Cyclic Chain Research Articles

High-performance vinyl-flanked diketopyrrolopyrrole–selenophene polymer semiconductors with branched, linear and cyclic alkyl side chains

Vinyl-containing conjugated polymers exhibiting extended conjugated skeletons with long-wavelength absorption and high carrier mobility have been widely investigated as polymer semiconductors.

Tuning the thermal properties of l-lactide/ε-caprolactone chain shuttled copolymers via catalyst selection

Cyclic esters chain shuttling copolymerization between yttrium and aluminum catalysts is reported for the first time. It allows to tune the thermal properties of the resulting copolymers.

Theoretical study on the role of magnesium chloride complexes induced by different magnesium-to-chlorine ratios in magnesium-sulfur batteries.

In magnesium-sulfur batteries, electrolyte exploration is vital for developing high-energy-density, safe, and reliable batteries. This study focused on cyclic THF and chain DME, representative solvents in ether electrolytes. MgCl2, an ideal anionic salt, forms mono-nuclear (MgCl2(DME)2), bi-nuclear ([Mg2(μ-Cl)2(DME)4]2+), and tri-nuclear ([Mg3(μ-Cl)4(DME)5]2+) complexes in DME. With increasing salt concentration, these complexes sequentially form. Under lower salt concentrations, THF and MgCl2 form mono-nuclear complexes ([MgCl2(THF)4]) and continue to form bi-nuclear complexes ([Mg2(μ-Cl)3(THF)6]+). However, at higher salt concentrations, bi-nuclear complexes ([Mg2(μ-Cl)3(THF)6]+) directly form in THF. Comparing HOMO-LUMO values, [Mg(DME)3]2+ is easily oxidized. Energy gaps decrease with Cl- ion addition, enhancing solution conductivity. Ratios of Mg2+ and Cl- in S-reduction complexes differ, suggesting DME is better at a low Mg/Cl ratio, and THF at a high Mg/Cl ratio. This study contributes to understanding complexes and enhancing Mg-S battery performance.

Toughening of a polymer network by the addition of a small amount of large-sized multicyclic chains

Topological interactions between cyclic and linear polymers have attracted significant attention to exploring the properties of soft materials. However, the complete picture of the cyclic–linear topological interactions is unknown. In this study, a blend system composed of a polymer network and a small amount of large-sized (multi)cyclic polymers (cyclic chain-mixed network, CMN) was prepared to achieve a reinforcing effect via rotaxane or catenane formation. CMNs can be toughened by tuning the topological variables of the (multi)cyclic chains (size and number of cyclic units) and the cross-link density of the network. The toughening was maximized when the molecular weights of the cyclic units were comparable to those of the network loops and the number of rings per molecule was approximately 5. This article suggests that CMNs can control the mechanical properties of networks containing cyclic chains using a single component and proposes a topological design for fabricating tough CMN materials.

Alkyl modified cationic COFs for preferential trapping of charge dispersed perrhenate: Synergistic hydrophobicity and anion-recognition effects

Charge dispersed oxoanionic pollutants (such as TcO4− and ReO4−) with low hydrophilicity are typically difficult to be preferentially extracted. Recently, cationic covalent organic frameworks (COFs) have received considerable attention for anions trapping. Two cationic COFs, denoted as Tp-S and Tp-D, were synthesized by incorporating ethyl and cyclic alkylated diquats into 2,2′-bipyridine-based COF. A synergistic effect of hydrophobic channel and anion-recognition sites were achieved by branched chains, which effectively surmounted the Hofmeister bias. Both Tp-S and Tp-D exhibited raising removal performance for surrogate ReO4− at high acidity with adsorption capacities of 435.6 and 291.4 mg g−1, respectively. Obvious variations caused by side chains were displayed in microstructures and adsorption performance. Specially, compared with Tp-D, Tp-S demonstrated desirable priority in uptake capacity and selectivity. In a real-scenario experiment, Tp-S could remove 72.8 % of ReO4− in a simulated Hanford LAW stream, which was attributed to the spatial effects and charge distribution arising from the open and flexible side chains of Tp-S. Otherwise, the rigid cyclic chains endowed pyridine-base Tp-D material an unprecedented alkaline stability. Spectra and theoretical calculations revealed a mechanism of preferential capture based on electrostatic interaction and hydrogen bonding between charge dispersed ReO4−/TcO4− and Tp-S/Tp-D. This work provides an innovative perspective to tailored materials for the treatment of oxoanionic contaminants.

