Article
Materials Science, Multidisciplinary
Eigo Shimaoka, Masaki Kunihiro, Masahiro Funahashi
Summary: Oligo(p-phenylenevinylene)-based chiral nematic liquid crystals were synthesized and showed tunable reflection band for circularly polarized fluorescence. The glassy chiral nematic films exhibited left-handed circularly polarized light at room temperature.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Karel Pomeisl, Natalia Podoliak, Petra Vankatova, Vera Hamplova, Vladimira Novotna, Damian Pociecha, Martin Cigl
Summary: We have designed new chiral mesogens, OXm/n, derived from natural L-serine amino acid with an oxazoline chiral motif. Our focus was on evaluating the synthesis accessibility and preserving the optical purity of these compounds, which was determined by chiral high-performance liquid chromatography. We characterized the mesomorphic properties of the materials and confirmed the phase identification through X-ray scattering studies. Comparisons were made between the conformationally rigid oxazoline chiral moieties in the derivatives OXm/n and the structurally similar smectogens, ZLm/n, with a flexible (S)-lactate chiral unit to investigate the effect of rigidity on the mesomorphic properties.
Article
Biochemistry & Molecular Biology
Emily E. Pocock, Richard J. Mandle, John W. Goodby
Summary: Liquid crystalline dimers and dimesogens have been studied for their twist-bend modulated nematic (N-TB) phases. By selecting mesogenic units with differing polarities and aspect ratios and a bent central spacer, a material has been obtained that exhibits both N-TB and intercalated smectic phases. The higher temperature smectic phase (SmCA) and the lower temperature smectic ''X'' phase with in-plane orthorhombic or monoclinic packing and anticlinic layer organisation have been analyzed.
Article
Biochemistry & Molecular Biology
Aisha Fahim, Onofrio Annunziata
Summary: The addition of small amounts of HEPES near physiological ionic strength is essential for converting protein-rich droplets into compact tetragonal crystalline microparticles, which exhibit small size, narrow size distribution, and guest-binding properties. The interactions between lysozyme and HEPES were found to be weakly attractive and exothermic. These findings suggest that salting-in type additives play an important role in controlling the fate of metastable protein-rich microdroplets.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2021)
Article
Chemistry, Multidisciplinary
Kennedy A. Borchardt-Setter, Lian Yu
Summary: A racemic mixture of chiral molecules can crystallize either as a racemic compound or as a conglomerate of enantiopure crystals. Achiral molecules usually form achiral crystals, but occasionally exhibit chiral structures. The relative energies of chiral and achiral crystals are analyzed, revealing that chiral crystals generally have lower energy when chiral separation occurs on crystallization, while achiral crystals have lower energy when no chiral separation occurs. This analysis suggests that chiral and achiral molecules should be studied together to better understand chirality generation by crystallization.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Organic
Zinaida M. Kaskova, Nadezhda S. Baleeva, Yulia V. Nelyubina, Anastasia A. Andrianova, Zinaida M. Kaskova, Aleksandra S. Tsarkova
Summary: A novel highly fluorescent benzothiophene-based dye with five fused rings was synthesized using a simple two-step method, showing a large Stokes shift in ethanol. The structural features of the compound allow for easy functionalization of the carbon core, potentially leading to the development of new classes of fluorescent dyes.
Article
Polymer Science
Piotr Cieciorski, Pawel W. Majewski, Elzbieta Megiel
Summary: A series of photoresponsive poly(meth)acrylates containing azobenzene groups were synthesized, showing reversible structural transformation under light illumination and high potential for energy storage applications. The enthalpy determined from DSC was relatively high, indicating liquid-crystalline behavior of the materials.
Article
Multidisciplinary Sciences
Sae Hee Ryu, Minjae Huh, Do Yun Park, Chris Jozwiak, Eli Rotenberg, Aaron Bostwick, Keun Su Kim
Summary: The research reports the observation of an unusual band structure at the interface between a crystalline solid (black phosphorus) and disordered alkali-metal dopants. It shows that the depth of the potential tuned by different types of disordered alkali metals leads to the classification of the pseudogap of p-wave and d-wave resonance. These findings may provide insights into the spectrum of various crystalline insulators doped by disordered dopants.
