Controlled Sequential Doping of Metal Nanocluster.

Atomically precise doping of metal nanoclusters provides excellent opportunities not only for subtly tailoring their properties but also for in-depth understanding of composition (structure)-property correlation of metal nanoclusters and has attracted increasing interest partly due to its significance for fundamental research and practical applications. Although single and multiple metal atom doping of metal nanoclusters (NCs) has been achieved, sequential single-to-multiple metal atom doping is still a big challenge and has not yet been reported. Herein, by introducing a second ligand, a novel multistep synthesis method was developed, controlled sequential single-to-multiple metal atom doping was successfully achieved for the first time, and three doped NCs Au25Cd1(p-MBT)17(PPh3)2, Au18Cd2(p-MBT)14(PPh3)2, and [Au19Cd3(p-MBT)18]- (p-MBTH: para-methylbenzenethiol) were obtained, including two novel NCs that were precisely characterized via mass spectrometry, single-crystal X-ray crystallography, and so forth. Furthermore, sequential doping-induced evolutions in the atomic and crystallographic structures and optical and catalytic properties of NCs were revealed.

Quantitative Analysis of TPU Microstructure and Performance Optimization across Various Processing Conditions.

Thermoplastic polyurethane (TPU) is essential in resource exploration, healthcare, automotive, and high-end recreational sports. Despite extensive research on TPU's microstructures and their macroscopic properties, the impact of processing conditions like compression and injection molding remains underexplored. This study investigates the influence of processing conditions on TPU by preparing samples with varying hard segment contents using compression molding at 205 °C and injection molding at melt temperatures of 205, 210, 215, and 220 °C, followed by heat treatment at 120 °C for 12 h. Results indicate that injection-molded TPU at 205 °C exhibits lower hydrogen bonding, crystallinity, long period, interfacial thickness, and lamella thickness than compression-molded TPU, leading to higher Young's modulus but lower elongation at break. As melt temperatures increase, these microstructural parameters decrease, reducing Young's modulus and increasing elongation at break. Post heat treatment, microstructural parameters increase, aligning Young's modulus with that of compression-molded samples, while elongation at break surpasses them. This suggests that heat treatment enhances microphase separation by rearranging hard and soft segments. our research reveals a consistent pattern across TPUs with varying hard segment contents, indicating that adjusting processing parameters can effectively regulate microstructure and performance, offering valuable insights for developing high-performance polyurethanes.

Atomically Precise Nanometer-Sized Pt Catalysts with an Additional Photothermy Functionality.

Atomically precise ~1-nm Pt nanoparticles (nanoclusters, NCs) with ambient stability are important in fundamental research and exhibit diverse practical applications (catalysis, biomedicine, etc.). However, synthesizing such materials is challenging. Herein, by employing the mixture ligand protecting strategy, we successfully synthesized the largest organic-ligand-protected (~1-nm) Pt23 NCs precisely characterized with mass spectrometry and single-crystal X-ray diffraction analyses. Interestingly, natural population analysis and Bader charge calculation indicate an alternate, varying charge -layer distribution in the sandwich-like Pt23 NC kernel. Pt23 NCs can catalyze the oxygen reduction reaction under acidic conditions without requiring calcination and other treatments, and the resulting specific and mass activities without further treatment are sevenfold and eightfold higher than those observed for commercial Pt/C catalysts, respectively. Density functional theory and d-band center calculations interpret the high activity. Furthermore, Pt23 NCs exhibit a photothermal conversion efficiency of 68.4 % under 532-nm laser irradiation and can be used at least for six cycles, thus demonstrating great potential for practical applications.

Concomitant Near-Infrared Photothermy and Photoluminescence of Rod-Shaped Au52(PET)32 and Au66(PET)38 Synthesized Concurrently.

