Cyclic Chain Research Articles

New insights into the functional group influence on CO2 absorption heat and CO2 equilibrium solubility by piperazine derivatives

Piperazine(PZ) derivatives which have been widely used in CO2 capture technology exhibit stable physicochemical properties, such as resistance to thermal degradation and low regeneration energy consumption. Both two parameters of CO2 absorbents, low CO2 absorption heat(ΔHabs) and large CO2 equilibrium solubility(αe), are important to CO2 capture performance. However, the influence of functional group types of PZ derivatives on their CO2 capture performance remained unclear. This research aimed to study the functional group influence on the ΔHabs and αe by PZ derivatives with two amines using experimental and quantum chemical methods. The results indicated that PZ derivatives with the ethyl side chain had larger ΔHabs and αe than those with the methyl side chain. The presence of the hydroxy group in PZ derivatives reduced the ΔHabs and the αe. The presence of cyclic methyl side chains on the N atom of PZ derivatives decreased the ΔHabs and increased αe at the same time. The findings show that PZ derivatives with cyclic methyl side chains, steric hindrance effect, and no hydroxy group are favorable for CO2 capture. Among the eight PZ derivatives, TEDA with lower ΔHabs(48.99 kJ/mol) and higher αe(0.917 mol CO2/mol amine) is an excellent absorbent. The results of this study are very important for screening efficient and low-energy consumption absorbents for CO2 capture.

Exploring the integrated potential of pyrolysis and low-temperature wet torrefaction for typical medical waste valorization: A multifaceted approach leveraging online TG-FTIR-MS, 2D-COS, iso-conversional kinetics, and reaction mechanisms

The rapid growth of medical waste, exacerbated by the COVID-19 pandemic and advancements in healthcare, has drawn increased public scrutiny regarding its proper disposal and treatment. This research aimed to characterize the wet torrefaction of a typical medical waste biomass (MWB) composition, comprising bamboo swabs, skewers, splints, cotton balls, tongue depressors, toothpicks, and chopsticks, followed by its co-pyrolysis with medical waste plastic (MWP) including catheter bags, drapes, IV tubing, IV bags, oxygen masks, syringes, and test tubes. The study employed thermogravimetric analysis, TG-FTIR, 2D correlation spectroscopy, iso-conversional kinetics, and mass spectrometry techniques elucidated the driving factors, behaviors, products, mechanisms, and pathways involved. The pyrolysis temperature ranges were 180.15 to 400 °C for TMWB and 380.04 to 550 °C for MWP, with average activation energies of 150.22 and 221.59 kJ/mol for their respective devolatilization processes. Incorporating 20 % and 40 % MWP into the co-pyrolysis process yielded the best performance, characterized by the lowest activation energy. The co-pyrolysis process promoted the release of cyclic hydrocarbons and chain hydrocarbons, but decreased the yields of alcohols, esters, ethers, phenols, and acids, through synergistic mechanisms. Unraveling the pyrolysis pathways and dynamics of these representative medical waste streams offers valuable insights into improving energy recovery, mitigating pollution, diminishing waste volumes, and optimizing industrial thermochemical conversion processes for safely treating these hazardous materials.

An effector protein of Fusarium graminearum targets chloroplasts and suppresses cyclic photosynthetic electron flow.

