Chain Growth Research Articles

Activation and Deactivation of Chirality Transfer in the Superbundles of Sequence-defined Stereoisomers.

Discrete oligomers can be used to precisely evaluate the structure-property relationship and enable unique chiroptical activities, however, the role of stereochemical sequences on chirality transfer is still unclear. Herein, we report the successful synthesis of a series of sequence-defined chiral azobenzene (Azo) oligomers via iterative stepwise chain growth strategy. Sequence-defined stereoisomers with one single chiral (L or D) stereocenter at the α-position, ω-position and middle- (m-) position have completely different self-assembly dynamics. ω-positional stereocenter can effectively command all Azo building blocks to adopt a tilted π-π stacking along the helical superbundles, exhibiting the activation of chirality transfer. However, discrete oligomers with the stereocenter at other positions can only self-assemble into non-helical nanowires, accompanied by the deactivation of chirality transfer.Cooperative supramolecular interactions, including the π-π interaction between Azo units, the intermolecular hydrogen bonding and steric hindrance, are intrinsic driving forces for these differentiations.

Activation and Deactivation of Chirality Transfer in the Superbundles of Sequence‐defined Stereoisomers

AbstractDiscrete oligomers can be used to precisely evaluate the structure–property relationship and enable unique chiroptical activities, however, the role of stereochemical sequences on chirality transfer is still unclear. Herein, we report the successful synthesis of a series of sequence‐defined chiral azobenzene (Azo) oligomers via iterative stepwise chain growth strategy. Sequence‐defined stereoisomers with one single chiral (L or D) stereocenter at the α‐position, ω‐position and middle‐ (m−) position have completely different self‐assembly dynamics. ω‐positional stereocenter can effectively command all Azo building blocks to adopt a tilted π–π stacking along the helical superbundles, exhibiting the activation of chirality transfer. However, discrete oligomers with the stereocenter at other positions can only self‐assemble into non‐helical nanowires, accompanied by the deactivation of chirality transfer.Cooperative supramolecular interactions, including the π–π interaction between Azo units, the intermolecular hydrogen bonding and steric hindrance, are intrinsic driving forces for these differentiations.

DIGITAL TRANSFORMATION IN SUPPLY CHAINS: BENEFITS, CHALLENGES AND TECHNOLOGICAL INNOVATIONS

Digitalization is revolutionizing supply chains, resulting in significant gains in efficiency and competitiveness. This study investigates the role of digital technologies, such as the Internet of Things (IoT), artificial intelligence (AI), big data, and blockchain, in transforming supply chain management. The research presents a review of the current literature and analyzes case studies of companies that have adopted these innovations. The results show that the integration of these technologies allows for better visibility into processes, facilitating informed and agile decision-making. The automation of routine tasks and demand prediction through AI algorithms contribute to cost reduction and waste minimization. In addition, the use of digital platforms improves collaboration between the various actors in the chain, optimizing the flow of information. However, the study also highlights the challenges associated with digitalization, such as resistance to change, the need for significant investments, and the shortage of technical skills. The analysis concludes that, despite the barriers, the benefits of digitalization outweigh the challenges, making it essential for the sustainability and growth of supply chains.

Exploration on structure-activity relationship over substituted Co-doped spinel AlFe2O4 for enhanced CO2 hydrogenation into C2-C4 hydrocarbons

