Article
Chemistry, Physical
Maria Pszona, Sylwester Gawinkowski, Regina Jaeger, Izabela Kaminska, Jacek Waluk
Summary: This study investigates the SERS detection limit of tert-butyl-substituted porphycene derivatives and finds that the ratio between SERS signal and fluorescence background is affected by the molecular structure. The probability of single molecule detection also decreases with the number of moieties attached to the pyrrole ring. These phenomena are attributed to steric hindrance caused by the spatial structure. Furthermore, the sensitivity of SERS technique can be improved by lowering the temperature.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Polymer Science
Ken Albrecht, Eri Hisamura, Minori Furukori, Yasuo Nakayama, Takuya Hosokai, Kohei Nakao, Hiroki Ikebe, Akira Nakayama
Summary: Carbazole dendrimers with bulky terminal substituents and a benzophenone core were synthesized and studied for their thermally activated delayed fluorescence (TADF) properties. The results showed that the choice of substituents directly affected the fluorescence emission and the triplet energy, which correlated with the TADF efficiency. Simple terminal modifications could minimize intermolecular interactions and tune the on-off behavior of TADF.
Article
Chemistry, Multidisciplinary
Axel Olesund, Shima Ghasemi, Kasper Moth-Poulsen, Bo Albinsson
Summary: This study aims to investigate the role of specific types and numbers of substituents in naphthalene annihilator compounds in visible-ultraviolet (UV) triplet-triplet annihilation photochemical upconversion (TTA-UC) processes. The research shows that the type of substituent attached to the naphthalene core is crucial for its performance as an annihilator, and larger substituents can enhance the upconverting ability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Shota Watanabe, Ayumi Tahara, Tasuku Isozaki, Sho Kinoshita, Ryo Takeuchi, Wataru Kashihara, Tadashi Suzuki
Summary: The two-photon absorption of DPA derivatives with different substituents was studied. The experimental two-photon absorption spectra and cross-sections were obtained, and the simulated spectra agreed well with the experimental ones. The enhancement mechanisms for centrosymmetric and non-centrosymmetric DPA derivatives were found to be different. This study provides important information for designing two-photon absorption materials.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Abdul Qaiyum Ramle, Edward R. T. Tiekink, Chee Chin Fei, Nurhidayatullaili Muhd. Julkapli, Wan Jefrey Basirun
Summary: A series of indolenine and barbituric acid zwitterion scaffolds were synthesized via the formation of C-C single bonds with a maximum yield of 98%. The structures were elucidated using various spectroscopic techniques including H-1, C-13 NMR, FT-IR, and HRMS. Single crystal X-ray crystallography analysis confirmed the presence of well-separated iminium and enolate centers in the compound, as well as the twisted nature of the BA ring relative to the indolenine ring. The presence of specific groups favored 1D-supramolecular assembly in the solid state, and the zwitterion exhibited intense molar absorption coefficients in the UV-vis region.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Nicolas Ledos, Thitiporn Sangchai, Iryna Knysh, Manon H. E. Bousquet, Payal Manzhi, Marie Cordier, Denis Tondelier, Bernard Geffroy, Denis Jacquemin, Pierre-Antoine Bouit, Muriel Hissler
Summary: The study shows that substituting lambda(5)-phosphinines with an amino group can alter their optical and redox properties. By combining experimental and theoretical approaches, it was found that the choice of donor diphenylamino group significantly impacts charge transfer nature. Additionally, the use of di(methoxyphenyl)amine can redshift optical properties and enable thermally activated delayed fluorescence in the solid state.
Article
Chemistry, Multidisciplinary
Patrycja Koza, Tomasz Koczorowski, Dariusz T. Mlynarczyk, Tomasz Goslinski
Summary: The aim of this study was to synthesize new unsymmetrical sulfanyl zinc(II) porphyrazines and characterize their physicochemical and electrochemical properties, as well as conduct an initial acute toxicity assessment. The researchers successfully synthesized different zinc(II) porphyrazines with various substituents and characterized them using various analytical techniques. The results showed that these porphyrazines have potential for use in photodynamic therapy, as they demonstrated high singlet oxygen generation quantum yield values. Additionally, the new derivatives were tested for their acute toxicity using a Microtox bioluminescence assay.
