Photochemical Synthesis of Nitriles from Alcohols.

Nickel-catalyzed hydrocyanation of 1,3-butadiene with hydrogen cyanide gas is the predominant method for the synthesis of adiponitrile, which is an important precursor for polymer production. However, the use of fossil-derived alkenes raises environmental concerns, and hydrogen cyanide is highly volatile and extremely toxic. Herein, we report the use of biomass-derived 1,4-butanediol, as well as other primary alcohols, for photochemical synthesis of linear and branched nitriles and dinitriles, including adiponitrile, with 1,4-dicyanobenzene as the CN source. This mild, sustainable method does not require hydrogen cyanide gas or an air- or moisture-sensitive metal catalyst and is applicable for the production of dinitriles as precursors of diamines, which have potential utility for the development of novel polyamides.

A novel strategy for calcium magnesium phosphate/carboxymethyl chitosan composite bone cements with enhanced physicochemical properties, excellent cytocompatibility and osteogenic differentiation.

Artificial bone substitutes for bone repair and reconstruction still face enormous challenges. Previous studies have shown that calcium magnesium phosphate cements (CMPCs) possess an excellent bioactive surface, but its clinical application is restricted due to short setting time. This study aimed to develop new CMPC/carboxymethyl chitosan (CMCS) comg of mixed powders of active MgO, calcined MgO and calcium dihydrogen phosphate monohydrate. With this novel strategy, it can adjust the setting time and improve the compressive strength. The results confirmed that CMPC/CMCS composite bone cements were successfully developed with a controllable setting time (18-70 min) and high compressive strength (87 MPa). In addition, the composite bone cements could gradually degrade in PBS with weight loss up to 32% at 28 d. They also promoted the proliferation of pre-osteoblasts, and induced osteogenic differentiation. The findings indicate that CMPC/CMCS composite bone cements hold great promise as a new type of bone repair material in further and in-depth studies.

CuSO4/H2O2induced polydopamine/polysulfobetaine methacrylate co-deposition on poly(amino acid) membranes for improved anti-protein adsorption and antibacterial activity.

Stopping postoperative soft tissue adhesions is one of the most challenging clinical problems that needs to be addressed urgently to avoid secondary injury and pain to patients. Currently, membrane materials with anti-protein adsorption and antibacterial activity are recognized as an effective and promising anti-adhesion barrier to prevent postoperative adhesion and the recurrent adhesion after adhesiolysis. Herein, poly(amino acid) (PAA), which is structurally similar to collagen, is selected as the membrane base material to successfully synthesize PAA-5 membranes with excellent mechanical and degradation properties by in-situ melt polymerization and hot-melt film-forming technology. Subsequently, the co-deposition of polydopamine/polysulfobetaine methacrylate (PDA/PSBMA) coatings induced by CuSO4/H2O2on PAA-5 membranes results in the formation of PDC-5S and PDC-10S, which exhibit excellent hemocompatibility, protein antifouling properties, and cytocompatibility. Additionally, PDC-5S and PDC-10S demonstrated significant antibacterial activity againstEscherichia coliandStaphylococcus aureus, with an inhibition rate of more than 90%. As a result, this study sheds light on newly discovered PAA membranes with anti-protein adsorption and antibacterial activity can sever as one of the promising candidates for the prevention of postoperative peritoneum adhesions.

Decolorization, spectral broadening, and luminescence enhancement in Tb:Y2O3 transparent ceramics through vacuum thermal reduction.

Tb3+ is extensively employed in magneto-optical devices and luminescent materials owing to its distinctive physical properties. However, under certain conditions, trivalent Tb3+ readily undergoes oxidation to tetravalent Tb4+, significantly reducing the performance of devices containing Tb3+. In this Letter, we report a technique called dual-annealing (DA) post-treatment, which effectively solves Tb oxidation issues by utilizing the reducibility of the vacuum environment. High-quality Tb:Y2O3 transparent ceramics were prepared with in-line transmittance of ∼80% at 800 nm. Subsequently, the prepared ceramics were subjected to DA treatment. The optical, photoluminescence, radioluminescence, and x-ray imaging properties of DA samples were comprehensively compared with those of conventionally single-annealed (SA) samples. The coloration of Tb:Y2O3 transparent ceramics due to Tb4+ absorption was eliminated by DA. Notably, the DA sample showed a 3.28-fold increase in photoluminescence intensity and a 2.73-fold increase in radioluminescence intensity compared with the traditional SA sample. DA post-treatment enables Tb: Y2O3 transparent ceramics to achieve x-ray imaging capabilities. This Letter presents a simple, efficient, and universally applicable post-treatment technique expected to replace conventional hydrogen annealing in numerous scenarios.

