Article
Chemistry, Multidisciplinary
Melissa A. Reith, Irene De Franceschi, Matthieu Soete, Nezha Badi, Resat Aksakal, Filip E. Du Prez
Summary: The study proposes a robust strategy for the synthesis of sequence-defined, discrete star-shaped macromolecules. The iterative approach allows for the preparation of asymmetrically branched macromolecules with high purity and yields, enabling sequence definition, precise insertion of branching points, and orthogonal end-group functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Alexander A. Puchkov, Nikita G. Sedush, Alexander I. Buzin, Timur N. Bozin, Artem V. Bakirov, Roman S. Borisov, Sergei N. Chvalun
Summary: The main goal of this research is to study the ring-opening polymerization of L-lactide in the presence of multifunctional alcohols in order to determine the optimal conditions for synthesizing star-shaped molecules with predetermined structures for biomedical applications. The study found that the polymerization rate and initiation rate of co-initiator's hydroxyl groups can vary significantly depending on the alcohol's structure and concentration. Various instrumental methods were used to prove the absence of cyclic, linear, and comet-like structures in the synthesized star-shaped PLLA. Additionally, DSC and WAXS analysis showed that branching limits segmental mobility of the PLLA chains and hinders crystallization of the star-shaped poly(L-lactides).
Article
Polymer Science
Justyna Jurek-Suliga, Zbigniew Grobelny, Sylwia Golba, Hubert Okla, Katarzyna Bednarczyk
Summary: Polyether-pentols (PEPOs) were synthesized from glycidyl ethers and butylene oxide using tripotassium salts of 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol (HMCH) activated 18C6 for ring-opening polymerization (ROP), resulting in the formation of bi- or trimodal polymers. In the crosslinked PUR synthesis, the hydrogen bond index for coupling of hard segments was calculated, and the range of phase separation was higher for PUR-containing aromatic rings as substituents.
Review
Polymer Science
N. Moini, A. Jahandideh, F. Shahkarami, K. Kabiri, F. Piri
Summary: This paper reviews the synthesis, doping, and properties of linear and multi-arm star-shaped oligoanilines, investigating how molecular design affects their morphology and electrochemical behavior, and how to tune these systems for a wide range of applications.
Article
Chemistry, Multidisciplinary
Xiang Li, Qin Zhou, Miao Zhu, Wei Chen, Beibei Wang, Ye Sha, Hong Yan
Summary: A novel star-shaped molecule based on TPE-o-carborane with a triphenylamine core has been synthesized, showing an improved luminescent quantum yield of 62% in the solid state.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhaopeng Yu, Xiaohu Feng, Chenqi Zhao, Jiajun Li, Ruofan Liu, Yushun Jin, Yibo Wu
Summary: Linear and star-shaped telechelic polyisobutylene with hydroxyl-terminated ends were successfully synthesized through living cationic polymerization using propylene oxide/Titanium tetrachloride as the initiator system. The one-step method using epoxide as the functional initiator shows potential for industrial application, and the polymerization mechanism was proposed based on end structure analysis and Gaussian calculation results.
Article
Chemistry, Multidisciplinary
Kotaro Obayashi, Keiichi Imato, Satoshi Aoyama, Toshiaki Enoki, Seiji Akiyama, Mio Ishida, Seiji Suga, Koichi Mitsudo, Yousuke Ooyama
Summary: The study focused on the design and synthesis of three 4,4'-bibenzo[c]thiophene derivatives, with subsequent characterization using various analytical techniques. Variations in photophysical properties and energy levels were observed in both solution and solid state environments for the derivatives.
Article
Polymer Science
Yulia S. Dyuzhikova, Anton A. Anisimov, Alexander S. Peregudov, Mikhail I. Buzin, Galina G. Nikiforova, Viktor G. Vasil'ev, Sergey A. Kostrov, Alexander I. Buzin, Alexei A. Stupnikov, Yulia N. Malakhova, Olga I. Shchegolikhina, Aziz M. Muzafarov
Summary: New non-crystallizable low-dispersity star-shaped polydimethylsiloxanes (PDMS) containing various substituents at silicon atoms were synthesized and their thermal and viscous properties were studied. The synthesized compounds were characterized using a range of physicochemical analysis methods.