Chloroplasts are important photosynthetic organelles that regulate plant immunity, growth, and development. However, the role of fungal secretory proteins in linking the photosystem to the plant immune system remains largely unknown. Our systematic characterization of 17 chloroplast-targeting secreted proteins of Fusarium graminearum indicated that Fg03600 is an important virulence factor. Fg03600 translocation into plant cells and accumulation in chloroplasts depended on its chloroplast transit peptide. Fg03600 interacted with the wheat (Triticum aestivum L.) proton gradient regulation 5-like protein 1 (TaPGRL1), a part of the cyclic photosynthetic electron transport chain, and promoted TaPGRL1 homo-dimerization. Interestingly, TaPGRL1 also interacted with ferredoxin (TaFd), a chloroplast ferredoxin protein that transfers cyclic electrons to TaPGRL1. TaFd competed with Fg03600 for binding to the same region of TaPGRL1. Fg03600 expression in plants decreased cyclic electron flow (CEF) but increased the production of chloroplast-derived reactive oxygen species (ROS). Stably silenced TaPGRL1 impaired resistance to Fusarium head blight (FHB) and disrupted CEF. Overall, Fg03600 acts as a chloroplast-targeting effector to suppress plant CEF and increase photosynthesis-derived ROS for FHB development at the necrotrophic stage by promoting homo-dimeric TaPGRL1 or competing with TaFd for TaPGRL1 binding.

Exploring novel antioxidant cyclic peptides in corn protein hydrolysate: Preparation, identification and molecular docking analysis

Antioxidant cyclic peptides were successfully identified from a corn protein hydrolysate. Hydrolysate by Alcalase + Flavourzyme showed the highest cyclic peptide purity (48.36 ± 1.81 %) and higher antioxidant activities compared with other hydrolysate. The success of peptide cyclization in hydrolysate was demonstrated by thermogravimetric analysis and thin-layer chromatography (TLC) analysis. Thermogravimetric analysis showed that the thermal stability of hydrolysate after cyclization was significantly increased, which was related to the formation of cyclic peptides. Peptides with molecular weight less than 1000 Da accounted for more than 80 % in hydrolysate after cyclization. After separation using gel silica chromatography and semi-preparative reverse phase high performance liquid chromatography (RP-HPLC), 22 novel antioxidant cyclic peptides were identified by ultra performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOF-MS) and orbitrap-tandem mass spectrometry (Orbitrap-MS/MS). Synthetic cyclic peptides with the same sequence were synthesized and characterized for their antioxidant activity. Molecular docking suggested that the free radical molecules could bind with the cyclic backbone and side chain of cyclic peptides through hydrogen bonding, hydrophobic interaction as well as electrostatic interaction. This study has important implications for the high-value utilization of corn protein and new cyclic peptides drugs or functional food development.

Synthesis of All‐Benzene Multi‐Macrocyclic Nanocarbons by Post‐Functionalization of meta‐Cycloparaphenylenes

AbstractExpanding the diversity of multi‐macrocyclic nanocarbons, particularly those with all‐benzene scaffolds, represents intriguing yet challenging synthetic tasks. Complementary to the existing synthetic approaches, here we report an efficient and modular post‐functionalization strategy that employs iridium‐catalyzed C−H borylation of the highly strained meta‐cycloparaphenylenes (mCPPs) and an mCPP‐derived catenane. Based on the functionalized macrocyclic synthons, a number of novel all‐benzene topological structures including linear and cyclic chains, polycatenane, and pretzelane have been successfully prepared and characterized, thereby showcasing the synthetic utility and potential of the post‐functionalization strategy.

Synthesis of All-Benzene Multi-Macrocyclic Nanocarbons by Post-Functionalization of meta-Cycloparaphenylenes.

Expanding the diversity of multi-macrocyclic nanocarbons, particularly those with all-benzene scaffolds, represents intriguing yet challenging synthetic tasks. Complementary to the existing synthetic approaches, here we report an efficient and modular post-functionalization strategy that employs iridium-catalyzed C-H borylation of the highly strained meta-cycloparaphenylenes (mCPPs) and an mCPP-derived catenane. Based on the functionalized macrocyclic synthons, a number of novel all-benzene topological structures including linear and cyclic chains, polycatenane, and pretzelane have been successfully prepared and characterized, thereby showcasing the synthetic utility and potential of the post-functionalization strategy.

State Transitions and Crystalline Structures of Single Polyethylene Rings: MD Simulations.