A Bioactive Degradable Composite Bone Cement Based on Calcium Sulfate and Magnesium Polyphosphate.

Calcium sulfate bone cement (CSC) is extensively used as a bone repair material due to its ability to self-solidify, degradability, and osteogenic ability. However, the fast degradation, low mechanical strength, and insufficient biological activity limit its application. This study used magnesium polyphosphate (MPP) and constructed a composite bone cement composed of calcium sulfate (CS), MPP, tricalcium silicate (C3S), and plasticizer hydroxypropyl methylcellulose (HPMC). The optimized CS/MPP/C3S composite bone cement has a suitable setting time of approximately 15.0 min, a compressive strength of 26.6 MPa, and an injectability of about 93%. The CS/MPP/C3S composite bone cement has excellent biocompatibility and osteogenic capabilities; our results showed that cell proliferation is up to 114% compared with the control after 5 days. After 14 days, the expression levels of osteogenic-related genes, including Runx2, BMP2, OCN, OPN, and COL-1, are about 1.8, 2.8, 2.5, 2.2, and 2.2 times higher than those of the control, respectively, while the alkaline phosphatase activity is about 1.7 times higher. Therefore, the CS/MPP/C3S composite bone cement overcomes the limitations of CSC and has more effective potential in bone repair.

Enhancing osteoblast proliferation and bone regeneration by poly (amino acid)/selenium-doped hydroxyapatite.

Among various biomaterials employed for bone repair, composites with good biocompatibility and osteogenic ability had received increasing attention from biomedical applications. In this study, we doped selenium (Se) into hydroxyapatite (Se-HA) by the precipitation method, and prepared different amounts of Se-HA-loaded poly (amino acid)/Se-HA (PAA/Se-HA) composites (0, 10 wt%, 20 wt%, 30 wt%) byin-situmelting polycondensation. The physical and chemical properties of PAA/Se-HA composites were characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and their mechanical properties. XRD and FT-IR results showed that PAA/Se-HA composites contained characteristic peaks of PAA and Se-HA with amide linkage and HA structures. DSC and TGA results specified the PAA/Se-HA30 composite crystallization, melting, and maximum weight loss temperatures at 203.33 °C, 162.54 °C, and 468.92 °C, respectively, which implied good thermal stability. SEM results showed that Se-HA was uniformly dispersed in PAA. The mechanical properties of PAA/Se-HA30 composites included bending, compressive, and yield strengths at 83.07 ± 0.57, 106.56 ± 0.46, and 99.17 ± 1.11 MPa, respectively. The cellular responses of PAA/Se-HA compositesin vitrowere studied using bone marrow mesenchymal stem cells (BMSCs) by cell counting kit-8 assay, and results showed that PAA/Se-HA30 composites significantly promoted the proliferation of BMSCs at the concentration of 2 mg ml-1. The alkaline phosphatase activity (ALP) and alizarin red staining results showed that the introduction of Se-HA into PAA enhanced ALP activity and formation of calcium nodule. Western blotting and Real-time polymerase chain reaction results showed that the introduction of Se-HA into PAA could promoted the expression of osteogenic-related proteins and mRNA (integrin-binding sialoprotein, osteopontin, runt-related transcription factor 2 and Osterix) in BMSCs. A muscle defect at the back and a bone defect at the femoral condyle of New Zealand white rabbits were introduced for evaluating the enhancement of bone regeneration of PAA and PAA/Se-HA30 composites. The implantation of muscle tissue revealed good biocompatibility of PAA and PAA/Se-HA30 composites. The implantation of bone defect showed that PAA/Se-HA30 composites enhanced bone formation at the defect site (8 weeks), exhibiting good bone conductivity. Therefore, the PAA-based composite was a promising candidate material for bone tissue regeneration.

Light-Triggered, Ni-Catalyzed Cyanation of Aryl Triflates with 1,4-Dicyanobenzene as the CN Source.

A light-triggered, Ni-catalyzed cyanation of aryl triflates was herein reported, which provides a benign photochemical synthesis of aryl nitriles using 1,4-dicyanobenzene as the CN source instead of HCN or a metallic CN source. This mild method uses a readily available bisphosphine ligand and a soluble organosilicon reagent as the reductant and is carried out under purple light without an external photocatalyst. This cyanation was effective for aryl triflates derived from phenols and bisphenols as well as lignin-derived phenolic compounds, demonstrating its potential utility for the synthesis of aryl nitriles from biomass.