Article
Engineering, Environmental
Jing He, Tao Yu, Weidong Yang, Yan Li
Summary: In this study, a biodegradable four-arm star-shaped poly(lactic acid) (4sPLA) was synthesized and its polymerization kinetics were studied. The optimal reaction conditions were determined to be a molar ratio of 12:1 for l-LA to PENTA and a reaction temperature of 160 degrees Celsius for 5 hours.
JOURNAL OF POLYMERS AND THE ENVIRONMENT
(2022)
Article
Polymer Science
Yiyang Liu, Shujie Ming, Yumei Zhou, Jinqing Qu
Summary: UV-curable coatings mainly consist of vinyl resin, active thinner, and photoinitiator. The viscosity and film hardness of vinyl star polyester were found to increase with the hydroxyl function of small molecular polyols. The inclusion of polyether polyol N210 in the reaction system reduced the resin viscosity and improved the film hardness and impact toughness.
POLYMERS FOR ADVANCED TECHNOLOGIES
(2023)
Article
Chemistry, Physical
Min Liu, Jacob R. Blankenship, Adam E. Levi, Qiang Fu, Zachary M. Hudson, Christopher M. Bates
Summary: Polymers with controlled structure and function are highly sought after in various fields, including life sciences and nanotechnology. Miktoarm stars, a type of branched block copolymers with different arm compositions, have gained significant attention due to their distinct physical properties compared to linear block copolymers. This perspective article highlights the recent developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools. It serves as a resource for inspiring future research in this exciting class of materials at the intersection of chemistry, physics, and advanced technology.
CHEMISTRY OF MATERIALS
(2022)
Article
Polymer Science
Hao Ge, Wencheng Shi, Chen He, Anchao Feng, San H. Thang
Summary: A series of core crosslinked star-shaped poly (styrene-b-isoprene-b-styrene) (SISs) and linear triblock SISs were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Both the star-shaped and linear SISs exhibited good tensile properties and a certain phase separation structure, demonstrating the characteristics of thermoplastic elastomers.
Article
Materials Science, Multidisciplinary
Rafal Bielas, Paulina Maksym, Karol Erfurt, Barbara Hachula, Robert Gawecki, Magdalena Tarnacka, Sylwia Waskiewicz, Lukasz Mielanczyk, Anna Mrozek-Wilczkiewicz, Anna Chrobok, Marian Paluch, Kamil Kaminski
Summary: Star-shaped glycopolymers have attracted increased attention as innovative agents in novel cancer therapies due to their attractive combination of physicochemical, morphological, self-assembly properties, and biological activity. However, their production remains a challenge in modern macromolecular chemistry. In this work, a new ionic sugar monomer was (co)polymerized for the first time via AGET ATRP to obtain star-like (co)polymers. The synthesized glycopolymers were found to be homogeneous and stable with varying glass transition temperatures based on the number of glycomonomer. Furthermore, the synthesized carbohydrate-based polymers exhibited high antiproliferative activity against several cancer cell lines.
JOURNAL OF MATERIALS SCIENCE
(2022)
Review
Polymer Science
Athanasios Skandalis, Theodore Sentoukas, Despoina Giaouzi, Martha Kafetzi, Stergios Pispas
Summary: RAFT polymerization is a versatile and precise technique for synthesizing linear ABC-type triblock terpolymers, which can self-assemble into different nanostructures based on their composition and external stimuli. Star-shaped polymers, on the other hand, exhibit a more stable nanostructure with distinct crosslinked core and arm blocks for smart applications.
Article
Chemistry, Applied
Bin Hu, Wen Luo, Xin-lei Zhang, Bo Zhang, Xian-qiu Hu, Lin Jin
Summary: This study investigated the relationship between chemical structure and switching time of electrochromic polymer materials by designing and synthesizing four star-shape monomers and characterizing their resulting polymer films. The findings showed that PM3 exhibited the fastest switching time due to its smaller grain size, lowest charge transfer resistance, and fastest diffusion coefficient values at the oxidation state.
Article
Chemistry, Multidisciplinary
Yuxuan Che, Dmitrii F. Perepichka
Summary: The study introduces a statistical method for quantifying the planarity of various conjugated systems. It investigates the effect of rotational disorder on planarization of common building blocks, and explores the correlations between gas-phase ⟨cos(2)φ⟩ and crystallographically observed planarity in the solid state. Additionally, the calculations reveal an interesting effect of increasing band gap upon planarization for conjugated systems coupling strong electron donor and acceptor units.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daling Cui, Cheng-Hao Liu, Federico Rosei, Dmitrii F. Perepichka
Summary: Using scanning tunneling microscopy and density functional theory calculations, researchers demonstrate reversible structural transition in a 2D supramolecular network formed by terthienobenzenetricarboxylic acid (TTBTA), in response to different molecular signals. This achievement represents important progress in controlling supramolecular surface nanostructures and holds potential applications in various areas of nanotechnology.
