Effects of phosphine ligands in nickel-catalyzed decarbonylation reactions of lactone.

Due to the ubiquity of carbonyl compounds and the abundance of nickel on the earth, nickel-catalyzed decarbonylation has garnered increasing attention in recent years. This type of reaction has seen significant developments in various aspects; however, certain challenges concerning reactivity, selectivity, and transformation efficiency remain pressing and demand urgent resolution. In this study, we employed DFT calculations to investigate the mechanism of nickel-catalyzed decarbonylation reactions involving lactones, as well as the effects of phosphine ligands. Mechanically, Ni(0) first activates the C(acyl)-O bond of the lactone, followed by a decarbonylation step, and ultimately results in reductive elimination under carbonyl coordination to yield the product. Through a comprehensive examination of the electronic and steric effects of the phosphine ligands, we deduced that the electronic effect of the ligand plays a dominant role in the decarbonylation reaction. By enhancing the electron-withdrawing ability of the ligand, the energy barrier of the entire reaction can be significantly reduced. The obtained insights should be valuable for understanding the detailed mechanism and the role of phosphine ligands in nickel catalysis. Moreover, they offer crucial clues for the rational design of more efficient catalytic reactions.

Effects of Tissue-engineered Bone by Coculture of Adipose-derived Stem Cells and Vascular Endothelial Cells on Host Immune Status.

AIM: The study aimed to explore the effects of tissue-engineered bone constructed with partially deproteinized biologic bone (PDPBB) and coculture of adipose-derived stem cells (ADSCs) and vascular endothelial cells (VECs) on host immune status, providing a very useful clue for the future development of bone engineering. METHODS: Tissue-engineered bones constructed by PDPBB and ADSCs, VECs or coculture of them were implanted into the muscle bag of bilateral femurs of Sprague-Dawley rats. Partially deproteinized biologic bone alone and blank control were also implanted. After transplantation, the proliferation of implanted seed cells in tissue-engineered bones was labeled by bromodeoxyuridine staining. Moreover, the changes of T-lymphocyte subpopulations, including CD3 + CD4+ and CD3 + CD8+ in peripheral blood were then detected using flow cytometry to analyze the immune rejection of tissue-engineered bone implantation based on peripheral blood CD4/CD8 ratios. RESULTS: After transplantation, the proliferation of implanted seed cells was observed in tissue-engineered bones of different groups. At different time points after transplantation, the CD4+/CD8+ ratio in peripheral blood of PDPBB + ADSCs, PDPBB + coculture, and blank control groups did not exhibit significant change. Although the CD4+/CD8+ ratio in peripheral blood of PDPBB + VECs group was significantly higher than other group at 1 week after transplantation, that of PDPBB + VECs and PDPBB + coculture group was significantly decreased at 8 week after transplantation compared with that of blank control group. CONCLUSIONS: Our results indicated that there was no significant immune rejection after transplantation of tissue-engineered bone constructed with PDPBB and coculture of ADSCs and VECs as seed cells.

Repair of Bone Defects With Endothelial Progenitor Cells and Bone Marrow-Derived Mesenchymal Stem Cells With Tissue-Engineered Bone in Rabbits.

PURPOSE: This study aimed to investigate the repair of bone defects in rabbits with tissue-engineered bones using cocultured endothelial progenitor cells (EPCs) and bone marrow mesenchymal stem cells (BMSCs) as seeding cells. METHODS: Endothelial progenitor cells and BMSCs were isolated and purified from the peripheral blood and bone marrow, respectively, of New Zealand rabbits. The third passage of BMSCs was cultured alone or with EPCs. Cells were characterized using specific markers and then seeded on partially deproteinized biologic bones from pigs as a scaffold. The engineered bones were used to repair bone defects in rabbits. Hematoxylin and eosin and Masson staining were performed to examine vascularization and osteogenesis in the engineered bone. RESULTS: The cocultured EPCs and BMSCs grew well on the surface of the scaffold. Compared with monocultured BMSCs, cocultured EPCs and BMSCs promoted the formation of blood vessels and bone on the scaffold, in addition to accelerating the repair of bone defects. The collagen content was significantly increased in the scaffold with cocultured EPCs and BMSCs, compared with the scaffold seeded with mono-cultured BMSCs. CONCLUSIONS: Tissue-engineered bones seeded with cocultured EPCs and BMSCs may be used effectively for the repair of bone defects.