As the main greenhouse gas, CO2 has caused some serious environmental problems. Hence the abatement of CO2 allows of no delay. Among all strategies for CO2 reduction, CO2 hydrogenation reveals the great potential for industrial application, and becomes the efficient path to achieve target of “Carbon Neutral”. In this work, the Co-doped AlFe2O4 catalysts were firstly reported for CO2 hydrogenation test, and the enhancement of Co doping on activity was explored systematically via a series of conventional characterization methods. The Fischer-Tropsch synthesis-based CO2 hydrogenation was conducted over Co-doped AlFe2O4, thus the dissociation of CO2 and the carbon chain growth were both important. The observation of CoFe2O4 in the composites indicated the strong electronic interaction between Co and Fe species. This could strengthen the electrons transfer to generate more metallic Co and Fe species during H2 reduction, and then increased the Fe3C percentage during CO2 hydrogenation process. Moreover, the generated Co0 species could provide the additional adsorption sites for reactant gas. Therefore, the strategy of Co doping could strengthen the CO2 hydrogenation performance, reflected in the increase of CO2 conversion, the selectivity and space time yield of C2-C4 products. However, the formed “too stable” structure in the condition of the excessive Co doping prohibited the electrons transfer and the generation of Fe3C active species, thus existing an optimum Co doping amount.

Exploring synthesis techniques for an imidazole-based one-component epoxy latent curing agent: Chemical capping and mechano-chemical capsuling

The increasing demand for one-component epoxy is driven by its eco-friendliness, convenience, and cost-effectiveness, underscoring the importance of developing latent curing agents that trigger reactions under specific conditions. This study introduces an imidazole-based latent curing agent (ICM-SU) characterized by superior storage stability and low-temperature curing capabilities, achieved through dual protections of chemical capping and mechano-chemical capsuling. The process commences with the synthesis of isophorone diisocyanate capped 2-methylimidazole (ICM), wherein the reactivity of 2-methylimidazole (2MI) is controlled via the inductive effect of isophorone diisocyanate, achieved through chemical capping. Subsequently, ICM-SU is produced by uniformly coating it with silica nanoparticles and a urea shell through mechano-fusion system’s dry processing for mechano-chemical capsuling, effectively isolating it from contact with epoxy. The curing mechanism and chemical structure of ICM-SU are identified in four stages: de-capping, de-shelling, formation of epoxy-imidazole adducts, and chain growth. Notably, the melting point of the urea shell (122 °C) closely matches the curing onset temperature, suggesting that the exposure of epoxy to restored 2MI initiates the curing process. As a result, ICM-SU demonstrates significantly enhances storage stability at 20 °C for over 42 days, a stark improvement over 2MI, which solidifies within 8 h. Moreover, specimens cured with ICM-SU exhibits a 32 % increase in tensile strength and a 25 % improvement in Young’s modulus compared to those cured with 2MI, attributed to the reinforcing filler effect of silica nanoparticles.

Effects of Crystallinity and Branched Chain on Thermal Degradation of Polyethylene: A SCC-DFTB Molecular Dynamics Study.

As a widely used plastic, the aging and degradation of polyethylene (PE) are inevitable problems, whether the goal is to prolong the life of PE products or address the issue of white pollution. Molecular simulation is a vital scientific tool in elucidating the mechanisms and processes of chemical reactions. To obtain the distribution and evolution process of PE's thermal oxidation products, this work employs the self-consistent charge-density functional tight binding (SCC-DFTB) method to perform molecular simulations of the thermal oxidation of PE with different crystallinity and branched structures. We discovered that crystallinity does not affect the thermal oxidation mechanism of PE, but higher crystallinity makes PE more susceptible to cross-linking and carbon chain growth, reducing the degree of PE carbon chain breakage. The branched structure of PE results in differences in free volumes between the carbon chains, with larger pores leading to a concentrated distribution of O2 and chemical defects subsequently formed. The breakdown of PE is slowed down when chemical defects are localized in low-density regions of the carbon chain. The specifics and mechanism of PE's thermal oxidation are clearly revealed in this paper, which is essential for understanding the process in depth and for the development of anti-aging PE products.