Macrocyclic Encapsulation in a Non-fused Tetrathiophene Acceptor for Efficient Organic Solar Cells with High Short-Circuit Current Density.

Non-fullerene acceptors have shown great promise for organic solar cells (OSCs). However, challenges in achieving high efficiency molecular system with conformational unicity and effective molecular stacking remain. In this study, we present a new design of non-fused tetrathiophene acceptor R4T-1 via employing the encapsulation of tetrathiophene with macrocyclic ring. The single crystal structure analysis reveals that cyclic alkyl side chains can perfectly encapsulate the central part of molecule and generate a conformational stable and planar molecular backbone. Whereas, the control 4T-5 without the encapsulation restriction displays cis- and twisted conformation. As a result, R4T-1 based OSCs achieved an outstanding power conversion efficiency (PCE) exceeding 15.10 % with a high short-circuit current density (Jsc ) of 25.48 mA/cm2 , which is significantly improved by ≈30 % in relative to that of the control. Our findings demonstrate that the macrocyclic encapsulation strategy could assist fully non-fused electron acceptors (FNEAs) to achieve a high photovoltaic performance and pave a new way for FNEAs design.

Macrocyclic Encapsulation in a Non‐fused Tetrathiophene Acceptor for Efficient Organic Solar Cells with High Short‐Circuit Current Density

AbstractNon‐fullerene acceptors have shown great promise for organic solar cells (OSCs). However, challenges in achieving high efficiency molecular system with conformational unicity and effective molecular stacking remain. In this study, we present a new design of non‐fused tetrathiophene acceptor R4T‐1 via employing the encapsulation of tetrathiophene with macrocyclic ring. The single crystal structure analysis reveals that cyclic alkyl side chains can perfectly encapsulate the central part of molecule and generate a conformational stable and planar molecular backbone. Whereas, the control 4T‐5 without the encapsulation restriction displays cis‐ and twisted conformation. As a result, R4T‐1 based OSCs achieved an outstanding power conversion efficiency (PCE) exceeding 15.10 % with a high short‐circuit current density (Jsc) of 25.48 mA/cm2, which is significantly improved by ≈30 % in relative to that of the control. Our findings demonstrate that the macrocyclic encapsulation strategy could assist fully non‐fused electron acceptors (FNEAs) to achieve a high photovoltaic performance and pave a new way for FNEAs design.

Reaction Mechanism of Nitrogen-Containing Heterocyclic Compounds Affecting Coal Spontaneous Combustion.

To uncover the reaction mechanism of nitrogen-containing heterocyclic compounds affecting coal self-heating, quantum chemical calculations and X-ray photoelectron spectroscopy (XPS) experiments were applied to elucidate the reaction pathways and thermodynamic characteristics of pyrrole, pyridine, indole, quinoline, and carbazole. Results show that in pyrrole, pyridine, indole, quinoline, and carbazole, the reaction with O2 captures the H atom and leads to the formation of ·OOH and pyrrolyl, pyridinyl, indolyl, quinolinyl, and carbazolyl radicals, respectively. The activation energies are 118.15, 86.642, 34.132, 21.004, and 47.259 kJ/mol, respectively. ROO· formed by spontaneous adsorption of O2 by nitrogen-containing radicals undergoes self-reaction, and the O-O bond is broken and dehydrogenated to generate ·OH. Subsequently, at room temperature, ·OH reacts with pyrrole, pyridine, indole, quinoline, and carbazole, resulting in the formation of H2O and pyrrolyl, pyridinyl, indolyl, quinolinyl, and carbazolyl radicals, respectively, thereby forming a cyclic chain reaction. The XPS analysis yielded the following findings: (i) when the temperature rises to 70 °C, the N-5 and N-6 content decrease, which is attributed to the activation energy; (ii) when the temperature reaches 200 °C, the N-5 content decreases, which can be attributed to the activation energy required for the oxidation of pyrrole (118.5 kJ/mol).