Article
Biochemistry & Molecular Biology
Juan Carlos Aledo
Summary: Methionine-rich prion-like proteins exhibit modular nature with larger molecular sizes and higher spatial compaction compared to average human proteins. Computational evidence suggests that the high compactness might be due to the aggregation of methionine residues, indicating a potential redox regulation. Gene ontology and network analyses reveal that methionine-rich prion-like proteins share more gene ontology terms among themselves than with non-methionine-rich counterparts.
Article
Engineering, Environmental
Lianshan Ni, Ruiting Guo, Wentao Deng, Baowei Wang, Jun Chen, Yu Mei, Jinqiang Gao, Xu Gao, Shouyi Yin, Huanqing Liu, Shu Zhang, Guoqiang Zou, Hongshuai Hou, Xiaobo Ji
Summary: This study successfully improved the structure stability and cycling durability of single-crystalline Ni-rich LiNi0.83Co0.11Mn0.06O2 cathode prepared by molten salt-assisted method, which showed superior capacity retention after 100 cycles. Moreover, increasing Ni fraction can effectively enhance the discharge capacity and energy density, but may lead to aggravated particle microcracking when Ni proportion is higher than 88%, affecting cycling performance.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Hoda A. Ahmed, Tariq Z. Abolibda, Yasser A. M. Ismail, Abdullah Almohammedi, K. A. Aly, Mohamed S. Ibrahim, Sobhi M. Gomha
Summary: A new class of liquid crystalline materials derived from maleic anhydride was synthesized and studied. These materials exhibit enantiotropic nematic mesophases, and the insertion of heterocyclic maleic anhydride moiety influences the stability and range of the nematic phase. The ester linkage group does not significantly promote molecular biaxiality.
FRONTIERS IN CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
R. Jay Braun, Jessica M. J. Swanson
Summary: Lipid droplets are organelles that store and transport neutral lipids. The core of lipid droplets can undergo a phase transformation from amorphous to liquid-crystalline. This transformation affects the physical properties of lipid droplets and can influence protein association. The ordering in the core permeates into the lipid/phospholipid interface, changing the arrangement of lipids and inducing ordering in the phospholipid monolayer. These findings have implications for the recruitment of proteins to lipid droplets under different metabolic conditions.
Article
Oncology
Dominika Radomska, Robert Czarnomysy, Anna Szymanowska, Dominik Radomski, Enrique Dominguez-Alvarez, Anna Bielawska, Krzysztof Bielawski
Summary: This study evaluated the anticancer activity of novel selenoesters in breast cancer cells, and the results showed that these compounds exhibited high cytotoxicity, induced apoptosis and autophagy, and hindered the cell cycle. These findings suggest that selenium-containing compounds have significant potential as candidates for anticancer agents.
Article
Chemistry, Multidisciplinary
Bing Yao, Ziyu Huang, Pengcheng Lin, Lanxu Li, Shifan Wang, Guizhen Gong, Yan Chen, Liming Dong, Xiaohui Wang, Yunxiao Zang
Summary: This study prepared fluorescent chiral liquid-crystalline networks (FCLCN) with liquid-crystalline properties and tunable fluorescence properties, showing reversible chiral texture and highly sensitive fluorescence evolution that can be precisely adjusted by temperature. The FCLCN can be manufactured into temperature-driven dynamic fluorescence patterns with a fast and reversible response.