Article
Chemistry, Physical
Daling Cui, Navathej Preetha Genesh, Oliver MacLean, Penghui Ji, Jennifer M. MacLeod, Maryam Ebrahimi, Andrey Lunchev, Andrew C. Grimsdale, Dmitrii F. Perepichka, Federico Rosei
Summary: Three types of moire patterns were observed on HOPG, with the incommensurate gamma-pattern being more stable than the commensurate alpha- and beta-patterns. The stability of the gamma-pattern can be explained by the presence of a static distortion wave exclusively observed in this pattern. Lateral relaxation of the TCPB lattice reduces the free energy of the gamma-pattern compared to the alpha- and beta-moire patterns.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Physical
Zhenzhe Zhang, Dmitrii F. Perepichka, Rustam Z. Khaliullin
Summary: This research examined the feasibility of adatom creation and adatom-catalyzed Ullmann coupling of chloro-, bromo-, and iodobenzene on Cu(111), Ag(111), and Au(111) surfaces using density functional theory modeling. It was found that strong phenyl-metal bonds facilitate the extraction of metal atoms, but too strong phenyl-adatom bonds can create barriers for subsequent adatom-catalyzed C-C coupling. Gold adatoms were found to catalyze C-C bond formation almost as efficiently as surface atoms due to their weaker binding to phenyl groups.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Penghui Ji, Dominik Dettmann, Ying-Hsuan Liu, Giulia Berti, Navathej Preetha Genesh, Daling Cui, Oliver MacLean, Dmytro F. Perepichka, Lifeng Chi, Federico Rosei
Summary: Surface-confined reactions are a powerful method for synthesizing low-dimensional organic materials. Understanding the reaction pathways can enable the rational synthesis of various molecules and polymers. In this study, different reaction pathways of tetrathienylbenzene and its extended congener on Cu(111) were investigated using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations.
Article
Chemistry, Physical
Cheng-Hao Liu, Allan Wei, Mailine Fok Cheung, Dmytro F. Perepichka
Summary: This paper introduces the concept of two-dimensional donor-acceptor hydrogen-bonded organic frameworks and demonstrates their potential for realizing low-band-gap flat-band materials. The research shows that these frameworks have strong charge transfer interactions, resulting in tiny band gaps but extremely flat bands. doping these bands can induce ferromagnetism. Stacking the layers of these frameworks can metallize the porous networks and modify the symmetry of the band structures.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Ehsan Hamzehpoor, Cory Ruchlin, Yuze Tao, Cheng-Hao Liu, Hatem M. Titi, Dmytro F. Perepichka
Summary: Organic room-temperature phosphorescence can be achieved by covalently synthesizing covalent organic frameworks (COFs) with halogen doping, which enhances phosphorescence and minimizes triplet-triplet annihilation. The rigidity of COFs suppresses vibrational relaxation, resulting in a high phosphorescence quantum yield at room temperature. COFs with permanent porosity and both singlet and triplet emitting channels can be used for highly efficient oxygen sensing.