A cytochrome c551 mediates the cyclic electron transport chain of the anoxygenic phototrophic bacterium Roseiflexus castenholzii

Roseiflexus castenholzii is a gram-negative filamentous phototrophic bacterium that carries out anoxygenic photosynthesis through a cyclic electron transport chain (ETC). The ETC is composed of a reaction center (RC)–light-harvesting (LH) complex (rcRC–LH); an alternative complex III (rcACIII), which functionally replaces the cytochrome bc1/b6f complex; and the periplasmic electron acceptor auracyanin (rcAc). Although compositionally and structurally different from the bc1/b6f complex, rcACIII plays similar essential roles in oxidizing menaquinol and transferring electrons to the rcAc. However, rcACIII-mediated electron transfer (which includes both an intraprotein route and a downstream route) has not been clearly elucidated, nor have the details of cyclic ETC. Here, we identify a previously unknown monoheme cytochrome c (cyt c551) as a novel periplasmic electron acceptor of rcACIII. It reduces the light-excited rcRC–LH to complete a cyclic ETC. We also reveal the molecular mechanisms involved in the ETC using electron paramagnetic resonance (EPR), spectroelectrochemistry, and enzymatic and structural analyses. We find that electrons released from rcACIII-oxidized menaquinol are transferred to two alternative periplasmic electron acceptors (rcAc and cyt c551), which eventually reduce the rcRC to form the complete cyclic ETC. This work serves as a foundation for further studies of ACIII-mediated electron transfer in anoxygenic photosynthesis and broadens our understanding of the diversity and molecular evolution of prokaryotic ETCs.

Increased Free Radical Generation during the Interaction of a Quinone-Quinoline Chelator with Metal Ions and the Enhancing Effect of Light.

Schiff bases and similar molecules forming metal complexes may cause redox effects, which may also be influenced by light. Anthraquinones such as doxorubicin and idarubicin are widely used antitumor agents, which can generate reactive oxygen species (ROS), stimulated by both the presence of iron and copper ions and also by light. The generated ROS can cause DNA scission, cell membrane oxidation, and many other toxic effects. The redox activity of the quinone-quinoline chelator 2-phenyl-4-(butylamino)naphtho [2,3-h]quinoline-7,12-dione (Q1) was investigated in the presence of iron, copper, and zinc. The influence of light in these interactions was also examined. The chemically induced dynamic nuclear polarization (CIDNP), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) methods were used to elucidate the molecular changes and ROS generation effects of the Q1 metal interactions. A model electron transfer reaction system between 1,4-dihydropyridine and Q1 was utilized to demonstrate that the chelate complexes of Q1 with both Fe(III) and Cu(II) ions were more redox active than Q1 itself. Similarly, CIDNP and NMR data showed that the concentration dependence of the free radicals yield is much higher in the presence of Fe(III) and Cu(II) ions, in comparison to Zn(II), and also that it increased in the presence of light. These findings underline the role of transition metal ions and Q1 in cyclic redox chain reactions and increase the prospect of the development of copper- and iron-based chelating agents, including Q1 and its derivatives, for anticancer therapy. Furthermore, these findings also signify the effect of light on enhancing ROS formation by Q1 and the prospect of utilizing such information for designing target specific anticancer drugs for photodynamic therapy.

Kinetic study of hydrogen abstraction reactions from n-propyl/n-butylcyclohexane by hydrogen atom

Hydrogen abstraction reactions of alkylated cycloalkane by radicals play a fundamental role in combustion and atmospheric chemistry. In this work, we select two representative molecules in alkylated cycloalkane fuels, n-propylcyclohexane (nPCH) and n-butylcyclohexane (nBCH), to investigate the kinetics of their hydrogen abstraction reactions with hydrogen atom. The rate constants over a broad temperature range of 298–2000 K were calculated by using canonical transition state theory coupled with the multistructural torsional anharmonicity effect (TST/MS-T). We stress the particular importance of considering the MS-T anharmonicity for the investigated species involved in the H-abstraction pathways. Due to the approximate cancelation of the anharmonicity factor between the transition-state species and the reactant, the anharmonicity factors for reactions are spread over a narrower range of 0.7–3.3. The anharmonicity will slightly accelerate the H-abstraction for the nBCH system over the whole temperature range. The current results show that the multistructural torsional anharmonicity will influence the accurate estimation of competing relationships. We found that the total H-abstraction rate constants of the nBCH system by the TST/MS-T method are larger by factors of 1.2–1.3 than those for the nPCH system. The present data show that nPCH + H channels are less important by factors of 1.41–5.48 than currently estimated by the commonly used nPCH pyrolysis model. The H-abstraction ratios from the cyclic ring and side chain groups reveal that the rate rule for secondary carbon in chain alkanes does not represent the reactivity of all cycloalkanes well, e.g. the ratio between the cyclic ring and side chain group is high up to 2.8.