APPLIED SCIENCES-BASEL
(2022)
Article
Chemistry, Multidisciplinary
Chidera C. Nnadiekwe, Ahmed Nada, Ismail Abdulazeez, Mohammad R. Imam, Muhammad Ramzan Saeed Ashraf Janjua, Abdulaziz A. Al-Saadi
Summary: The ability to tune the structural properties of dendrimers with respect to size, polarity, and terminal functionalities makes them highly attractive for potential biological and catalytic applications. The synthesized Janus (J) and Twin (T) benzamide-based branched structures were characterized using spectroscopic and theoretical techniques, revealing the orientation of aliphatic chains and linkage configurations. UV-Vis spectra showed consistent absorption around 290 nm, with assigned prominent bands correlating with the molecules' structural and electronic aspects.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Mahmoud M. Ali, Ayman A. Gouda, Khaled F. Alshammari, Mubark Alshareef, Ahmed Alharbi, Aisha Nawaf Al Balawi, Mohamed Ali
Summary: In this study, Ciprofloxacin was used to synthesize a series of charge transfer complexes, which were identified and evaluated using various analytical methods. The results showed that these CT complexes exhibited characteristic spectroscopic properties and demonstrated certain levels of toxicity, antimicrobial activity, antioxidant activity, and biofilm formation capability.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Biochemistry & Molecular Biology
Gamal A. E. Mostafa, Ahmed Bakheit, Najla AlMasoud, Haitham AlRabiah
Summary: This study evaluated the reactions of ketotifen fumarate (KT) with DDQ and TCNQ to form CT complexes using experimental and theoretical approaches. Spectrophotometric methods were validated for KT determination and the stability of the CT complexes was assessed. The molar ratio of KT:DDQ and KT:TCNQ was estimated as 1:1, and the complexes were successfully used for the quantitative determination of KT in its dosage form.
Article
Nanoscience & Nanotechnology
Hongsik Kim, Youngnam Lee, Hyeonho Lee, Jong-In Hong, Dongwhan Lee
Summary: The study developed a triazole-based acceptor unit using a click-to-twist strategy to control the excited-state photophysics of TADF emitters. Six different emitters were prepared using a modular approach, leading to high external quantum efficiency and luminance in organic light emitting diodes.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Maxime Hodee, Julien Massue, Sylvain Achelle, Arnaud Fihey, Denis Tondelier, Gilles Ulrich, Francoise Robin-le Guen, Claudine Katan
Summary: This study investigates the absence of thermally activated delayed fluorescence (TADF) in styrylpyrimidines with bulky electron-donating substituents. The experimental and theoretical investigations reveal that efficient spin-orbit coupling between the energy states cannot be achieved, resulting in the lack of TADF.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Polymer Science
Malgorzata Sypniewska, Anna Kaczmarek-Kedziera, Alexandra Apostoluk, Vitaliy Smokal, Anastasiia Krupka, Robert Szczesny, Beata Derkowska-Zielinska
Summary: The aim of this study was to investigate the influence of various StQ substituents on the luminescence, structural, and optical properties of StQ-containing copolymers. The study found that the change in the nature of the substituent affects the emission band wavelength and can cause a transition in fluorescence color. FTIR and Raman spectroscopies were used to measure the structural properties, while absorbance measurements provided the optical parameters. Computational DFT analysis supported the application of these systems in optoelectronic devices.