Optimized spacing of active sites in Ni-Mo catalysts enhances ethanol production in syngas conversion

The direct conversion of syngas to ethanol is highly attractive but remains challenging due to low CO conversion and poor EtOH/ROH. We investigated the conversion of syngas over a KNiMo2C catalyst modified with carbon dots (CDs) derived from Ligustrum lucidum leaves. On the Ni0.54Mo-A catalyst, a CO conversion of 43.4 % was achieved, with oxygenates selectivity and EtOH/ROH，reaching 48.2 % and 63.7 %, the space-time yield of ethanol was 132.5 mg/gcat/h. Comprehensive characterization revealed that CDs regulate the distance between Ni-Mo active sites, preventing excessive proximity and maintaining an optimal separation. This adjustment significantly enhances EtOH/ROH by modulating the probability of carbon chain growth. A potential new reaction pathway for directly converting syngas to ethanol is proposed, The C-C coupling of CHx* with *COOH or *CO2 is identified as a key step in carbon chain growth. This work provides a new catalytic pathway for the syngas to ethanol industry.

Electrochemical reduction of nitrate to ammonia using Fe-based catalyst: Insights into N2, CO2, and CO environments

Electrochemical (EC) reduction of nitrate/nitrite for ammonia production is a key area of research in the realm of nitrogen pollutant treatment and recycling efforts. In this study, we utilized a commercial Fe(Mn) alloy to investigate EC reductions of nitrate/nitrite ions under N2, CO, and CO2-saturated conditions, shedding light on the influences of different feeding gases. Under N2 conditions, the ammonia production Faradaic efficiency (FE) reached 60 %; however, it significantly decreased under CO2 conditions. The presence of CO as a feeding gas proved detrimental, resulting in no ammonia production. Surprisingly, the Fe(Mn) alloy demonstrated superior EC Fischer-Tropsch (F-T) synthesis chemistry under CO conditions, generating CH4 and long-chain hydrocarbons (CnH2n+2 and CnH2n, where n=2–7). This contrasts with existing literature, where such alloys typically perform better under CO2 conditions. Notably, alkanes were found to be more predominant than their corresponding alkenes. The Anderson-Schulz-Flory equation plots exhibited significant linearity, resembling the traditional Fischer-Tropsch chain growth mechanism. This original discovery introduces new possibilities for employing commercial-grade Fe alloy in the direct EC F-T synthesis using CO, facilitating the production of long-chain hydrocarbons. Moreover, it paves the way for nitrate/nitrite ion treatments in analogous processes within diverse gas environments.

Surface‐Functionalization of Oleate‐Capped Nano‐Emitters for Stable Dispersion in 3D‐Printable Polymers

AbstractTwo‐photon polymerization 3D‐printing is a well‐known technique for fabricating passive micro/nanoscale structures, such as microlenses and inversely designed polarization splitters. The integration of light emitting nanoparticle (NP) dopants, such as quantum dots (QDs) and rare‐earth doped nanoparticles (RENPs), into a polymer resist would enable 3D printing of active polymer micro‐photonic devices, including sensors, lasers, and solid‐state displays. Many NPs contain oleic acid ligands to prevent degradation, but oleate‐capped NPs (oc‐NPs) tend to agglomerate in nonpolar media despite the hydrophobicity of the ligand. This results in an uneven nanoparticle distribution and increased optical extinction. In this work, a general approach is proposed for dispersing oc‐NPs in commercial 3D printable polymers. Controlled growth of small carbon chains around the oc‐NPs is achieved by functionalizing them with methyl‐methacrylate monomers. The proposed approach is validated on RENPs (≈65 nm) and CdSe/ZnS quantum dots (≈12 nm) using commercial polymer resists (IP‐Dip and IP‐Visio). Dispersions of functionalized NPs (f‐NPs) have improved the NP density by an order of magnitude and are shown to be stable for several weeks with minimal impact on printing quality. The approach is generalizable to other oc‐NPs, enabling synthesis of functional resins for high‐quality polymer‐based optical and electronic devices.