Gold nanoclusters exhibiting concomitant photothermy (PT) and photoluminescence (PL) under near-infrared (NIR) light irradiation are rarely reported, and some fundamental issues remain unresolved for such materials. Herein, we concurrently synthesized two novel rod-shaped Au nanoclusters, Au52(PET)32 and Au66(PET)38 (PET = 2-phenylethanethiolate), and precisely revealed that their kernels were 4 × 4 × 6 and 5 × 4 × 6 face-centered cubic (fcc) structures, respectively, based on the numbers of Au layers in the [100], [010], and [001] directions. Following the structural growth mode from Au52(PET)32 to Au66(PET)38, we predicted six more novel nanoclusters. The concurrent synthesis provides rational comparison of the two nanoclusters on the stability, absorption, emission and photothermy, and reveals the aspect ratio-related properties. An interesting finding is that the two nanoclusters exhibit concomitant PT and PL under 785 nm light irradiation, and the PT and PL are in balance, which was explained by the qualitative evaluation of the radiative and non-radiative rates. The ligand effects on PT and PL were also investigated.

Coexistent, Competing Tunnelling, and Hopping Charge Transport in Compressed Metal Nanocluster Crystals.

Understanding charge transport among metal particles with sizes of approximately 1 nm poses a great challenge due to the ultrasmall nanosize, yet it holds great significance in the development of innovative materials as substitutes for traditional semiconductors, which are insulative and unstable in less than ∼10 nm thickness. Herein, atomically precise gold nanoclusters with well-defined compositions and structures were investigated to establish a mathematical relation between conductivity and interparticle distance. This was accomplished using high-pressure in situ resistance characterizations, synchrotron X-ray diffraction (XRD), and the Murnaghan equation of state. Based on this precise correlation, it was predicted that the conductivity of Au25(SNap)18 (SNap: 1-naphthalenethiolate) solid is comparable to that of bulk silver when the interparticle distance is reduced to approximately 3.6 Å. Furthermore, the study revealed the coexisting, competing tunneling, and incoherent hopping charge transport mechanisms, which differed from those previously reported. The introduction of conjugation-structured ligands, tuning of the structures of metal nanoclusters, and use of high-pressure techniques contributed to enhanced conductivity, and thus, the charge carrier types were determined using Hall measurements. Overall, this study provides valuable insight into the charge transport in gold nanocluster solids and represents an important advancement in metal nanocluster semiconductor research.

Recent Advances of Lignin Functionalization for High-Performance and Advanced Functional Rubber Composites.

The biomass lignin is the only large-volume renewable feedstock that is composed of aromatics but has been largely underutilized and is sought for valorization as a value-added material. Recent research has highlighted lignin as a promising alternative to traditional petrol-based reinforcements and functional additives for rubber composites. This review summarized the recent advances in the functionalization of lignin for a variety of rubber composites, as well as the compounding techniques for effectively dispersing lignin within the rubber matrix. Significant progress has been achieved in the development of high-performance and advanced functional rubber/lignin composites through carefully designing the structure of lignin-based additives and the optimization of interfacial morphologies. This Review discussed the effect of lignin on composite properties, including mechanical reinforcement, dynamic properties, antiaging performance, and oil resistance, and also the advanced stimuli-responsive performance in detail. A critical analysis for the future development of rubber/lignin composites is presented as concluding remarks.

Sandwich-Kernelled AgCu Nanoclusters with Golden Ratio Geometry and Promising Photothermal Efficiency.

Metal nanoclusters have recently attracted extensive interest from the scientific community. However, unlike carbon-based materials and metal nanocrystals, they rarely exhibit a sheet kernel structure, probably owing to the instability caused by the high exposure of metal atoms (particularly in the relatively less noble Ag or Cu nanoclusters) in such a structure. Herein, we synthesized a novel AgCu nanocluster with a sandwich-like kernel (diameter≈0.9 nm and length≈0.25 nm) by introducing the furfuryl mercaptan ligand (FUR) and the alloying strategy. Interestingly, the kernel consists of a centered silver atom and two planar Ag10 pentacle units with completely mirrored symmetry after a rotation of 36 degrees. The two Ag10 pentacles and some extended structures show an unreported golden ratio geometry, and the two inner five-membered rings and the centered Ag atom form an unanticipated full-metal ferrocene-like structure. The featured kernel structure causes the dominant radial direction transition of excitation electrons, as determined via time-dependent density functional theory calculations, which affords the protruding absorption at 612 nm and contributes to the promising photothermal conversion efficiency of 67.6 % of the as-obtained nanocluster, having important implications for structure-property correlation and the development of nanocluser-based photothermal materials.