Metabolome and transcriptome analyses identify the characteristics and expression of related saponins of the three genealogical plants of bead ginseng.

Objective: The classification and clinical usage of the different species of bead ginseng are often confused. Therefore, we conducted an integrated metabolomics and transcriptome analysis of three main species of Panax, including Panax japonicas, Panax pseudoginseng, and Panax pseudo-ginseng var. elegantior. Methods: A broad metabolome and transcriptome analysis for three origins of bead ginseng plants was performed using UPLC-ESI-MS/MS, RNA sequencing and annotation, and bioinformatic analysis of transcriptome data. Results: The levels of 830 metabolites were determined. A total of 291 differentially accumulated metabolites (DAMs) between Panax pseudo-ginseng var. elegantior and Panax japonicas (Group A), with 73 upregulated and 218 downregulated. A total of 331 DAMs (110 upregulated and 221 downregulated) were found between Panax pseudoginseng and Panax japonicas (group B). There were 160 DAMs (102 up-regulated and 58 down-regulated) between Panax pseudoginseng and Panax pseudo-ginseng var. elegantior (group C). In addition, RNA sequencing was performed in the above three ways. A total of 16,074 differential expression genes (DEGs) were detected between Group A, in which 7,723 genes were upregulated and 8,351 genes were downregulated by RNA sequencing. Similarly, 15,705 genes were differentially expressed between group B, in which 7,436 genes were upregulated and 8,269 genes were downregulated. However, only 1,294 genes were differentially expressed between group C, in which 531 genes were upregulated and 763 genes were downregulated. We performed differential gene analysis on three groups of samples according to the Venn diagram and found that 181 differential genes were present. A total of 3,698 and 2,834 unique genes were in groups A and B, while 130 unique genes were in group C. Conclusions: This study provides metabolome and transcriptome information for three bead ginseng plants. The analysis of the metabolite content showed differences in the attributes of the three bead ginseng, contained mainly flavonoids, phenolic acids as well as terpenes.

Effects of ATP on the Physicochemical Properties and Cytocompatibility of Calcium Sulfate/Calcium Citrate Composite Cement.

Adenosine triphosphate (ATP), acting as a source of energy, has effects on cellular activities, such as adhesion, proliferation, and differentiation. In this study, ATP-loaded calcium sulfate hemihydrate/calcium citrate tetrahydrate cement (ATP/CSH/CCT) was successfully prepared for the first time. The effect of different contents of ATP on the structure and physicochemical properties of ATP/CSH/CCT was also studied in detail. The results indicated that incorporating ATP into the cement did not significantly alter their structures. However, the addition ratio of ATP directly impacted the mechanical properties and in vitro degradation properties of the composite bone cement. The compressive strength of ATP/CSH/CCT gradually decreased with an increasing ATP content. The degradation rate of ATP/CSH/CCT did not significantly change at low concentrations of ATP, but it increased with a higher ATP content. The composite cement induced the deposition of a Ca-P layer in a phosphate buffer solution (PBS, pH = 7.4). Additionally, the release of ATP from the composite cement was controlled. The ATP was controlled releasing at the 0.5% and 1% ATP in cement by the diffusion of ATP and the degradation of the cement, whereas it was controlled by the diffusion process merely at the 0.1% ATP in cement. Furthermore, ATP/CSH/CCT demonstrated good cytoactivity with the addition of ATP and is expected to be used for the repair and regeneration of bone tissue.

Injectable Self-Setting Ternary Calcium-Based Bone Cement Promotes Bone Repair.

Bone defects, especially large ones, are clinically difficult to treat. The development of new bone repair materials exhibits broad application prospects in the clinical treatment of trauma. Bioceramics are considered to be one of the most promising biomaterials owing to their good biocompatibility and bone conductivity. In this study, a self-curing bone repair material having a controlled degradation rate was prepared by mixing calcium citrate, calcium hydrogen phosphate, and semi-hydrated calcium sulfate in varying proportions, and its properties were comprehensively evaluated. In vitro cell experiments and RNA sequencing showed that the composite cement activated PI3K/Akt and MAPK/Erk signaling pathways to promote osteogenesis by promoting the proliferation and osteoblastic differentiation of mesenchymal stem cells. In a rat model with femoral condyle defects, the composite bone cement showed excellent bone repair effect and promoted bone regeneration. The injectable properties of the composite cement further improved its practical applicability, and it can be applied in bone repair, especially in the repair of irregular bone defects, to achieve superior healing.