This study investigates the structural changes of cyclic polyethylene (PE) single chains during cooling through molecular dynamics simulations. The influence of topological constraint on a ring is examined by comparing it with the results of its linear counterpart. A pseudo phase diagram of state transition for PE rings based on length and temperature is constructed, revealing a consistent chain-folding transition during cooling. The shape anisotropy of short crystallized cyclic chains exhibits oscillations with chain length, leading to a more pronounced odd-even effect in single cyclic chains compared with the linear ones. A honeycomb model is proposed to elucidate the odd-even effect of chain folding in crystalline structures of single linear and cyclic chains, and we discuss its potential to predict surface tension. Analyses of the tight folding model and the re-entry modes demonstrate that a cyclic chain possesses a shorter average crystalline stem length and a more compact folded structure than its linear counterpart. The findings highlight the impact of topological change on crystallization and the odd-even effect of chain length, providing valuable insights for understanding polymer crystallization with different topologies.

Rational design and efficient synthesis of cyclic polymers with visualized molecular topology and unique dielectric properties

Cyclic polymers without chain ends have attracted increasing attention because of the unique physical properties. However, the direct visualization of cyclic topology remains a formidable challenge, because the cyclic chains with flexible backbone or strong intramolecular interaction usually existed in a coiled state rather than cyclic topology. Herein, monocyclic and bicyclic polymers were prepared via blocking-cyclization technique, and the molecular topology of cyclic polymer containing phenyl pendant was directly observed depending on the reduced intrachain entanglement. The structure and characteristics of cyclic polymers were investigated, and the difference between cyclic polymer and linear counterpart was demonstrated. Compared to linear polymer, cyclic polymer exhibited improved dielectric properties, and bicyclic polymer displayed further increased dielectric constant and energy storage density than monocyclic polymer possessing the same repeating units. Therefore, this research presents a facile strategy in the design and construction of cyclic polymers with directly visualized topology and unique dielectric properties.

Cyclization of ubiquitin chains reinforces their recognition by ZNF216.

Lys48-linked ubiquitin chains, regulating proteasomal protein degradation, are known to include cyclized forms. This cyclization hinders recognition by many downstream proteins by occluding the Ile44-centered patch. In contrast, the A20-like Znf domain of ZNF216 (a ubiquitin-binding protein, A20 Znf) is expected to bind to cyclic ubiquitin chains via constitutively solvent-exposed surfaces. However, the underlying interaction mechanism remains unclear. Here, our ITC and NMR experiments collectively showed that cyclization did not interfere with and even slightly enhance the molecular recognition of diubiquitin by A20 Znf. This effect is explained by the cyclization-induced repression of conformational dynamics in diubiquitin and an enlarged molecular interface in the complex. Thus, these results suggest that cyclic ubiquitin chains can be involved in regulation of ZNF216-dependent proteasomal protein degradation.

Proscan: a structure-based proline design web server.

The ability to control protein conformations and dynamics through structure-based design has been useful in various scenarios, including engineering of viral antigens for vaccines. One effective design strategy is the substitution of residues to proline amino acids, which due to its unique cyclic side chain can favor and rigidify key backbone conformations. To provide the community with a means to readily identify and explore proline designs for target proteins of interest, we developed the Proscan web server. Proscan provides assessment of backbone angles, energetic and deep learning-based favorability scores, and other parameters for proline substitutions at each position of an input structure, along with interactive visualization of backbone angles and candidate substitution sites on structures. It identifies known favorable proline substitutions for viral antigens, and was benchmarked against datasets of proline substitution stability effects from deep mutational scanning and thermodynamic measurements. This tool can enable researchers to identify and prioritize designs for prospective vaccine antigen targets, or other designs to favor stability of key protein conformations. Proscan is available at: https://proscan.ibbr.umd.edu.