Polyurethanes Based on Polylactic Acid for 3D Printing and Shape-Memory Applications.

Polylactic acid (PLA) has received increased attention in the development of shape-memory polymers and biomedical materials owing to its excellent physical properties and good biocompatibility and biodegradability. However, the inherent brittleness and high shape-recovery temperature of this material limit its application in the human body. Herein, we fabricated a PLA-based thermoplastic polyurethane (PLA-TPU) prepared from modified PLA-diol, dicyclohexylmethane-4,4'-diisocyanate, and 1,4-butanediol to solve the limitations of pure PLA. The glass transition temperature (Tg) of the designed TPU can be tailored from 6 to 40.5 °C by adjusting the content of hard segments or molecular weight of soft segments. The shape of the designed TPU can be fixed at room temperature and recovered at temperatures above 37 °C. Moreover, the prepared PLA-TPUs exhibited recyclability, three-dimensional printing capability, non-cytotoxicity, blood compatibility, and biodegradability. The shape of PLA-TPU/nano-Fe3O4 composites can be recovered by exposure to near-infrared light. These results collectively indicate that PLA-TPUs and their composites may have potential applications as intelligent flexible medical scaffolds for surgical and medical implantation equipment.

Thermal Reprocessing and Closed-Loop Chemical Recycling of Styrene-Butadiene Rubber Enabled by Exchangeable and Cleavable Acetal Linkages.

The covalent cross-linking is an essential prerequisite for achieving the unique entropic elasticity of rubber products; however, the formation of a 3D cross-linked network and permanent cross-links makes thermosetting rubbers difficult to be recycled, causing serious environmental pollution at the end of their life. Herein, a facile, green, and promising strategy to introduce the exchangeable and cleavable acetal bonds into the chemically cross-linked networks of diene-typed rubbers is reported. For the first time, the hydroxyl-functionalized styrene-butadiene rubber (ESBR-HEMA) is prepared by introducing 2-hydroxyethyl methacrylate (HEMA) during the emulsion polymerization of styrene-butadiene rubber (ESBR). Then, based on hydroxyl-vinyl ether addition reactions, divinyl ether (DVE) could serve as a cross-linking agent to facilely and effectively cross-link hydroxyl-functionalized rubbers without additional additives, producing exchangeable and hydrolyzable acetal linkages. What's more, the acetal-containing cross-linked network in ESBR-HEMA vulcanizates could rearrange their topologies at elevated temperatures, endowing them with malleable and thermal reprocessing abilities. Moreover, the hydrolyzable acetal bonds could be selectively cleaved into hydroxyl and aldehyde groups in acidic conditions, resulting in a closed-loop chemical recycling of the ESBR-HEMA rubber. Hence, this work provides a facile and green cross-linking strategy for hydroxyl-functionalized rubbers to address the inherent problems brought from the covalent cross-linking of rubbers.

Machine-learning-assisted molecular design of phenylnaphthylamine-type antioxidants.

In this study, a total of 302 molecular structures of phenylnaphthylamine antioxidants based on N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine skeletons with various substituents were modeled by exhaustive methods. Antioxidant parameters, including the hydrogen dissociation energy, solubility parameter, and binding energy, were calculated through molecular simulations. Then, a group decomposition scheme was determined to decompose 302 antioxidants. The antioxidant parameters and decomposition results constituted machine-learning data sets. Using an artificial neural network model, a correlation coefficient between the predicted and true values above 0.88 and an average relative error within 6% were achieved. Random forest models were used to analyze the factors affecting antioxidant activity from chemical and physical perspectives; the results showed that amino and alkyl groups were conducive to improving antioxidant performance. Moreover, substituent positions 1, 7, and 10 of N-phenyl-1-naphthylamine and 3, 7, and 10 of N-phenyl-2-naphthylamine were found to be the optimal positions for modifications to improve antioxidant activity. Two potentially efficient phenylnaphthylamine antioxidant structures were proposed and their antioxidant parameters were also calculated; the hydrogen dissociation energy and solubility parameter decreased by more than 9% and 7%, respectively, whereas the binding energy increased by more than 16% compared with the benchmark of N-phenyl-1-naphthylamine. These results indicate that molecular simulation and machine learning could provide alternative tools for the molecular design of new antioxidants.