Cyclic-polymer grafted colloids in spherical confinement: insights for interphase chromosome organization

Interphase chromosomes are known to organize non-randomly in the micron-sized eukaryotic cell nucleus and occupy certain fraction of nuclear volume, often without mixing. Using extensive coarse-grained simulations, we model such chromosome structures as colloidal particles whose surfaces are grafted by cyclic polymers. This model system is known as Rosetta. The cyclic polymers, with varying polymerization degrees, mimic chromatin loops present in interphase chromosomes, while the rigid core models the chromocenter section of the chromosome. Our simulations show that the colloidal chromosome model provides a well-separated particle distribution without specific attraction between the chain monomers. As the polymerization degree of the grafted cyclic chains decreases while maintaining the total chromosomal length (e.g. the more potent activity of condensin-family proteins), the average chromosomal volume becomes smaller, inter-chromosomal contacts decrease, and chromocenters organize in a quasi-crystalline order reminiscent of a glassy state. This order weakens for polymer chains with a characteristic size on the order of the confinement radius. Notably, linear-polymer grafted particles also provide the same chromocenter organization scheme. However, unlike linear chains, cyclic chains result in less contact between the polymer layers of neighboring chromosome particles, demonstrating the effect of DNA breaks in altering genome-wide contacts. Our simulations show that polymer-grafted colloidal systems could help decipher 3D genome architecture along with the fractal globular and loop-extrusion models.

Cyclic landslide-flood chains along a major mountain river

Landslides are a crucial Earth surface process in mountain landscapes, rapidly transporting large amounts of sediment into lower-elevation areas, and periodically negatively impacting people and their livelihoods. Most studies focus on their immediate, local-scale impacts, but few recognize their remote impacts in mountain environments. In particular, major landslides along rivers can block river channels to form lakes through backwater inundation, posing a flood hazard to downstream areas. In 2018, two landslides occurred along the Baige section of the Jinsha River, eastern Tibetan Plateau, forming two landslide lakes and subsequently, causing two flood events. In this study, we explore the impacts of these events on hillslopes along the river banks, upstream and downstream of the Baige site. Using small baseline subset Interferometric synthetic-aperture radar (SBAS InSAR), we find many active landslides along the Jinsha River and detect a sudden acceleration in these instabilities following the 2018 events. We attribute upstream instabilities to an increase in river width and depth, related to the remains of the landslide dam, while downstream slope instability is likely caused by undercutting along the outburst route. Modelling indicates that failure of these newly detected landslides may block the river again and potentially extend the hazard chain. This work demonstrates that landslides along major rivers can initiate new instabilities, and that even a short-lived landslide-dammed lake can have long-term impacts on stability of hillslopes in river valleys.

Analysis of the response of damped and parametrically driven, strongly anharmonic Klein-Gordon chain - Part 2: Beat-waves