Ultrasensitive detection of Salmonella typhi using a PAM-free Cas14a-based biosensor

The effectiveness of Clustered Regularly Interspaced Short Palindromic Repeats (CRISPR)-Cas14a1, widely utilized for pathogenic microorganism detection, has been limited by the requirement of a protospacer adjacent motif (PAM) on the target DNA strands. To overcome this limitation, this study developed a Single Primer isothermal amplification integrated-Cas14a1 biosensor (SPCas) for detecting Salmonella typhi that does not rely on a PAM sequence. The SPCas biosensor utilizes a novel primer design featuring an RNA-DNA primer and a 3′-biotin-modified primer capable of binding to the same single-stranded DNA (ssDNA) in the presence of the target gene. The RNA-DNA primer undergoes amplification and is blocked at the biotin-modified end. Subsequently, strand replacement is initiated to generate ssDNA assisted by RNase H and Bst enzymes, which activate the trans-cleavage activity of Cas14a1 even in the absence of a PAM sequence. Leveraging both cyclic chain replacement reaction amplification and Cas14a1 trans-cleavage activity, the SPCas biosensor exhibits a remarkable diagnostic sensitivity of 5 CFU/mL. Additionally, in the assessment of 20 milk samples, the SPCas platform demonstrated 100% diagnostic accuracy, which is consistent with the gold standard qPCR. This platform introduces a novel approach for developing innovative CRISPR-Cas-dependent biosensors without a PAM sequence.

Cyclic movement and chain resolution in Swahili relative clauses

Swahili relative clauses have three different constructions, characterized by different linear positions of a relative marker. The relative marker follows C, T and the verbal complex in each case. While some previous analyses propose construction-specific operations such as T to C or V to C movement in amba-less relatives, this study shows that the distribution of the relative marker can in fact be derived from a set of independently motivated assumptions without substantial ad-hoc proposals. I argue that the relative marker is an operator that undergoes cyclic A' movement to Spec,CP, and its various linear position results from Landau (2006)’s chain resolution algorithm conditioned by a disyllabic minimality requirement of words in Swahili (Park 1997; Scott 2015).

Synthesis of Spiro[indoline-pyridine]-dicarboxylates and Substituted Alkylidene Oxindoles by Azomethine Ylides and MBH Carbonates of Isatins.

We have developed an efficient protocol for the synthesis of spiro[indoline-pyridine]dicarboxylates and substituted alkylidene oxindoles through [3 + 3] cycloaddition and Michael addition individually by azomethine ylides and various MBH carbonates of isatins. The selective generation of cyclic products and chain products was achieved by changing the substituents at the 3-position of the oxindoles. The features of this method include convenient catalysts, mild reaction conditions, and broad substrate scopes.

Remarkable impact of chain backbone on the performance of Poly(norbornene derivatives)-based anion exchange membranes

Chemical stability and the trade-off between ion conductivity and dimensional stability are two primary challenges for the development of suitable anion exchange membranes (AEMs). Herein, a series of non-crosslinked poly(norbornene derivatives)-based AEMs containing a bulky steric hindrance hydrophobic arylene substituent were prepared by vinyl addition polymerization (VAP), ring-opening metathesis polymerization (ROMP), and ROMP followed post-hydrogenation, respectively. Compared with ROMP and hydrogenated type membranes, VAP-type membranes, especially the VAP-N-50, exhibited excellent dimensional stability with limited swelling ratio (SR = 27.9 %) while higher water uptake (WU = 213.8 %) at 80 °C, which is attributed to its rigid VAP-type cyclic chain backbone. Microtopography study demonstrated the existence of nanoscale phase separation in VAP-type AEMs and its association with water uptake and swelling behavior. VAP-N-60 showed excellent hydroxide conductivity up to 105.5 mS cm−1 at 80 °C, while exhibited superior alkaline stability that was not found in ROMP-type membrane ROMP-N-50 and the hydrogenated-type membrane H-ROMP-N-50. After being immersed in 2 M NaOH solution at 80 °C for 1200 h, the hydroxide conductivity loss of VAP-N-60 was only 3.0 %. Furthermore, a H2/O2 single cell using VAP-N-50 membrane achieved the highest peak power density of 722 mW cm−2 at 60 °C without back pressure.