Clinical efficacy of celecoxib for osteoarthritis and bone anchor assisted knee extensor reconstruction.

Celecoxib is the most recent non steroidal anti-inflammatory analgesic, and has been gradually used in the treatment of acute pain, rheumatism and osteoarthritis. This paper analyzes the analgesic effect of celecoxib in the treatment of knee osteoarthritis and put forward a new mechanism of knee joint extensor reconstruction assisted by bone anchor. The experimental group was given celecoxib 200 mg/ time and 1 time /d. The results showed that VAS (Visual Analogue Scale) decreased gradually in both groups on the 1st, 3rd and 7th day of treatment and VAS in experimental group was lower than that in control group at the same time point (P<0.05). At the 1 year follow-up, experience group had a significant improvement on the Lysholm (69.33 ± 8.38 preoperatively and 88.65 ± 12.93 postoperatively) and Kujula (69.33 ± 8.38 preoperatively and 88.65 ±12.93 postoperatively) knee scores (P<0.05). The results showed that celecoxib had a good analgesic effect in patients with knee osteoarthritis and reducing the release of inflammatory factors may be its mechanism..

High-performance thermoelectric materials based on ternary TiO2/CNT/PANI composites.

In the present work, we report the fabrication of high-performance thermoelectric materials using TiO2/CNT/PANI ternary composites. We showed that a conductivity of ∼2730 S cm-1 can be achieved for the binary CNT (70%)/PANI (30%) composite, which is the highest recorded value for the reported CNT/PANI composites. We further demonstrated that the Seebeck coefficient of CNT/PANI composites could be enhanced by incorporating TiO2 nanoparticles into the binary CNT/PANI composites, which could be attributed to lower carrier density and the energy scattering of low-energy carriers at the interfaces of TiO2/a-CNT and TiO2/PANI. The resulting TiO2/a-CNT/PANI ternary system exhibits a higher Seebeck coefficient and enhanced thermoelectric power. Further optimization of the thermoelectric power was achieved by water treatment and by tuning the processing temperature. A high thermoelectric power factor of 114.5 µW mK-2 was obtained for the ternary composite of 30% TiO2/70% (a-CNT (70%)/PANI (30%)), which is the highest reported value among the reported PANI based ternary composites. The improvement of thermoelectric performance by incorporation of TiO2 suggests a promising approach to enhance power factor of organic thermoelectric materials by judicial tuning of the carrier concentration and electrical conductivity.

Self-Assembly and Applications of Amphiphilic Hybrid POSS Copolymers.

Understanding the mechanism of molecular self-assembly to form well-organized nanostructures is essential in the field of supramolecular chemistry. Particularly, amphiphilic copolymers incorporated with polyhedral oligomeric silsesquioxanes (POSSs) have been one of the most promising materials in material science, engineering, and biomedical fields. In this review, new ideas and research works which have been carried out over the last several years in this relatively new area with a main focus on their mechanism in self-assembly and applications are discussed. In addition, insights into the unique role of POSSs in synthesis, microphase separation, and confined size were encompassed. Finally, perspectives and challenges related to the further advancement of POSS-based amphiphilics are discussed, followed by the proposed design considerations to address the challenges that we may face in the future.

Directed self-assembly of sub-10 nm particle clusters using topographical templates.

Directed self-assembly of nanoparticles (DSA-n) is an approach that creates suitable conditions to capture nanoparticles randomly dispersed in a liquid and position them into predefined locations on a solid template. Although DSA-n is emerging as a potential bottom-up patterning technique to build nanostructures using nanoparticles of various sizes, geometries and material compositions, there are still several outstanding challenges. In this paper, we focus on the DSA-n of sub-10 nm particles using topographical templates to guide them into 1D and 2D ordered arrays. The process mechanism leading DSA-n at sub-10 nm size scale has been reviewed and experimental evidence of the impact of the template on the positioning both individual and clusters of particles with low level of structure defects have also been demonstrated. Furthermore, by controlling the drying direction of the liquid within polygonal traps, we are also able to tune the spacing between the trapped nanoparticle clusters. This self-structuring phenomenon is of crucial importance for various applications such as plasmonics and charge transport within quantum circuits, whereby the coupling effects are highly dependent on the size of the nanoparticles and their separation.

Regiospecific protonation of organic chromophores.