This paper continues a series of publications devoted to the analysis of strongly nonlinear wave phenomena, emerging in genuinely anharmonic, Klein-Gordon cyclic chains, subjected to a traveling-wave parametric excitation. In this study, we analyze a special type of nonlinear waves, which will be further referred to as beat-waves. These are spatially extended, and strongly modulated waves manifested by the extreme amplitude modulation, which can be of stationary or nonstationary type. Stationary beat-waves of Klein-Gordon chains propagate with constant group velocity, that depends on the beat-wave amplitude. In the vicinity of 2:1 parametric resonance, we derive the parametrically driven, discrete p-Schrödinger (PD-DpS) model, which depicts the slow modulation of the response of a parametric oscillator chain. Special coordinates' transformation applied on the PD-DpS model allows the exact reduction of extremely modulated beat-waves to an invariant manifold of this slow-flow system. The system dynamics reduced to the beat-wave invariant manifold is depicted by three collective coordinates. In the undamped case, the analysis of the slow-flow system dynamics on the invariant manifold reveals a special family of nonlinear beat-waves characterized by an extreme amplitude modulation. Among these beat-wave solutions lying on the manifold, our analysis identifies some special solutions manifested by the solitary-pulse like, temporal evolution of the beat-wave amplitude which can either decay to zero or to a constant nonzero value. We derive the exact analytical solutions for these special types of waves as well as obtain an explicit analytical approximation for the beat-waves of other types. In the damped case, analysis of the slow-flow system dynamics on the invariant manifold fully recovers the mechanism of system synchronization on the special, stationary beat-wave solutions characterized by the harmonically modulated envelope. Importantly, the derived reduced order model accurately captures the transient evolution stage as well as the steady-state stage of the collective beat-wave response of PD-DpS model, initialized on the beat-wave invariant manifold. A detailed bifurcation analysis of the stationary undamped as well as the stationary damped beat-waves recovers their entire bifurcation structure and enables to fully characterize the zones of system parameters guaranteeing the existence of this special type of non-linear wave solutions. The results of analytical study of various types of beat wave solutions are in excellent agreement with the results of numerical simulation of both PD-DpS as well as the original, parametrically driven, genuinely an-harmonic, discrete Klein-Gordon model.

The cytochrome b6f complex: plastoquinol oxidation and regulation of electron transport in chloroplasts.

In oxygenic photosynthetic systems, the cytochrome b6f (Cytb6f) complex (plastoquinol:plastocyanin oxidoreductase) is a heart of the hub that provides connectivity between photosystems (PS) II and I. In this review, the structure and function of the Cytb6f complex are briefly outlined, being focused on the mechanisms of a bifurcated (two-electron) oxidation of plastoquinol (PQH2). In plant chloroplasts, under a wide range of experimental conditions (pH and temperature), a diffusion of PQH2 from PSII to the Cytb6f does not limit the intersystem electron transport. The overall rate of PQH2 turnover is determined mainly by the first step of the bifurcated oxidation of PQH2 at the catalytic site Qo, i.e., the reaction of electron transfer from PQH2 to the Fe2S2 cluster of the high-potential Rieske iron-sulfur protein (ISP). This point has been supported by the quantum chemical analysis of PQH2 oxidation within the framework of a model system including the Fe2S2 cluster of the ISP and surrounding amino acids, the low-potential heme b6L, Glu78 and 2,3,5-trimethylbenzoquinol (the tail-less analog of PQH2). Other structure-function relationships and mechanisms of electron transport regulation of oxygenic photosynthesis associated with the Cytb6f complex are briefly outlined: pH-dependent control of the intersystem electron transport and the regulatory balance between the operation of linear and cyclic electron transfer chains.

Fabrication and biological investigation of a novel star polymer based on magnetic cyclic aromatic polyimide chains

Herein, a novel nanostructure based on cyclic aromatic polyimide with statistical star polymer structure was synthesized via the functionalization of the CuFe2O4 MNPs surface. The polymerization process on the functionalized surface of CuFe2O4 MNPs was performed with pyromellitic dianhydride and phenylenediamine derivatives. All analytical methods such as Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric (TG) analysis, X-ray diffraction (XRD) pattern, energy-dispersive X-ray (EDX), field-emission scanning electron microscope (FE-SEM), vibrating-sample magnetometer (VSM) were performed to characterize the structure of CuFe2O4@SiO2-polymer nanomagnetic. The cytotoxicity of CuFe2O4@SiO2-Polymer was investigated for biomedical application by MTT test. The results proved that this nanocmposite was biocompatible with HEK293T healthy cells. Also, the evaluation antibacterial property of CuFe2O4@SiO2-Polymer showed that its MIC in Gram-negative and Gram-positive bacteria were 500–1000 µg/mL, so it had antibacterial activity.