Synthesis and Properties of a Novel Reactive and Low-Migration-Resistant Antioxidant and Its Application in Rubber Composites.

The addition of antioxidants to rubber is one of the most economical and effective methods for delaying rubber aging. However, antioxidant migration can cause environmental pollution. To address this issue, a new reactive antioxidant was synthesized via the chemical bonding of glycidyl methacrylate (GMA) and p-aminodiphenylamine (PPDA). The product was characterized by Fourier-transform infrared spectroscopy, which confirmed the successful reaction between GMA and PPDA, resulting in a compound with the expected structure. The mixture was then combined with a composite of styrene-butadiene rubber and carbon black. The tensile strength, antioxidant properties, migration, and RPA of the resulting materials were tested and compared with those of the commercial antioxidants N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-1,4-phenylenediamine, and poly(1,2-dihydro-2,2,4-trimethylquinoline). After the glycidyl methacrylate antioxidant was grafted onto p-aminodiphenylamine, it became highly compatible with and dispersed in the rubber matrix. The antiaging and antimigration properties of the rubber antioxidants were enhanced without damaging the mechanical properties of the rubber matrix. The short-term and long-term antiaging and antimigration properties of this antioxidant are superior to those of commercially available antioxidants.

Solvent-Free Environmentally Friendly Method to Prepare Thermo-Reversible Fully Bio-Based Elastomers.

Most rubber products come from petrochemical resources, which are increasingly in short supply. Rubber products that formed irreversible chemical bonds in the vulcanization process are difficult to recycle, resulting in a serious waste of resources. Therefore, it is important to prepare a kind of reprocessable biobased elastomers. Using furfuryl methacrylate (FMA) as the modified monomer, poly(dibutyl itaconate-myrcene-furfuryl methacrylate) (PDBIMFA) was synthesized by high-temperature emulsion polymerization successfully. The structure and compositions of PDBIMFA were characterized by Fourier transform infrared and 1H NMR, and the effects of different FMA contents on the structures and properties of PDBIMFA were systematically studied. Based on the Diels-Alder reaction, bismaleimide (BMI) and carbon black (CB) were introduced into PDBIMFA as cross-linking agents and reinforcing fillers, respectively, by the melt blending method, and PDBIMFA-BMI elastomer materials and CB/PDBIMFA-BMI elastomer composites with thermo-reversible cross-linking characteristics were prepared. The effects of the ratio of FMA and BMI on the mechanical properties of PDBIMFA-BMI were studied. PDBIMFA-BMI and CB/PDBIMFA-BMI were reprocessed twice, and the recovery rate of tensile strength was both more than 90%. The addition of CB was found to play a reinforcing role in the elastomer and with the introduction of the amount of CB, the reprocessability of composite remained at a good level. It is hoped that this research will provide a new strategy for the sustainable development of bio-based elastomer materials.

Use of lignin-based crude carbon dots as effective antioxidant for natural rubber.

Rubber is widely recognized as an important material, whose irreplaceable applications range from damping materials to tires. Generally, rubber is vulnerable to oxidative degradation, leading to a deterioration in the material's performance. Therefore, antioxidants are often added to extend the service life of rubber. In this study, crude lignin-based carbon dots (CLCDs) were prepared by a simple hydrothermal treatment of lignin with H2O2 and triethylenetetramine. The thus prepared CLCDs exhibit excellent radical scavenging capability, and were incorporated into natural rubber with vinyl pyridine-styrene-butadiene terpolymer (VPR) as coupling agent. The results revealed that CLCDs could endow NR with excellent antioxidative performance. Interestingly, CLCDs even show superior antioxidant effect towards rubber compared to purified lignin-based carbon dots (PLCDs). This work provides a unique source of inspiration for the preparation of low-cost, highly effective CLCDs from plant biomass waste, most of lignin being used to produce steam and energy, with excellent antioxidant capability for rubber, which is beneficial for a green and sustainable world.

Unprecedented Strength Polysiloxane-Based Polyurethane for 3D Printing and Shape Memory.