Article
Chemistry, Inorganic & Nuclear
Yanna Chen, Wenyao Zhang, Donghai An, Maierhaba Abudoureheman, Zhaohui Chen, Hongyu Mi
Summary: A new polymorph of Ba3Zn2(BO3)(3)F, alpha-Ba3Zn2(BO3)(3)F, was synthesized and studied for its structural properties, including an anomalous phase transition with different densities in the two polymorphous phases. This was confirmed by detailed structural analyses using powder X-ray diffraction and differential scanning calorimetry.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Victoria G. Isoppo, Marieli Oliveira Rodrigues, Fabiano S. Rodembusch, Angelica V. Moro
Summary: Herein, we report the synthesis of bis-silylated 2,1,3-benzothiadiazole derivatives and their application in the preparation of photoactive organic-inorganic hybrid materials. The obtained hybrid materials exhibit high quantum yields and fluorescence emission in the solid state.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Physical
Mauro Safir, Emmanuel Santos Moraes, Lilian Camargo da Luz, Fabiano da Silveira Santos, Anthony R. Martin, Rachid Benhida, Luis Gustavo Teixeira Alves Duarte, Fabiano Severo Rodembusch
Summary: This study synthesized a series of benzothiazole-based fluorophores and investigated their photophysical properties in solution and in solid state. The fluorophores showed a large Stokes shift in the solid state.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Elise Ane Maluf Rios, Carla M. B. Gomes, Gabriel L. Silverio, Eduardo Q. Luz, Sher Ali, Caroline da Ros Montes D'Oca, Breidi Albach, Renan B. Campos, Daniel S. Rampon
Summary: In this article, the Ag(i)-catalyzed direct selanylation of indoles with diorganoyl diselenides is described. The reaction efficiently yielded 3-selanylindoles with high regioselectivity, and it also provided direct access to 2-selanylindoles through a Plancher rearrangement-like process when the C3 position of the indole ring was blocked. Experimental analyses and density functional theory calculations were employed to elucidate the reaction mechanism. Among the considered pathways, our findings support a classic electrophilic aromatic substitution via Lewis adducts between Ag(i) and diorganoyl diselenides. The results also offer new insights into the interactions between Ag(i) and diorganoyl diselenides.
Article
Chemistry, Physical
Caroline Gross Jacoby, Jorge Hugo Sbardelotto, Tales da Silva Daitx, Bianca Thais Dalberto, Raquel Santos Mauler, Paulo Henrique Schneider
Summary: This study investigates the application of organocatalysts in polyesters, which are rarely used for this purpose. The proposal is to use the hydroxyl groups in chosen chiral compounds to promote the polymerization of epsilon-caprolactone, generating a support and anchoring the organocatalyst in a single step. A simple acid catalysis method was employed, which showed versatility in generating supported catalysts with different structures and functional groups. The materials were applied as organocatalysts in an aldol addition test reaction, yielding excellent product yields and good stereoselectivity. However, a recycling process seems to be necessary for their reuse.
Article
Chemistry, Analytical
Louise Kommers Reimann, Daniela de Souza Fortes, Fabiano da Silveira Santos, Henrique de Castro Silva Junior, Ana Moira Moras, Dinara Jaqueline Moura, Rodrigo da Costa Duarte, Fabiano Severo Rodembusch
Summary: In this study, heptamethine cyanine dyes were synthesized and their meso-substituted derivatives were prepared. These dyes exhibited UV-Vis absorption and NIR fluorescence emission without aggregation in both ground and excited states. The substitution at the meso position played a crucial role in their photophysics, with the main absorption in the green-orange region. The excited state photophysics showed dependence on the excitation wavelengths, complicating the correlation between spectroscopy and structure. Density Functional Theory and OO-SCS-MP2 calculations revealed the significant impact of conjugation effects on the geometries and electronic configurations of these compounds in both ground and excited states. Finally, the fluorescent properties of the meso-substituted heptamethine cyanine dyes were successfully utilized as stable staining probes in biological media.
Article
Spectroscopy
Natali P. Debia, Jenifer M. Muller, Paulo F. B. Gonsalves, Fabiano S. Rodembusch, Diogo S. Ludtke
Summary: A series of amino acid-derived 1,2,3-triazoles connected by a triazole-4-carboxylate spacer were studied for enantioselective recognition using steady-state fluorescence spectroscopy. Optical sensing was performed with chiral analytes, and the sensors showed specific interactions and photophysical responses with each pair of enantiomers. DFT calculations confirmed the specific interaction between the fluorophores and the analytes, supporting the observed high enantioselectivity of these compounds.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Spectroscopy
Tiago E. A. Frizon, Cristian A. M. Salla, Felipe Grillo, Fabiano S. Rodembusch, Viktor S. Camara, Henrique C. Silva, Eduardo Zapp, Eduardo Junca, Fabio Z. Galetto, Angelica M. de Costa, Gabriela J. Pedroso, Antonio A. Chepluki, Sumbal Saba, Jamal Rafique
Summary: This study synthesized new PMDI derivatives through proton-transfer reactions in the excited state (ESIPT). These compounds exhibited absorption maxima in the ultraviolet region and showed redshifted absorptions compared to the non-ESIPT dye. They also displayed fluorescence emissions dependent on solvent polarity and chemical structure, with ESIPT derivatives showing dual fluorescence and a large Stokes shift. The compounds demonstrated good thermal stability and electrochemical properties.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Chemistry, Applied
Marcelo M. Vieira, Bianca T. Dalberto, Nathalia B. Padilha, Henrique C. S. Junior, Fabiano S. Rodembusch, Paulo H. Schneider
Summary: We developed an efficient and sustainable method for synthesizing fluorescent indolizine derivatives using ultrasound irradiation. These derivatives exhibit UV absorption and violet-to-blue fluorescence emission with a large Stokes shift. Some derivatives show aggregation-induced enhanced emission in water/acetone systems, which is influenced by the substituents. The solid-state derivatives also display tunable full-color fluorescence determined by the substituents. Theoretical calculations accurately reproduce the electronic features of these derivatives.