Highly conductive, acid doped polymers such as PEDOT/PSS and polyaniline (PANI) have attracted much attention due to their potential applications in flexible electronics. However, the understanding of the mechanism behind the doping process is still lacking. In this paper, we conduct a systematic and detailed investigation on the acid doping behaviors of four model compounds which were synthesized by combining different protonatable units such as pyridal[2,1,3]thiadiazole (PT), benzo[2,1,3]thiadiazole (BT), cyclopentadithiophene (CPDT), and azulene. DFT simulation and UV-vis-NIR spectral studies show that while the site of first protonation was mainly determined by proton affinity, the subsequent site of protonation and doping density were determined by the nature of the first protonation and influenced by the following two factors: (1) electrostatic charge repulsion and (2) the possible delocalization of protonated charge in the conjugated structure. If the first protonation occurs at heteroatoms and results in a coplanar structure, the subsequent sites of protonation are mainly determined by the distance from the positive charge center to lower the effect of static repulsion and charge delocalization. On the other hand, if the first protonation occurs on the main chain carbon atoms which induce a large torsional angle (non-coplanar) as the carbon hybridization changes from sp(2) to sp(3), the conformation and the possible charge delocalization in the protonated molecules will play an important role in determining the subsequent protonation. Our study provides new insight into the acid-doping mechanism of conductive polymers, which could be used as a guide to design new acid doped highly conductive polymers.

Large Area Directed Self-Assembly of Sub-10 nm Particles with Single Particle Positioning Resolution.

Directed self-assembly of nanoparticles (DSA-n) holds great potential for device miniaturization in providing patterning resolution and throughput that exceed existing lithographic capabilities. Although nanoparticles excel at assembling into regular close-packed arrays, actual devices on the other hand are often laid out in sparse and complex configurations. Hence, the deterministic positioning of single or few particles at specific positions with low defect density is imperative. Here, we report an approach of DSA-n that satisfies these requirements with less than 1% defect density over micrometer-scale areas and at technologically relevant sub-10 nm dimensions. This technique involves a simple and robust process where a solvent film containing sub-10 nm gold nanoparticles climbs against gravity to coat a prepatterned template. Particles are placed individually into nanoscale cavities, or between nanoposts arranged in varying degrees of geometric complexity. Brownian dynamics simulations suggest a mechanism in which the particles are pushed into the template by a nanomeniscus at the drying front. This process enables particle-based self-assembly to access the sub-10 nm dimension, and for device fabrication to benefit from the wealth of chemically synthesized nanoparticles with unique material properties.

Second-Harmonic Generation from Sub-5 nm Gaps by Directed Self-Assembly of Nanoparticles onto Template-Stripped Gold Substrates.

Strong field enhancement and confinement in plasmonic nanostructures provide suitable conditions for nonlinear optics in ultracompact dimensions. Despite these enhancements, second-harmonic generation (SHG) is still inefficient due to the centrosymmetric crystal structure of the bulk metals used, e.g., Au and Ag. Taking advantage of symmetry breaking at the metal surface, one could greatly enhance SHG by engineering these metal surfaces in regions where the strong electric fields are localized. Here, we combine top-down lithography and bottom-up self-assembly to lodge single rows of 8 nm diameter Au nanoparticles into trenches in a Au film. The resultant "double gap" structures increase the surface-to-volume ratio of Au colocated with the strong fields in ∼2 nm gaps to fully exploit the surface SHG of Au. Compared to a densely packed arrangement of AuNPs on a smooth Au film, the double gaps enhance SHG emission by 4200-fold to achieve an effective second-order susceptibility χ((2)) of 6.1 pm/V, making it comparable with typical nonlinear crystals. This patterning approach also allows for the scalable fabrication of smooth gold surfaces with sub-5 nm gaps and presents opportunities for optical frequency up-conversion in applications that require extreme miniaturization.

Template-induced structure transition in sub-10 nm self-assembling nanoparticles.

We report on the directed self-assembly of sub-10 nm gold nanoparticles confined within a template comprising channels of gradually varying widths. When the colloidal lattice parameter is mismatched with the channel width, the nanoparticles rearrange and break their natural close-packed ordering, transiting through a range of structural configurations according to the constraints imposed by the channel. While much work has been done in assembling ordered configurations, studies of the transition regime between ordered states have been limited to microparticles under applied compression. Here, with coordinated experiments and Monte Carlo simulations we show that particles transit through a more diverse set of self-assembled configurations than observed for compressed systems. The new insight from this work could lead to the control and design of complex self-assembled patterns other than periodic arrays of ordered particles.