Growing polyion complex micelles: kinetics and mechanism of electrostatic template polymerization and assembly

HypothesisElectrostatic-templated polymerization (ETP) is a recently developed strategy for robust fabrication of stable polyion complex (PIC) micelles with regulated size and morphology, yet the kinetics and mechanism about this one pot process remain elusive. ExperimentsIn ETP method, ionic monomers are polymerized in the presence of an oppositely charged ionic-neutral diblock copolymer as template. We investigate the monomer conversion and electrostatic assembly as a function of time, under different polymerization conditions of ionic strength, pH, template/monomer molar ratio and the presence of a cross-linker. FindingsThe template copolymer accelerates the monomer conversion and formation of PIC micelles dependent on ionic strength and pH. The process follows the “Pick-up” mechanism, where monomers first convert into oligomers which complex with template to induce further chain growth and electrostatic assembly. Introducing cross-linker hardly impacts the reaction kinetics and “Pick-up” route, while it creates PIC micelles containing cross-linked ionic network assembly with the template. Further removing the template by concentrated salt provides purified ionic nanogels. The disclosed findings not only provide a better understanding of the polymerization-assembly process, but also optimize the controls of electrostatic-templated polymerization for the rational design and fabrication of diverse PIC micelles and polyelectrolyte particles.

Insight into the synthesis of alkali metal modified Co-doped ZnFe2O4 with faveolate spinel structure and their enhanced selectivity of olefins during CO2 hydrogenation

Emission reduction of CO2 allows of no delay, and CO2 hydrogenation strategy reveals the great potential to achieve target of “Carbon Neutral”. Trapped with the low selectivity of olefins in our previous work of Co-doped ZnFe2O4, the alkali metal (Na, K) modified Co-doped ZnFe2O4 were synthesized, and their enhanced selectivity of olefins were present. The promotion caused by alkali metal modification revealed that more generation of metallic Fe and the additional generation of Fe5C2 species could be ascribed for the enhanced selectivity of C2-C4 olefins and C5+ products. The introduced alkali metal via the strong electronic interaction increased the outer electrons density around Fe atoms, which could promote the adsorption of CO2 and prohibited the secondary hydrogenation reaction of the formed olefins. Therefore, the enhanced selectivity of C2-C4 olefins over the alkali metal (Na, K) modified Co-doped ZnFe2O4 was emerged, while the CO2 conversion was suppressed (caused by the less generation of Fe3O4). Compared with Na-modified samples, the introduced K could make more generation of Fe5C2 to promote the carbon chain growth, due to its stronger alkalinity, thus leading to the highest selectivity of C5+ products over K-modified samples while the highest selectivity of C2-C4 olefins over Na-modified samples.

Manufacture of Solid Propellants Based on Renewable Succinic Acid Polyols

AbstractModern energy policies encourage the replacement of fossil fuels with a more sustainable type. Succinic acid is a promising renewable material that can react with ethylene glycol and 1,4‐butanediol in a two‐step polycondensation reaction to form hydroxylated polyesters. Copolymerization reactions were investigated to produce novel green binders for manufacture of solid propellants. The ester of the first step of polycondensation was used as a plasticizer in the propellant formulation. These products can be an alternative to binders of fossil sources, such as hydroxyl‐terminated polybutadiene (HTPB), frequently used as fuel of commercial propellants. Initially, analyses of Fourier transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography indicated the formation of polymeric products and adequate chain growth at reaction conditions. Then, the obtained copolymers were characterized by rheological analyses, which revealed that the processability of the copolymer materials was similar to that of the HTPB samples. Additionally, thermogravimetric analyses indicated that the copolymers presented good thermal stability below 200°C. Furthermore, differential scanning calorimetric (DSC) analyses indicated that the glass transition temperatures of the obtained copolymer samples ranged from −20 to −60°C, a suitable range for the intended use. Solid propellants were then prepared with solid loadings above 70 wt %, heat of combustion above 11,300 J g−1 and heat of explosion above 4,980 J g−1, which are compatible with values expected for solid propellants. Finally, oxygen balance calculations showed that the intrinsic oxygen content of the polyesters can allow the reduction of amounts of oxidizers in the final propellants.

Impact of Temperature on the Self-Assembly of Fibrinogen in Thrombin-Free Solutions.