Article
Chemistry, Multidisciplinary
Roiney Beal, Danillo Valverde, Paulo F. B. Goncalvez, Antonio Carlos Borin
Summary: The UV-VIS photoinduced events of (tz)A and (tz)G embedded into DNA and RNA are described using the Extended Multi-State Second-Order Perturbation Theory (XMS-CASPT2) and electrostatic embedding molecular mechanics methods (QM/MM). The S-1 (1)(pp* L-a) state is found to be the bright state in both environments. The excess energy from the photoexcitation can be dissipated through fluorescence as the electronic population evolves towards its minimum energy structure.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Gul Badshah, Carla M. B. Gomes, Sher Ali, Eduardo Q. Luz, Gabriel L. Silverio, Francielli S. Santana, Diego Seckler, Douglas B. Paixao, Paulo H. Schneider, Daniel S. Rampon
Summary: The direct and selective conversion of a C-H bond into a C-Se bond is a significant challenge. In this study, we successfully achieved the selective selanylation of substrates by using palladium, copper, and the 2-(methylthio)amide directing group. This chelation-assisted direct selanylation method is also applicable for mono and double ortho functionalization of arenes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wystan K. O. Teixeira, Danilo Yano de Albuquerque, Julio Zukerman-Schpector, Diego Seckler, Daniel S. Rampon, Ricardo S. Schwab
Summary: In this study, a copper-mediated domino CuAAC intramolecular selanylation was described for the synthesis of unprecedented fused benzo[4,5][1,3]selenazolo[3,2-c][1,2,3]triazoles from 1,2-bis(2-azidoaryl)diselenides and terminal alkynes under microwave irradiation. It is a pioneering method for the synthesis of these fused heterocycles, which can proceed under mild conditions, tolerate several functional groups, and be carried out using environmentally benign solvents such as dimethyl carbonate. The transformation has also been successfully extended to TMS-protected alkynes and bioactive alkynes. A plausible reaction mechanism is proposed based on several control experiments and previous reports.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Electrochemistry
Fabiele C. Tavares, Camila M. Cholant, Emerson C. Kohlrausch, Gustavo R. Bolzan, Paulo F. B. Goncalves, Eduarda S. Gil, Sherdil Khan, Jairton Dupont, Cesar O. Avellaneda, Marcos Leite J. Santos
Summary: In this study, a new biopolymer gel electrolyte based on xanthan was developed. The addition of ionic liquids BMMI.I and EMMI.I significantly enhanced the ionic conductivity. The interaction between the ionic liquid and the polymer was investigated, and the incorporation of EMMI.I resulted in an electrolyte with the shortest relaxation time and higher ionic conductivity. DSSCs assembled with biopolymer gel electrolytes containing ionic liquids showed an improvement in short-circuit current, indicating the importance of high ionic conductivity.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Marcelo M. Vieira, Bianca T. Dalberto, Nathalia B. Padilha, Henrique C. S. Junior, Fabiano S. Rodembusch, Paulo H. Schneider
Summary: In this report, we synthesized substituted indolizines using ultrasound irradiation in a one-pot and multicomponent strategy, and studied their photophysical properties. The compounds exhibited absorption maxima in the UV-A-violet region and their electronic transitions were related to allowed 1 pi ->pi* transitions. Indolizines showed fluorescence in the violet-to-green region, and the ground and excited states were influenced by the substituents in the indolizine core. The role of solvent in the deactivation of excited states was critical for exploring these compounds as optical sensors for benzene.
JOURNAL OF MOLECULAR STRUCTURE
(2024)