Bond topology of chain, ribbon and tube silicates. Part II. Geometrical analysis of infinite 1D arrangements of (TO4)n- tetrahedra.

In Part I of this series, all topologically possible 1-periodic infinite graphs (chain graphs) representing chains of tetrahedra with up to 6-8 vertices (tetrahedra) per repeat unit were generated. This paper examines possible restraints on embedding these chain graphs into Euclidean space such that they are compatible with the metrics of chains of tetrahedra in observed crystal structures. Chain-silicate minerals with T = Si4+ (plus P5+, V5+, As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+) have a grand nearest-neighbour ⟨T-T⟩ distance of 3.06±0.15 Å and a minimum T...T separation of 3.71 Å between non-nearest-neighbour tetrahedra, and in order for embedded chain graphs (called unit-distance graphs) to be possible atomic arrangements in crystals, they must conform to these metrics, a process termed equalization. It is shown that equalization of all acyclic chain graphs is possible in 2D and 3D, and that equalization of most cyclic chain graphs is possible in 3D but not necessarily in 2D. All unique ways in which non-isomorphic vertices may be moved are designated modes of geometric modification. If a mode (m) is applied to an equalized unit-distance graph such that a new geometrically distinct unit-distance graph is produced without changing the lengths of any edges, the mode is designated as valid (mv); if a new geometrically distinct unit-distance graph cannot be produced, the mode is invalid (mi). The parameters mv and mi are used to define ranges of rigidity of the unit-distance graphs, and are related to the edge-to-vertex ratio, e/n, of the parent chain graph. The program GraphT-T was developed to embed any chain graph into Euclidean space subject to the metric restraints on T-T and T...T. Embedding a selection of chain graphs with differing e/n ratios shows that the principal reason why many topologically possible chains cannot occur in crystal structures is due to violation of the requirement that T...T > 3.71 Å. Such a restraint becomes increasingly restrictive as e/n increases and indicates why chains with stoichiometry TO<2.5 do not occur in crystal structures.

Biotinylated cyclic naphthalene diimide as a searching tool for G4 sites on the genome

A biotinyl cyclic naphthalene diimide (biotinyl cNDI) (1), in which biotin is introduced on the cyclic linker chain of cNDI with high G-quadruplex (G4) specificity, was synthesized. 1 was used for binding analysis to G4 DNAs such as c-myc, c-kit, CEGF, or TA-core. The results showed that 1 bind to G4 DNAs with high affinity and, especially, two molecules of 1 bind to c-myc DNA from top and bottom of G4 site at K = 3.9 × 10−6 M−1 without changing the G4 structure. As a pulldown assay, 1 and streptavidin magnetic beads could be used to recover a c-myc DNA or 120-mer DNA fragment having single c-myc sequence. The qPCR results for the 120-meric DNAs showed that more than 50% of genomic DNA fragments could be recovered by this pulldown assay. The results obtained here might allow the recovery of G4-containing DNA fragments from genomic DNA to analyze the true G4 present in the genome.Graphic abstract

Zwitterionic ring expansion polymerization of tert‐butyl glycidyl ether with B(C6F5)3 towards the generation of cyclic chains