Pure blue-light emissive poly(oligofluorenes) with bifunctional poss in the main chain.

Emission of conjugated polymers is known to undergo bathochromic shift from solution to film formation due to π-π stacking in the solid state. In this report, a series of pearl-necklace-like hybrid polymers is designed via the hydrosilylation condensation between bifunctional polyhedral oligomeric silsesquioxanes (B-POSS) and oligofluorene segments. Optoelectronic analyses unequivocally show that the presence of these interconnecting B-POSS can effectively reduce red-shift in photoluminescence and electroluminescence during film formation. These hybrid poly(oligofluorenes) display stable blue emission with high color purity. Thermal analyses also indicate that they are vitrified polymers with high glass transition temperature (up to 125 °C). We believe that this strategy can be extended to other conjugated systems to control color purity in electroactive materials and holds promise as new emissive materials for various applications.

Protonation induced shifting of electron-accepting centers in intramolecular charge transfer chromophores: a theoretical study.

A new series of chameleonic molecules containing azulene and benzothiadiazole (BT) were designed and synthesized. In the neutral state, BT functions as an electron accepting center, while upon protonation, the electron accepting center shifts to azulene moieties, leading to a remarkable extension of absorption to the NIR region, i.e. up to 2.5 µm. The interchange between donor and acceptor characters upon protonation was confirmed by UV-vis-NIR spectral studies and supported by DFT calculations. Furthermore, the HOMO-LUMO level of ICT chromophores could be finely tailored by a different arrangement of azulenes and BTs in the molecules. The interchange between donor and acceptor characters upon protonation provides an alternative yet effective approach to fine tune optical and electronic properties of NIR chromophores.

Sustainable Vat Photopolymerization-Based 3D-Printing through Dynamic Covalent Network Photopolymers.

Vat photopolymerization (VPP) based three-dimensional (3D) printing, including stereolithography (SLA) and digital light projection (DLP), is known for producing intricate, high-precision prototypes with superior mechanical properties. However, the challenge lies in the non-recyclability of covalently crosslinked thermosets used in these printing processes, limiting the sustainable utilization of printed prototypes. This review paper examines the recently explored avenue of VPP 3D-printed dynamic covalent network (DCN) polymers, which enable reversible crosslinks and allow for the reprocessing of printed prototypes, promoting sustainability. These reversible crosslinks facilitate the rearrangement of crosslinked polymers, providing printed polymers with chemical/physical recyclability, self-healing capabilities, and degradability. While various mechanisms for DCN polymer systems are explored, this paper focuses solely on photocurable polymers to highlight their potential to revolutionize the sustainability of VPP 3D printing.

Near-infrared responsive conjugated polymers to 1.5 µm and beyond: synthesis and electrochromic switching application.

Azulene-containing conjugated polymers with near-infrared absorption up to 1.5 µm and beyond are achieved by treating with trifluoroacetic acid (TFA). Density functional theory calculations reveal that the near-infrared absorption arises from a strong intramolecular charge transfer transition on the polymer backbone, and the near-infrared absorption can be tuned by the degree of protonation. Furthermore, TFA treated polymers show a ten-fold enhancement in electrochromic contrast and significantly improved switching stability, suggesting that these polymers are promising candidates for fabrication of the first generation organic near-infrared devices.

[Research progress of tibial-graft fixation methods on anterior cruciate ligament reconstruction].

Objective: To review the studies about the tibial-graft fixation methods on anterior cruciate ligament (ACL) reconstruction, in order to provide clinical reference. Methods: The literature about the tibial-graft fixation methods on ACL reconstruction at home and abroad was extensively reviewed, and the factors that affect the selection of fixation methods were summarized. Results: The knee flexion angle, graft tension, and graft fixation device are mainly considered when the tibial-graft was fixed on ACL reconstruction. At present, the graft is mainly fixed at 0°/30° of knee flexion. The study shows that the knee joint is more stable after fixed at 30°, while the incidence of knee extension limitation decrease after fixed at 0°. In terms of graft tension, a good effectiveness can be obtained when the tension level is close to 90 N or the knee flexion is 30° to recover the affected knee over-restrained 2 mm relative to the healthy knee. In terms of the graft device, the interference screw is still the most commonly used method of tibial-graft fixation, with the development of all-inside ACL reconstruction in recent years, the cortical button fixation may become the mainstream. Conclusion: Arthroscopic reconstruction is the main treatment of ACL rupture at present. However, there is no optimal fixation method for the tibial-graft, the advantages and disadvantages of each fixation methods need to be further studied.