Thermoplastic polysiloxane-based polyurethane (Si-TPU) has been attracting a great deal of attention because of the dual advantages of polysiloxane and polyurethane. However, the strength of Si-TPU with a traditional structure is low, and improvement is urgently needed for diverse applications. Herein, we design a polysiloxane-based soft segment (SS) with two urethane groups at the end of the polysiloxane chain, and then we prepare a series of Si-TPUs through a designed SS, isophorone diisocyanate and 1,4-butanediol. Such structural design improves the polarity of the SS and endows more regular hydrogen bonds to the polymer molecular chain. As a result, the prepared Si-TPUs exhibit a good microphase separation structure, unprecedentedly high strength, repeatable processing, noncytotoxicity, shape memory properties, and three-dimensional printing capabilities. Moreover, a maximum tensile strength of Si-TPUs can reach 20.3 MPa, exceeding that of other existing Si-based polymer materials. Si-TPUs show great potential for biomedical applications.

Effect of caffeic acid esters on antioxidant activity and oxidative stability of sunflower oil: Molecular simulation and experiments.

Polyphenol, though used as antioxidants in food industry, suffers from poor solubility issues in vegetable oil. Usually, its solubility would be enhanced through esterification. This work investigated the antioxidant activity and oxidative stability of caffeic acid (CA) and its derivative modified esters by molecular simulation and experiments. Density functional theory (DFT) and molecular dynamic analysis revealed the antioxidant mechanism of CA esters attributing to the comprehensive effects. The lower hydrogen dissociation energy (ΔG) of CA esters with catechol moiety caused the transformation of antioxidant into quinone via the double hydrogen atom transfer reaction. Particularly, the second reduced hydrogen dissociation energy was the keypoint. The strong non-bond energy and hydrogen bond allowed CA esters and oil molecules to interact more efficiently. Hence, the ester moieties enhanced the antioxidant activity with 4.5-6.5 % ΔG reduction compared to CA. Rancimat and DSC assays validated the theoretical predictions. This result shows that the antioxidant activity of CA and its esters could be predicted by this molecular simulation way, which may aid in designing of new polyphenol antioxidant structure.

Reverse atom transfer radical polymerization of dimethyl itaconate initiated by a new azo initiator: AIBME.

Reverse atom transfer radical polymerization (RATRP) was used to synthesize poly(dimethyl itaconate) (PDMI) using an AIBME/CuBr2/dNbpy system. The number average molecular weight (M n) of PDMI was as high as M n = 15 000 g mol-1, the monomer conversion rate reached up to 70%, and the dispersity remained low (D = 1.06-1.38). The first-order kinetics of PDMI are discussed in detail. The AIBME initiator had a higher initiation efficiency than the AIBN initiator. As the ratio of initiator (AIBME) to catalyst (CuBr2) decreased, the M n and D of PDMI decreased. At 60 °C and 80 °C, the M n of PDMI was much higher than the theoretical number average (M n,th), and the D of PDMI broadened with the conversion rate. At 100 °C, the D of PDMI remained low, and the M n of PDMI was closer to the M n,th. As the ratio of monomer (DMI) to initiator (AIBME) increased, the M n of PDMI changed little over time. These phenomena could be explained by the influence of the initiator and catalyst on polymerization kinetics.

Novel Three-Dimensional-Printing Strategy Based on Dynamic Urea Bonds for Isotropy and Mechanical Robustness of Large-Scale Printed Products.

Additive manufacturing via fused deposition modeling (FDM) has become one of the most widely used technologies owing to its ease of operation and effective cost. However, the disappointing interlayer adhesion produced by FDM often results in inferior mechanical properties, which has become a technical bottleneck for industrial production. Herein, we demonstrate a facile and efficient printing strategy to enhance interlayer adhesion by introducing a self-healing mechanism into the printing material, thereby concurrently enhancing the mechanical properties and isotropy of the printed products. This strategy relies on the self-healing property of three-dimensional-printing materials. This self-healing property is endowed by introducing dynamic urea bonds on the thermoplastic polyurethane (TPU) molecular chains, and then, such dynamic bonds can be activated through thermal heating. Accordingly, the synthesized TPU reveals an efficient self-healing property and excellent printability owing to the existence of dynamic reversible covalent bonds. Moreover, objects with complex structures can be split and printed and then assembled using this strategy, avoiding the need for supporting structures and realizing the rapid prototyping of large-sized objects. The printing strategy proposed paves a candidate way to overcome the current challenges in obtaining high-quality products via FDM.