AbstractThe synthesis of cyclic polymers via zwitterionic ring expansion polymerization is limited to a few number of monomer and catalyst pairs. Herein we report the synthesis of cyclic poly(tert‐butyl glycidyl ether) through the polymerization of tert‐butyl glycidyl ether (tBGE) with B(C6F5)3 in different reaction conditions that include different solvents, monomer to initiator ratio, monomer concentration and temperature. We found that bimodal molecular weight distribution is formed in almost all reaction conditions caused by cyclization of short chains. Subsequent chain elongation leads to the formation of cycles of higher molecular weight, particularly in cyclohexane and under bulk conditions. The formation of non‐cyclic byproducts is common in all the systems investigated. Low molecular weight cyclic chains (Mn = 0.7 kDa, Ð = 1.1) of high topological purity were successfully isolated by preparative gel permeation chromatography. By using a click scavenging protocol, the non‐cyclic byproducts were eliminated from the high molecular weight fraction (Mn = 3 kDa, Ð = 1.3) generating pure cyclic chains. Mechanistic investigation using density functional theory calculations was performed on the formation of zwitterionic intermediates and the transfer reaction to the monomer, which notably affects chain growth by the attack of the glycidyl oxygen of the monomer on the growing chain.

Functionalization of zinc ferrites nanoparticles by cyclic aromatic polyimide chains as a novel star polymer with antibacterial activity and low toxicity

The creation and development of biocompatible nanostructures pose significant challenges for biomedical purposes. This study presents a novel magnetic star polymer structure composed of cyclic polyimide chains as grown arms and a central ZnFe2O4 core with low toxicity and antibacterial activity for use in biological applications such as Targeted drug delivery, hyperthermia therapy and wound healing. To preparate this structure, the surface of MNPs was activated with anchor molecules, and then cyclic aromatic polyamide chains were polymerized using pyromellitic dianhydride and phenylenediamine derivatives on the surface-functionalized ZnFe2O4 MNPs. The cytotoxicity of this nanocomposite was evaluated using MTT tests on MCF10A cells, showing low cytotoxicity against healthy cells. Additionally, the MIC/MBC tests of the prepared star polymer were assessed against Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and showed that this has antibacterial effect against these bacterial strains. From the results, it can be concluded that the prepared nanocomposite can be introduced as a new biological structure for biomedical applications.

EMPIRICAL COMPARISONS AND CORRELATIONS BETWEEN CETANE NUMBER AND PHYSICOCHEMICAL PROPERTIES OF BIODIESEL FUELS

CO2 emissions due to transportation have been increasing since records have been kept, only in recent years there has been a 6 % increase in CO2 emissions from 2015 to 2019. So, it is a sector in constant increase and where there is much work to do to reduce emissions of this global warming precursor gas. Comparatively, carbon dioxide (CO2) emissions from biodiesel, obtained from rapeseed oil, with respect to diesel are significantly reduced. In the same sense, and adding an economic component, biodiesel produced from raw materials such as olive oil, olive pomace oil, sunflower oil, soybean seed oil, algae, castor or castor oil, rapeseed, palm, corn, Brassica carinata or Ethiopian rapeseed, and sea buckthorn, shows that it is more competitive in terms of price and environmental protection. An additional advantage of biodiesel over conventional diesel, thanks to its vegetable origin, is that it lacks cyclic chain hydrocarbons and aromatics, so its use in combustion does not produce carbonaceous residues, furans or dioxins. In addition, they produce less CO emissions due to the greater amount of oxygen in biodiesel and SO2 emissions are almost negligible. On the other hand, their combustion in both small and large engines gives somewhat lower power than with conventional diesel. In this work, analyses of the different properties of biodiesel produced by a total of 24 types of raw material, including blends between them, have been carried out. The main properties of the product have been characterized and found. One of the most remarkable results is that the increase in the cetane number of the samples implies a uniform increase or decrease in the rest of the properties. No significant differences were found between the properties of biodiesel from frying oil residues and those of un-fried or fresh oils, and even those of diesel. Keywords: biofuels, biodiesel,wastes, sustainable, development, correlations, cetane number, cetane index

Commutativity degree of cyclic chains of some of finite groups

For a finite group G, we introduce the concept of commutativity degree of its cyclic chains. We denote the commutativity degree of cyclic chains of a group G by ccd(G), and compute this measure for some famous groups such as dihedral groups D2n, quaternion groups Q2n, quasi-dihedral groups QD2n, and modular groups Mpn.