Alavi-Rad
Summary: The study investigates the electronic and excitonic optical properties of the newly synthesized two-dimensional material WSi2N4. Results show that WSi2N4 monolayer is a semiconductor with an indirect band gap, and exhibits stable excitonic states at room temperature, making it a promising candidate for optoelectronic applications.
Article
Nanoscience & Nanotechnology
L. van Deurzen, J. Singhal, J. Encomendero, N. Pieczulewski, C. S. Chang, Y. Cho, D. A. Muller, H. G. Xing, D. Jena, O. Brandt, J. Laehnemann
Summary: Using low-temperature cathodoluminescence spectroscopy, the properties of N- and Al- polar AlN layers grown on bulk AlN{0001} by molecular beam epitaxy are studied. Both polarities of layers exhibit a suppression of deep-level luminescence compared to the bulk AlN substrate, a total absence of the prevalent donor with an exciton binding energy of 28 meV, and a much increased intensity of the emission from free excitons. The dominant donor in these layers has an associated exciton binding energy of 13 meV. Additionally, the observation of excited exciton states up to the exciton continuum allows for the direct extraction of the Γ(5) free exciton binding energy of 57 meV.
Article
Chemistry, Physical
Rama Dhali, D. K. Andrea Phan Huu, Francesca Terenziani, Cristina Sissa, Anna Painelli
Summary: This paper warns chemists, physicists, and material scientists about the necessity of precise control over the singlet-triplet gap and strength of spin-orbit coupling for optimized dyes for TADF. It emphasizes the crucial role of low-energy excited states with charge-transfer and local character in TADF efficiency, and calls for the abandonment of the adiabatic approximation in favor of an antiadiabatic approach for fast solvation in models.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Pharmacology & Pharmacy
Martina Ghezzi, Silvia Pescina, Andrea Delledonne, Ilaria Ferraboschi, Cristina Sissa, Francesca Terenziani, Paula De Freitas Rosa Remiro, Patrizia Santi, Sara Nicoli
Summary: The study aimed to improve the solubility and skin retention of Imiquimod using micelles of TPGS and oleic acid, which showed significant enhancement in drug solubility and micellar stability. The delivery efficiency of this formulation was found to be 42- and 25-folds higher than that of commercial creams after application.
Article
Chemistry, Multidisciplinary
Brunella Bardi, Anna Painelli, Monica Panigati, Pierluigi Mercandelli, Francesca Terenziani
Summary: A computational study has rationalized the different phosphorescence colors of two highly emitting crystal polymorphs of a dinuclear Re(I) complex. The electrostatic interactions between the charge distributions on neighboring molecules inside the crystal are responsible for the different stabilization of the emitting triplet state due to the different molecular packing. These self-consistent effects play a major role in the phosphorescence of crystals made of polar and polarizable molecular units, offering a powerful handle to tune the luminescence wavelength in the solid state through supramolecular engineering.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Physical
Andrea Delledonne, Martina Orlandini, Paolo P. Mazzeo, Cristina Sissa, Alessia Bacchi, Francesca Terenziani, Paolo Pelagatti
Summary: A series of new extended linkers containing various polyaromatic chromophores were synthesized through Pd-catalyzed cross-coupling reactions. These linkers exhibited fluorescence in the solid state, making them suitable for the fabrication of fluorescent MOFs.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Giuseppe Soavi, Alessandro Pedrini, Anjali Devi Das, Francesca Terenziani, Roberta Pinalli, Neal Hickey, Barbara Medagli, Silvano Geremia, Enrico Dalcanale
Summary: The effect of the host-guest interaction between cucurbit[8]uril and a model trimethine indocyanine on dye spectral properties and aggregation in water was investigated. The addition of cucurbit[8]uril disrupted the dye aggregates, forming a 1:1 host-guest complex. Supramolecular polymer formation and precipitation were observed at suitable concentrations for NMR experiments.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Martina Ghezzi, Ilaria Ferraboschi, Andrea Delledonne, Silvia Pescina, Cristina Padula, Patrizia Santi, Cristina Sissa, Francesca Terenziani, Sara Nicoli
Summary: This study identified a micellar formulation that can solubilize a significant amount of cyclosporine and promote its transport across ocular barriers. Results showed that TPGS micelles can retain the drug in both the cornea and sclera, with different penetration mechanisms. The study also found that TPGS, as a permeation enhancer, has reversible effects on corneal permeability. This research is of importance for the development of novel drug delivery systems for ocular application.
JOURNAL OF CONTROLLED RELEASE
(2022)
Article
Chemistry, Multidisciplinary
K. Swathi, Meleppatt Sujith, P. S. Divya, P. Merin Varghese, Andrea Delledonne, D. K. Andrea Phan Huu, Francesco Di Maiolo, Francesca Terenziani, Andrea Lapini, Anna Painelli, Cristina Sissa, K. George Thomas
Summary: The phenomenon of excited-state symmetry breaking is often observed in multipolar molecular systems, significantly affecting their photophysical and charge separation behavior. In this study, the intrinsic factors regulating excited-state symmetry breaking in multibranched systems are explored using a combination of experimental and theoretical investigation. It is found that the large Stokes shifts observed in highly symmetric phenyleneethynylenes can be explained by the presence of low-lying dark states, as confirmed by two-photon absorption measurements and TDDFT calculations. In addition, an intense fluorescence emission is observed in these systems contrary to Kasha's rule, and this behavior is explained by a novel phenomenon called symmetry swapping, which describes the inversion of the energy order of excited states as a result of symmetry breaking.