Article
Materials Science, Multidisciplinary
K. Laxman, Yuxuan Che, K. Aswani Raj, Dmytro F. Perepichka, M. Rajeswara Rao
Summary: We have demonstrated a TFA-induced absorption shift of pi-extended ketoenamine-substituted triphenylamines from blue to near-infrared region. This shift is highly specific to TFA and only a mild shift is observed in other studied acids. The unexpected near-infrared absorption is due to the formation of a radical cation through a series of proton and electron transfer events, which is confirmed by EPR spectroscopy.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Nanoscience & Nanotechnology
Pegah Ghamari, Muhammad Rizwan Niazi, Dmytro F. Perepichka
Summary: This study demonstrates that intentional doping of a benchmark p-type semiconducting polymer (DPP-DTT) with 2,4,5,7-tetranitrofluorenone (TeNF) can significantly improve the operational and environmental stability of organic field-effect transistors (OFETs). Doping suppresses electron-induced traps and increases hole mobility in an oxygen-rich environment, while mitigating water-induced traps and shifting the threshold voltage. The doped OFETs exhibit environmentally independent performance and superior long-term stability for up to 4 months in ambient air due to enhanced microstructural order.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Cheng-Hao Liu, Zhechang He, Cory Ruchlin, Yuxuan Che, Kyle Somers, Dmytro F. Perepichka
Summary: This study reports the synthesis of Thiele's fluorocarbon (TFC) and its derivatives, which exhibit exceptional thermal, oxidative, and photostability. TFCs have remarkable luminescent properties with yellow to NIR fluorescence and up to 100% quantum yields. The absorption spectra of TFCs show no solvent effect due to their symmetric nonpolar structure, while their emission spectra reveal an extraordinarily large Stokes shift, which increases with solvent polarity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Durbis J. Castillo-Pazos, Juan D. Lasso, Ehsan Hamzehpoor, Jorge Ramos-Sanchez, Jan Michael Salgado, Gonzalo Cosa, Dmytro F. Perepichka, Chao-Jun Li
Summary: Recently, the photochemistry of Electron Donor-Acceptor (EDA) complexes using electron donors as catalytic agents has gained interest in the field of catalysis. This methodology allows for the separation of electron transfer from the bond-forming event. In this study, an EDA complex between triarylamines and alpha-perfluorosulfonylpropiophenone reagents was discovered. It catalyzes C-H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions. The mechanism of this reaction was elucidated through a detailed photophysical characterization of the EDA complex, triarylamine radical cation, and its turnover event.
Article
Materials Science, Multidisciplinary
Yuxuan Che, Muhammad Rizwan Niazi, Ting Yu, Thierry Maris, Cheng-Hao Liu, Dongling Ma, Ricardo Izquierdo, Igor F. F. Perepichka, Dmytro F. F. Perepichka
Summary: We investigated nitrofluorene derivatives as adjustable electron-withdrawing groups for non-fullerene acceptors of the acceptor-donor-acceptor type. We reported their optoelectronic properties and performance in bulk heterojunction solar cells with PBDB-T donor polymer. Introducing up to four nitro groups to the fluorene unit resulted in deeper frontier orbital levels, reduced HOMO-LUMO gap, and red-shifted absorption bands. The best device performance was achieved with trinitrofluorene acceptors containing a solubilizing ester group, striking a balance between decreased voltage and increased photocurrent. The 2D brickwork packing of the tetranitrofluorene derivative, as determined by single crystal X-ray analysis, differed from the interpenetrating 3D network found in high-efficiency acceptors of the acceptor-donor-acceptor type, which might be the reason for the relatively poor charge transport properties. Steric hindrance between benzothiadiazole and nitrofluorene units could be alleviated by the use of furan linkers, which planarized the conjugated backbone but decreased solubility.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Jogirdas Vainauskas, Tristan H. Borchers, Mihails Arhangelskis, Laura J. McCormick McPherson, Toni S. Spilfogel, Ehsan Hamzehpoor, Filip Topic, Simon J. Coles, Dmytro F. Perepichka, Christopher J. Barrett, Tomislav Friscic
Summary: This study presents a different paradigm for the assembly of carbon-only aromatic systems into predictable supramolecular architectures using specific and directional halogen bonding. It highlights the fundamental importance in solid-state and supramolecular chemistry of aromatic compounds and enables the creation of materials with exciting properties.
Article
Chemistry, Multidisciplinary
Jogirdas Vainauskas, Tristan H. Borchers, Mihails Arhangelskis, Laura J. McCormick McPherson, Toni S. Spilfogel, Ehsan Hamzehpoor, Filip Topic, Simon J. Coles, Dmytro F. Perepichka, Christopher J. Barrett, Tomislav Friscic
Summary: Carbon-only aromatic systems can be reliably assembled into predictable supramolecular architectures through specific and directional halogen bonding, instead of non-directional pi-stacking. The C-I & ctdot;pi(C) bonds form a ladder motif in the majority of the structures presented in this study, establishing a unique example of a supramolecular synthon based on carbon-only molecules. Besides fundamental importance in the solid-state and supramolecular chemistry of arenes, this synthon enables the creation of materials with exciting properties.
Review
Chemistry, Multidisciplinary
Hannah E. Hackney, Dmitrii F. Perepichka
Summary: This mini-review discusses recent literature on room temperature phosphorescence (RTP) of crystalline boroorganic compounds, analyzing the connections between molecular structure, intermolecular interactions, and resulting phosphorescence.