Step-growth polymerization of supracolloidal chains from patchy micelles of diblock copolymers

HypothesisThe formation of supracolloidal chains from the patchy micelles of diblock copolymers bears a close resemblance to traditional step-growth polymerization of difunctional monomers in many aspects, including chain-length evolution, size distribution, and initial-concentration dependence. Thus, understanding the colloidal polymerization based on the step-growth mechanism can offer potential control over the formation of supracolloidal chains in terms of chain structure and reaction rate. ExperimentsWe analyzed the size evolution of supracolloidal chains of patchy micelles of PS-b-P4VP by investigating a large number of colloidal chains visualized in SEM images. We varied the initial concentration of patchy micelles to achieve a high degree of polymerization and a cyclic chain. To manipulate the polymerization rate, we also changed the ratio of water to DMF and adjusted the patch size by employing PS(25)-b-P4VP(7) and PS(145)-b-P4VP(40). FindingsWe confirmed the step-growth mechanism for the formation supracolloidal chains from patchy micelles of PS-b-P4VP. Based on this mechanism, we were able to achieve a high degree of polymerization early in the reaction by increasing the initial concentration and form cyclic chains by diluting the solution. We also accelerated colloidal polymerization by increasing the ratio of water to DMF in the solution and patch size by using PS-b-P4VP with a larger molecular weight.

New cyclic C-geranylflavanones isolated from Paulownia fortunei fruits with their anti-proliferative effects on three cancer cell lines

Seven new C-geranylated flavanones, fortunones F - L (1–7), were isolated from the fresh mature fruits of Paulownia fortunei (Seem.) Hemsl. Their structures were determined by extensive spectroscopic data interpretation (UV, IR, HRMS, NMR, and CD). These new isolated compounds were all with a cyclic side chain modified from the geranyl group. Among them, compounds 1–3 all possessed a dicyclic geranyl modification, which was described firstly for Paulownia C-geranylated flavonoids. All the isolated compounds were subjected to the cytotoxic assay on human lung cancer cell A549, mouse prostate cancer cell RM1 and human bladder cancer cell T24, respectively. Results indicated A549 cell line was more sensitive to C-geranylated flavanones than the other two cancer cell lines and compounds 1, 7 and 8 exhibited potential anti-tumor effects (IC50 ˂ 10 μM). Further research revealed the effective C-geranylated flavanones could exert their anti-proliferative activity on A549 cells by inducing apoptosis and blocking cells in G1 phase.

Physical Mechanism of Nonlinear Spectra in Triangene.

In this work, we theoretically investigate the linear and nonlinear optical absorption properties of open triangulene spin chains and cyclic triangulene spin chains in relation to their lengths and shapes. The physical mechanism of local excitation within the triangular alkene unit and the weak charge transfer between the units are discussed. The uniformly distributed electrostatic potential allows the system to have a small permanent dipole moment that blocks the electronic transition in the light excitation such that the electronic transition can only be carried out between adjacent carbon atoms. The one-photon absorption (OPA) spectra and two-photon absorption (TPA) spectra are red-shifted with the addition of triangulene units compared to N = 3TSCs (triangulene spin chains, TSCs). Here, TPA is mainly caused by the first step of the transition. The length of the spin chain has a significant adjustment effect on the photon cross-section. TSCs of different lengths and shapes can control chirality by adjusting the distribution of the electric dipole moment and transition magnetic dipole moment. These analyses reveal the photophysical properties of triangulene and provide a theoretical basis for studying the photophysical properties of triangulene and its derivatives.

Electron transport in cyanobacterial thylakoid membranes: Are cyanobacteria simple models for photosynthetic organisms?

Cyanobacteria are structurally the simplest oxygenic phototrophs, which makes it difficult to understand the regulation of photosynthesis because the photosynthetic and respiratory processes share the same thylakoid membranes and cytosolic space. This review aimed to summarise the molecular mechanisms and in vivo activities of electron transport in cyanobacterial thylakoid membranes based on the latest progress in photosynthesis research in cyanobacteria. Photosynthetic linear electron transport for CO2 assimilation has the dominant electron flux in the thylakoid membranes. The capacity of O2 photoreduction in cyanobacteria is comparable to the photosynthetic CO2 assimilation, which is mediated by flavodiiron proteins. Additionally, cyanobacterial thylakoid membranes harbour the significant electron flux of respiratory electron transport through a homologue of respiratory complex I, which is also recognized as the part of cyclic electron transport chain if it is coupled with photosystem I in the light. Further, O2-independent alternative electron transports through hydrogenase and nitrate reductase function with reduced ferredoxin as the electron donor. Whereas all these electron transports are recently being understood one by one, the complexity as the whole regulatory system remains to be uncovered in near future.