Construction of spin-crossover dinuclear cobalt(II) compounds based on complementary terpyridine ligand pairing.

The self-assembly of multinuclear SCO complexes is appealing in which unique properties may be discovered due to enhanced intramolecular and intermolecular interactions. In this work, three dinuclear cobalt(II) complexes, named Co-1, Co-2, and Co-3, were prepared based on a complementary terpyridine ligand pair strategy. The complexes were accurately synthesized by the solvothermal method in which dinuclear complexes were directional assemblies from cobalt(II) ions, terpy bearing 2,6-dimethoxyphenyl substituents at the terpyridyl 6,6''-positions, and ditopic terpy built with different linkers (alkynyl for 1, diynyl for 2, and phenyl for 3). Single-crystal structure determinations reveal that all compounds possess a central symmetric molecular structure, so that two cobalt(II) units are identical in the solid state. Their spin crossover behaviours were investigated through variable-temperature magnetic susceptibility studies. Co-1 undergoes limited SCO with a large population of low spin state (S = 1/2) in the measured temperatures. Co-2 and Co-3 exhibit solvent-modulated SCO behaviour. Impressively, the de-solvated samples show a repeatable thermal hysteresis loop around the room temperature region. This work demonstrates that complementary terpyridine ligand pairing is a practical approach to accurate and directional construction of multinuclear SCO-active compounds.

Ligand symmetry significantly affects spin crossover behaviour in isomeric [Fe(pybox)2]2+ complexes.

The understanding of the correlation between the spin-state behaviour and the structural features in transition-metal complexes is of pronounced importance to the design of spin crossover compounds with high performance. However, the study of the influence of ligand symmetry on the spin crossover properties is still limited due to the shortage of suitable structural systems. Herein we report the magneto-structural correlations of three mononuclear Fe(ii) isomers with respect to their ligand symmetry. In this work, two phenyl-substituted meso and optically pure pybox ligands were employed to construct meso (1), optically pure (2), and racemic (3) ligand types of [Fe(pybox)2]2+ complexes. Their magnetic susceptibilities were measured via temperature-dependent paramagnetic 1H NMR spectroscopy. We fitted the midpoint temperatures of the transition (T1/2) of 260 K for 1(ClO4), 247 K for 2(ClO4), and 281 K for 3(ClO4). The influence of structural symmetry on spin crossover was rationalized through density functional theory calculations. The optimized structures of [Fe(pybox)2]2+ complex cations show that the geometric distortion of the central FeN6 coordination sphere is mainly caused by the steric congestions between adjacent phenyl substituents. In these compounds, there is a distinct correlation that more steric congestions produce larger coordination distortion and favor the electron configuration in the high-spin state, which reflects in the increase of T1/2. Additionally, the influence of the counter anion and lattice solvent on the meso series compounds was inspected. It is revealed that multiple factors dominate the spin-state behaviour in the solid state. This work provides deep insight into the effect of ligand symmetry on the spin transition behaviour in spin crossover compounds. It demonstrates that molecular symmetry should be considered in the design of spin crossover compounds.

Research of TPU Materials for 3D Printing Aiming at Non-Pneumatic Tires by FDM Method.

3D printing technology has been widely used in various fields, such as biomedicine, clothing design, and aerospace, due to its personalized customization, rapid prototyping of complex structures, and low cost. However, the application of 3D printing technology in the field of non-pneumatic tires has not been systematically studied. In this study, we evaluated the application of potential thermoplastic polyurethanes (TPU) materials based on FDM technology in the field of non-pneumatic tires. First, the printing process of TPU material based on fused deposition modeling (FDM) technology was studied through tensile testing and SEM observation. The results show that the optimal 3D printing temperature of the selected TPU material is 210 °C. FDM technology was successfully applied to 3D printed non-pneumatic tires based on TPU material. The study showed that the three-dimensional stiffness of 3D printed non-pneumatic tires is basically 50% of that obtained by simulation. To guarantee the prediction of the performance of 3D printed non-pneumatic tires, we suggest that the performance of these materials should be moderately reduced during the structural design for performance simulation.