Self-assembly of thrombin-free solutions of fibrinogen can be triggered not only by a drop in the ionic strength but also by an appropriate decrease in temperature. Accordingly, an in situ study of self-assembly of fibrinogen in saline buffered solution is carried out by means of time-resolved light scattering providing the molar mass, geometric size, and hydrodynamic radius of the growing intermediates. The resulting data provide access to the morphology of the intermediates and to the mechanism in which these intermediates grow during the early stages of self-assembly. Modeling the results of concentration dependent experiments based on temperature gradients in terms of a chain growth mechanism leads to the corresponding molar standard enthalpy and entropy of aggregation.

Exploring C1-C3 variations and Fischer–Tropsch chemistry via electrochemical CO2 reduction on electrodeposited Cu/Ag and Ag/Cu electrodes

Ag and Cu bimetallic electrodes are extensively studied for producing C-C coupled C2+ reduction products through electrochemical CO2 reduction. In this study, we prepared electrodes with Cu electrodeposited on Ag supports (CuED/Ag) and Ag electrodeposited on Cu supports (AgED/Cu) via electrodeposition, demonstrating behaviors for reduction products under various electrochemical conditions. The products were categorized as H2, C1 (CO, CH4, formate, methanol), C2 (C2H4, ethanol, acetate, acetaldehyde, glycolaldehyde, and ethylene glycol), C3 (propanol, isopropanol), and Fischer–Tropsch (F-T) synthesis products (CnH2n and CnH2n+2, n ≥ 2). Notably, ethylene glycol was only observed over AgED/Cu. The reduction products dynamically changed with applied potentials and electrolyte concentrations. The mechanism was understood to involve surface H* adsorption, CO2 adsorption, C-C coupling, hydrogenation, and dehydration. Minor F-T synthesis chemistry was observed, explained by *CO and *CH2 insertion chain growth. The distinct product behaviors over the CuED/Ag and AgED/Cu electrodes provide valuable insights into the development of electrodes for producing value-added carbon products via CO2 utilization.

Effect of surface carbon of iron carbide on Fischer-Tropsch synthesis: A density functional theory study

The surface iron of iron carbide has been identified as active in Fischer-Tropsch synthesis (FTS), but the effect of surface carbon remains a topic of debate. Herein, to clarify the effect of surface carbon of iron carbide on FTS, we conducted a density functional theory (DFT) study on CO adsorption, H2 activation and CO hydrogenation over ε-Fe2C and θ-Fe3C. Compared to Fe3C(111), the Fe2C(111) facet exhibits more low-coordinated carbon, benefiting for CO adsorption and H2 activation. Because of the low-coordinated carbon, the Fe2C(111) is more active for FTS than Fe3C(111), not only through the formation of CH2 species with H atoms, but also through the direct C–C coupling for the carbon chain growth. The consumed carbon on Fe2C(111) can be recovered timely by absorption and direct dissociation of CO, ensuring the sustainability of the carbon chain growth. This work contributes to a comprehensive understanding of the FTS mechanism over iron carbide surface.

Tailoring Surface Engineering with Expanded Precursor Libraries via Rapid Mussel-Inspired Chemistry.

Mussel-inspired coating is a substrate-independent surface modification technology. However, its application is limited by time-consuming, tailoring specific functions require tedious secondary reaction. To overcome those drawbacks, a strategy for the rapid fabrication of diverse coatings by expanding the library of precursors using oxidation coupled with polyamine was proposed. Based on DFT simulations of the reaction pathways, a method was developed to achieve rapid deposition of coatings by coupling oxidation and polyamines, which simultaneously accelerated the oxidation of precursors and polymer chain growth. The feasibility and generalizability of the strategy was validated by the rapid coating of 10 catechol derivatives and polyamines on various substrates. The surface properties of the substrates such as functional group densities, Zeta potential and contact angles can be easily tuned. The tailored surface engineering application of the strategy was demonstrated by the heavy metal adsorbents and superwetting materials prepared through the delicate combination of different building blocks. Our strategy was flexible in terms of diverse surface engineering design which greatly enriched the connotation of mussel-inspired technique.