Article
Chemistry, Multidisciplinary
Carolin Dusold, Corinna Weiss, Frank Hampel, Andreas Hirsch
Summary: This study presents an unprecedented library of single and double bay-substituted perylene-pentaphenylbenzenes (PPBs), confirming extreme core-distortion and successful elimination of aggregation interactions of perylenes through X-ray analysis. Isomerically pure perylene-PPB hybrids exhibit remarkable differences in their photophysical properties with respect to their regiochemistry and peri-functionalization.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Diana L. Nossa Gonzalez, Jovanny A. Gomez Castano, Carlos A. Franca, Gustavo A. Echeverria, Oscar E. Piro, Mauricio F. Erben
Summary: The synthesis of novel amide compounds with bulky and hydrophilic substituents is reported. These compounds exhibit unique properties due to the combination of steric hindrance and hydrophilicity. Characterization using NMR, IR, and Raman spectroscopy as well as X-ray diffraction analysis reveals their vibrational properties, molecular arrangements, and electronic features. The presence of resonance-assisted hydrogen bonds within the amide core is observed, indicating pi electronic delocalization.
Article
Chemistry, Physical
D. Giavazzi, S. Saseendran, F. Di Maiolo, A. Painelli
Summary: This paper introduces a model that combines molecular aggregates and resonance energy transfer (RET) by utilizing electrostatic intermolecular interactions. The model can describe both RET and energy delocalization and is applicable in both weak and strong coupling regimes, while considering the quantum nature of molecular vibrations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Silvia D'Auria, Alessandro Pedrini, Ilaria Ferraboschi, Jerome Vachon, Cristina Sissa, Roberta Pinalli, Enrico Dalcanale
Summary: In this study, the researchers used two-photon microscopy (2PM) to investigate the compatibility between PE-HEMA and EVOH at the sub-micrometer level. 2PM is a nonlinear fluorescence imaging technique commonly used for thick biological tissue analysis. Polymer blending was visualized using 3D images obtained through 2PM. It was observed that the functionalized PE-HEMA, when reacted with ODIN, formed uniformly distributed blends on the surface and in the bulk, and repeated reprocessing partially reversed the compatibilization by forming ODIN dimers as the most stable H-bonding array in the solid state.
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.
Article
Pharmacology & Pharmacy
Felipe M. Gonzalez-Fernandez, Andrea Delledonne, Sara Nicoli, Paolo Gasco, Cristina Padula, Patrizia Santi, Cristina Sissa, Silvia Pescina
Summary: This research aims to develop nanostructured lipid carriers (NLC) for periocular administration of dexamethasone acetate for the treatment of ocular inflammation. The NLC was formulated using solid and liquid lipid mixtures, resulting in a particle size of 106.9 +/- 1.2 nm, PDI = 0.104 +/- 0.019, and zeta potential = -6.51 +/- 0.575 mV. Ex vivo permeation studies showed that dexamethasone acetate was metabolized into free dexamethasone and exhibited higher permeation capabilities across both sclera and choroid tissues.
Article
Pharmacology & Pharmacy
Adriana Fantini, Luca Giulio, Andrea Delledonne, Silvia Pescina, Cristina Sissa, Sara Nicoli, Patrizia Santi, Cristina Padula
Summary: The optimization of non-invasive formulations for the delivery of high molecular weight compounds is the greatest achievement in the field of advanced drug delivery. Permeation experiments using fatty acids and bile salts as penetration enhancers showed that it is feasible to increase the mucosa permeation of high molecular weight dextrans. This study suggests that buccal administration can be used for the delivery of high molecular weight compounds.
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, Medicinal
Francesco Bertocchi, Cristina Sissa, Anna Painelli
Summary: In this tutorial, we present two alternative methods for calculating the circular dichroism (CD) spectra of non-chiral chromophores in chiral supramolecular assemblies. Despite their apparent differences, these two approaches are based on the same underlying approximations, and are expected to yield similar results. By providing explicit analytical expressions for the CD responses of a dimer in both approaches, we demonstrate their perfect equivalence. Numerical results for larger systems further validate this outcome. This tutorial aims to provide young students and scientists entering the field with a useful introduction to the fascinating topic of supramolecular chirality.