4D-Printed Hydrogel Actuators through Diffusion-Path Architecture Design.

Recently, smart hydrogels have garnered considerable attention as biomedical devices, and several approaches have been introduced for their fabrication, including the incorporation of stimulus-responsive additives, utilization of molecular imprinting techniques, and application of multilayered hydrogels. However, the nonuniform properties resulting from these approaches limit the practical applications of hydrogels by causing inconsistent performance and behavior. In this study, we propose a novel approach to manipulating the swelling kinetics of hydrogels by engineering their diffusion-path architecture. By simply adjusting the diffusion path length within the hydrogel, we achieved a significant change in swelling kinetics. This approach enables precise control over the diffusion and transport processes within the hydrogel, resulting in enhanced swelling kinetics when reducing the diffusion path length. Furthermore, by strategically designing the diffusion-path architecture of a 3D-printed hydrogel specimen, we can fabricate smart hydrogel actuators that exhibit reversible shape transformations during swelling and deswelling through a nonequilibrium differential swelling. The proposed approach eliminates the need to modify the spatial properties of hydrogel structures such as cross-linking density, polymer, or additive compositions, thereby achieving uniform properties throughout the hydrogel and creating new possibilities for the development of advanced 4D-printed biomedical devices.

Study on the Reactivity Activation of Coal Gangue for Efficient Utilization.

In this study, the research aim is to enhance the activity index of activated coal gangue and study its activation mechanism. The activation process of coal gangue was optimized through orthogonal tests, and the Back-Propagation (BP) neural network model was improved using a genetic algorithm. With the effects of grinding duration, calcination temperature, and calcination duration, the morphological changes and phase transformation processes of coal gangue were studied at the micro and meso levels to clarify the activation mechanism. The results indicated that the effect of calcination temperature on the strength activity index of coal gangue was most significant, followed by grinding duration and calcination duration. The potential activity of coal gangue can be effectively stimulated through mechanical and thermal activation, and the content of potential active minerals in coal gangue powders was also increased. The activation process of coal gangue for the optimal scheme was obtained as grinding at 76 min first and thermal treatment at 54 min at 749 °C. As the thermal activation under 950 °C, some unstable external hydroxyls, and internal hydroxyls in kaolinite from coal gangue were removed, the AlⅥ-O octahedron was destroyed, and kaolinite was transformed into spatially disordered metakaolinite with very high activity.

Directed self-assembly of densely packed gold nanoparticles.

Directing the self-assembly of sub-10-nm nanoparticles has been challenging because of the simultaneous requirements to achieve a densely packed monolayer and rearrange nanoparticles to assemble within a template. We met both requirements by separating the processes into two steps by first forming a monolayer of gold nanoparticles on a suitable liquid subphase of anisole and then transferring it edgewise onto a silicon substrate with a prepatterned template comprising nanoposts and nanogratings. Doing so resulted in nanoparticles that assembled in commensuration with the template design while exhibiting appreciable template-induced strain. These dense arrays of nanostructures could either be directly applied or used as lithographic masks in applications for light collection, chemical sensing, and data storage.

Reconstruction of tissue-engineered bone with bone marrow mesenchymal stem cells and partially deproteinized bone in vitro.

We have explored the optimal seeding density and timing for transplantation of the tissue-engineered bone with BMMSCs (bone marrow mesenchymal stem cells) and PDPB (partially deproteinized bone) in vitro. Rabbit BMMSCs of different densities were seeded into PDPB generated from fresh pig vertebrates to reconstruct tissue-engineered bone in vitro. Adhesion and proliferation of BMMSCs were analysed by MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide] assay from which growth curves of BMMSCs on the PDPB materials were generated. The data show that BMMSCs began to adhere to PDPB after 24 h of primary culture, all groups reaching peak growth on the 6th day, after which the value of A decreased gradually and reached a plateau phase. The optimal BMMSCs seeding density of 5 × 10(6)/ml achieved an excellent adhesion and proliferation activity on PDPB. In summary, the best cell seeding density of constructing tissue-engineered bone with BMMSCs in vitro is 5 × 10(6)/ml, the optimal timing to transplant is the 6th day.