Review
Pharmacology & Pharmacy
Guillem Vargas-Nadal, Mariana Kober, Audrey Nsamela, Francesca Terenziani, Cristina Sissa, Silvia Pescina, Fabio Sonvico, Amirah Mohd Gazzali, Habibah A. Wahab, Luca Grisanti, Maria Eugenia Olivera, Maria Celeste Palena, Maria Laura Guzman, Laura Carolina Luciani-Giacobbe, Alvaro Jimenez-Kairuz, Nora Ventosa, Imma Ratera, Kevin D. Belfield, Ben M. Maoz
Summary: Fluorescent organic nanoparticles (FONs) are a class of nanostructures made up of organic components, which have high tunability and multifunctionality for diagnostic and therapeutic applications in biology and medicine. This review provides a tutorial overview of the design, preparation, characterization, and applications of FONs, as well as recent biomedical applications.
Article
Chemistry, Multidisciplinary
Brunella Bardi, Katerina V. Vygranenko, Beata Koszarna, Olena Vakuliuk, Lukasz Dobrzycki, Daniel T. Gryko, Francesca Terenziani, Anna Painelli
Summary: A new method has been developed to prepare merocyanines, including rhodols, from readily available tetrafluorohydroxybenzaldehyde and aminophenols. This method enables the synthesis of merocyanines with three fluorine atoms and additional conjugated rings under neutral, mild conditions. The transformation of the rhodol chromophore into π-expanded merocyanines allows for the modulation of photophysical properties, such as shifting absorption and emission bands across the visible spectrum, achieving a large Stokes shift, high brightness, strong two-photon absorption, and solvatofluorochromism. Detailed investigation provides insights into the different spectroscopic behavior of rhodols and new merocyanines, including solvatochromism and two-photon absorption.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Francesco Bertocchi, Andrea Delledonne, Guillem Vargas-Nadal, Francesca Terenziani, Anna Painelli, Cristina Sissa
Summary: Aggregates of cyanine dyes are investigated for their tunable spectral properties in this study. The study presents a joint experimental and theoretical analysis of different types of aggregates formed by a family of cyanine dyes. The analysis rationalizes the optical spectra using an essential-state model that takes into account intermolecular interactions, molecular polarizability, and vibronic coupling.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Food Science & Technology
Francesca Accardo, Barbara Prandi, Francesca Terenziani, Tullia Tedeschi, Stefano Sforza
Summary: Flavonoids in cocoa and derived products can interact with proteins, but this interaction does not affect protein bioaccessibility and digestibility during digestion. The interaction between whey proteins and catechins was evaluated in a model system and commercial milk chocolate. The solubilization, hydrolysis, and peptide profile of proteins were determined using in vitro digestion methods. The slight interaction between flavonoids and proteins did not hinder protein digestion and solubilization. The digestibility of proteins in milk chocolate was found to be complete.
FOOD RESEARCH INTERNATIONAL
(2023)
Article
Chemistry, Multidisciplinary
Andrea Delledonne, Martina Orlandini, Francesca Terenziani, Paolo Pio Mazzeo, Alessia Bacchi, Lucia Carlucci, Angiolina Comotti, Jacopo Perego, Paolo Pelagatti
Summary: Three new microporous mixed-ligand MOFs (PUM310, PUM310Me(2), and PUM310CO) were synthesized through solvothermal reactions between bis-pyridine-bis-amide ligands and 2,6-naphthalenedicarboxylic acid. The structural characterization revealed polycatenated frameworks with truncated Zn-paddle wheels, and solvent removal resulted in framework rearrangement and shrinkage. The MOFs exhibited fluorescence in the solid state, and the optical spectra indicated efficient Forster resonance energy transfer (FRET) between the ndca(2-) donor and bis-pyridine acceptors, particularly in PUM310CO.
Article
Chemistry, Physical
Nerea Gonzalez-Pato, Davide Blasi, Domna M. Nikolaidou, Francesco Bertocchi, Jesus Cerda, Francesca Terenziani, Nora Ventosa, Juan Arago, Andrea Lapini, Jaume Veciana, Imma Ratera
Summary: This article reports the preparation and characterization of organic nanoparticles doped with polychlorinated trityl radicals as nanothermometers for temperature sensing. The nanoparticles show excellent thermal sensitivity and have the potential to be used as nanothermometers in bio applications.
Article
Chemistry, Physical
Akriti Mishra, Puspendu Kumar Das
Summary: We investigated the thermodynamics of protein adsorption on negatively charged colloidal gold nanoparticles (GNPs) at pH 7.0. The protein adsorption on GNPs was found to follow Langmuir-type adsorption isotherms at low protein concentrations, but shifted to BET adsorption isotherms at higher protein concentrations, indicating multilayer formation on the GNP surface. The equilibrium binding constants and monolayer thickness were obtained from the measurements. The size of the GNPs influenced the monolayer binding constant, while the size of the protein did not significantly affect the subsequent layer binding constant. The first layer on the GNP surface was stable but removable by centrifugation, while the subsequent layers were weakly bound. The Gibbs free energy changes indicated that the proteins were physiosorbed on the GNP surface. Temperature-dependent data showed that the protein adsorption on GNPs was endothermic with a large increase in entropy. The BET fits suggested that the multilayer adsorption started before monolayer formation and did not occur in a layer-by-layer sequence.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
Federica Faroldi, Brunella Bardi, Irene Tosi, Sandra Doria, Jacopo Isopi, Laura Baldini, Mariangela Di Donato, Massimo Marcaccio, Francesco Sansone, Francesca Terenziani
Summary: The study demonstrates the fast and efficient formation of long-lived excited triplet localized on the fullerene moiety in toluene and chloroform. Electron transfer from Nile Red to fullerene results in the formation of a charge-separated state, leading to the efficient triplet formation due to the singlet/triplet state mixing induced by the weak interaction between the donor and acceptor.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