Polymeric Microbubble Shell Engineering: Microporosity as a Key Factor to Enhance Ultrasound Imaging and Drug Delivery Performance.

Microbubbles (MB) are widely used as contrast agents for ultrasound (US) imaging and US-enhanced drug delivery. Polymeric MB are highly suitable for these applications because of their acoustic responsiveness, high drug loading capability, and ease of surface functionalization. While many studies have focused on using polymeric MB for diagnostic and therapeutic purposes, relatively little attention has thus far been paid to improving their inherent imaging and drug delivery features. This study here shows that manipulating the polymer chemistry of poly(butyl cyanoacrylate) (PBCA) MB via temporarily mixing the monomer with the monomer-mimetic butyl cyanoacetate (BCC) during the polymerization process improves the drug loading capacity of PBCA MB by more than twofold, and the in vitro and in vivo acoustic responses of PBCA MB by more than tenfold. Computer simulations and physisorption experiments show that BCC manipulates the growth of PBCA polymer chains and creates nanocavities in the MB shell, endowing PBCA MB with greater drug entrapment capability and stronger acoustic properties. Notably, because BCC can be readily and completely removed during MB purification, the resulting formulation does not include any residual reagent beyond the ones already present in current PBCA-based MB products, facilitating the potential translation of next-generation PBCA MB.

Phosphoric acid salts of amino acids as a source of oligopeptides on the early Earth

Because of their unique proton-conductivity, chains of phosphoric acid molecules are excellent proton-transfer catalysts. Here we demonstrate that this property could have been exploited for the prebiotic synthesis of the first oligopeptide sequences on our planet. Our results suggest that drying highly diluted solutions containing amino acids (like glycine, histidine and arginine) and phosphates in comparable concentrations at elevated temperatures (ca. 80 °C) in an acidic environment could lead to the accumulation of amino acid:phosphoric acid crystalline salts. Subsequent heating of these materials at 100 °C for 1–3 days results in the formation of oligoglycines consisting of up to 24 monomeric units, while arginine and histidine form shorter oligomers (up to trimers) only. Overall, our results suggest that combining the catalytic effect of phosphate chains with the crystalline order present in amino acid:phosphoric acid salts represents a viable solution that could be utilized to generate the first oligopeptide sequences in a mild acidic hydrothermal field scenario. Further, we propose that crystallization could help overcoming cyclic oligomer formation that is a generally known bottleneck of prebiotic polymerization processes preventing further chain growth.

Narrowly Distributed Conjugated Polymers Synthesized Through Acid‐Catalyzed Aldol Polycondensations in Nanoreactors

AbstractConjugated polymers are typically synthesized through transition metal‐mediated coupling reactions, which are often costly and have significant environmental impacts. Aldol condensation represents a more cost‐effective and sustainable synthetic technique for developing next‐generation organic functional materials. However, controlling the molecular weight and distribution of the resulting polymers remains challenging due to the uncontrollable step‐growth polymerization mechanism of aldol polycondensations. To this end, by selectively anchoring sulfonic acids inside the mesochannels of SBA‐15, the aldol polycondensation is exclusively confined within the pores. Experimental results demonstrate that this nanoreactor, by providing a spatially confined reaction environment, aids in controlling the progression of the polymerization and the growth of polymer chains, thereby achieving good control over polymer molecular weight and distribution, giving linear conjugated polymers and soluble conjugated polymeric nanoparticles with polymer dispersity down to 1.31.

Copolymerization of Isothiocyanates and Nonactivated Aziridines Mediated by Zwitterionic Intermediates through Condensation and Chain Growth

Copolymerization of Isothiocyanates and Nonactivated Aziridines Mediated by Zwitterionic Intermediates through Condensation and Chain Growth