Article
Chemistry, Inorganic & Nuclear
Silvia Ruggieri, Silvia Mizzoni, Chiara Nardon, Enrico Cavalli, Cristina Sissa, Michele Anselmi, Pier Giorgio Cozzi, Andrea Gualandi, Martina Sanadar, Andrea Melchior, Francesco Zinna, Oliver G. Willis, Lorenzo Di Bari, Fabio Piccinelli
Summary: This study synthesized and characterized three complexes and investigated their photophysical and thermodynamic properties. The results showed that the nature of the ligands had a significant impact on the properties of the complexes, and the properties of the complexes also affected their sensitization efficiency towards the metal ions. The ttaligand was found to be the optimal antenna for sensitizing Eu-(III) luminescence, while the Coum ligand sensitized better Tb-(III) luminescence.
INORGANIC CHEMISTRY
(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
Chemistry, Multidisciplinary
Francesco Bertocchi, Danilo Marchetti, Sandra Doria, Mariangela di Donato, Cristina Sissa, Mauro Gemmi, Enrico Dalcanale, Roberta Pinalli, Andrea Lapini
Summary: Our study investigates the impact of hydrogen bond-assisted H-aggregate formation on the optical properties of two functionalized naphthyridine derivatives, ODIN-EtPh and ODIN-But. Through a combination of techniques including X-ray and electron crystallography, spectroscopy, and pump-probe spectroscopy, we reveal that the formation of dimers for ODIN derivatives is inhibited in polar solvents while favored in solvents with poor hydrogen bond-forming capabilities. The presence of a phenyl group linked to the ureidic unit stabilizes the charge-transfer excited state of ODIN derivatives, leading to a reduction in fluorescence emission.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Nanoscience & Nanotechnology
Andrea Delledonne, Elisa Guazzelli, Silvia Pescina, Annalisa Bianchera, Giancarlo Galli, Elisa Martinelli, Cristina Sissa
Summary: The self-assembly properties of unimer micelles were utilized to prepare fluorescent nanocarriers encapsulating hydrophobic fluorophores. These nanocarriers were composed of a copolymer containing oligoethyleneglycol and perflurohexylethyl side chains, and formed small nanoparticles (<10 nm) with tunable properties in water. An easy procedure for encapsulating a small hydrophobic molecule within the nanocarriers was presented, and experimental data showed that the fluorophore was effectively embedded and maintained its emissive properties in water. Additionally, the dye-loaded nanocarriers demonstrated efficacy as a fluorescent probe in two-photon imaging of thick ex vivo porcine scleral tissue.
ACS APPLIED NANO MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Davide Giavazzi, Marvin F. Schumacher, Luca Grisanti, Mattia Anzola, Francesco Di Maiolo, Jennifer Zablocki, Arne Luetzen, Manuela Schiek, Anna Painelli
Summary: This study provides a combined experimental and theoretical investigation of a new type of chiral aggregates with structure-correlated excitonic properties in the visible to near-infrared spectral range. It is found that different alkyl chain lengths can lead to different aggregation scenarios and spectroscopic features, including simultaneous blue- and red-shifted signatures, as well as dominant blue-shifted signatures. The calculation of circular dichroism including intermolecular charge transfer is explicitly expressed for the first time.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Ettore Crovini, Rama Dhali, Dianming Sun, Tomas Matulaitis, Thomas Comerford, Alexandra M. Z. Slawin, Cristina Sissa, Francesco Azzolin, Francesco Di Maiolo, Anna Painelli, Eli Zysman-Colman
Summary: We have studied the synthesis, optoelectronic properties, and theoretical analysis of DMAC-py-TRZ, a novel TADF emitter. The structural difference between DMAC-py-TRZ and DMAC-TRZ leads to significant changes in their steric interactions and photophysics. While the bent structure of DMAC-py-TRZ hinders TADF, emission can be observed from a relaxed orthogonal excited-state geometry. The presence of both conformers in amorphous matrices contributes to the efficiency of DMAC-py-TRZ devices through efficient energy transfer.
JOURNAL OF MATERIALS CHEMISTRY C
(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.