Light-Promoted Ni-Catalyzed Cross-Coupling of Aryl Chlorides with Hydrazides: Application to the Synthesis of Rizatriptan.

A general and highly efficient photochemical C-N coupling reaction of challenging (hetero)aryl chlorides with hydrazides is reported. Catalyzed by a Ni(II)-bipyridine complex, this reaction provides an efficient tool for the synthesis of arylhydrazines in the presence of a soluble organic amine base without an external photosensitizer. The reaction features a wide substrate range (54 examples) and excellent functional group tolerance. The method has also been successfully applied to the three-step concise synthesis of rizatriptan, an effective drug for migraine and cluster headaches.

Calibration Model Optimization for Strain Metrology of Equal Strength Beams Using Deflection Measurements.

Strain sensors, especially fiber Bragg grating (FBG) sensors, are of great importance in structural health monitoring, mechanical property analysis, and so on. Their metrological accuracy is typically evaluated by equal strength beams. The traditional strain calibration model using the equal strength beams was built based on an approximation method by small deformation theory. However, its measurement accuracy would be decreased while the beams are under the large deformation condition or under high temperature environments. For this reason, an optimized strain calibration model is developed for equal strength beams based on the deflection method. By combining the structural parameters of a specific equal strength beam and finite element analysis method, a correction coefficient is introduced into the traditional model, and an accurate application-oriented optimization formula is obtained for specific projects. The determination method of optimal deflection measurement position is also presented to further improve the strain calibration accuracy by error analysis of the deflection measurement system. Strain calibration experiments of the equal strength beam were carried out, and the error introduced by the calibration device can be reduced from 10 µÎµ to less than 1 µÎµ. Experimental results show that the optimized strain calibration model and the optimum deflection measurement position can be employed successfully under large deformation conditions, and the deformation measurement accuracy is improved greatly. This study is helpful to effectively establish metrological traceability for strain sensors and furthermore improve the measurement accuracy of strain sensors in practical engineering scenarious.

Fabricating biodegradable calcium phosphate/calcium sulfate cement reinforced with cellulose: in vitro and in vivo studies.

Osteoporosis is a growing public health concern worldwide. To avoid extra surgeries, developing biodegradable bone cement is critical for the treatment of osteoporosis. Herein, we designed calcium phosphate/calcium sulfate cement reinforced with sodium carboxymethyl cellulose (CMC/OPC). It presents an appropriate physicochemical performance for clinical handling. Meanwhile, CMC/OPC bone cement promotes osteogenic differentiation in vitro. Results of the immune response in vitro and in vivo confirmed that increasing the cellulose content triggered macrophage switching into the M2 phenotype and CMC/OPC exhibited significant anti-inflammation. Furthermore, in vitro and in vivo degradation demonstrated that cellulose tailors the degradation rate of composite bone cement, which achieved a linear degradation process and could degrade by more than 90% for 12 weeks. In summary, the composite bone cement CMC/OPC is a promising candidate for bone repair applications.

Ni(I)-Catalyzed Hydroxylation of Aryl Halides with Water under Thermal Catalysis.

A highly efficient hydroxylation of (hetero)aryl halides using water as a hydroxyl source via Ni catalysis promoted by PhSiH3 under thermal catalysis is reported. This methodology provides a general procedure to obtain diverse multifunctional pharmaceutically phenols and polyphenols, some of which are proven challenging to be synthesized using literature methods. Mechanism studies demonstrated that the addition of PhSiH3 led to the generation of active Ni(I) species, which catalyze the hydroxylation via a Ni(I)-Ni(III) pathway.

Effect of ZnO-doped magnesium phosphate cements on osteogenic differentiation of mBMSCs in vitro.

The insufficient osteogenesis of magnesium phosphate cements (MPCs) limits its further application. It is significant to develop a bioactive MPC with osteogenic properties. In this work, MPCs were reinforced by zinc oxide nanoparticles (ZnO-NPs). The composition, microstructure, setting time, compressive strength and degradation of ZnO-NPs/MPCs (ZNMPCs) were evaluated. The results showed that the setting times of MPCs were prolonged from 8.2 to 25.3 min (5.0ZNMPC). The exothermic temperatures were reduced from 45.8 ± 0.4℃ (MPCs) to 39.3 ± 0.5℃ (1.0ZNMPC). The compressive strength of ZNMPC composite cement with 1 wt. % ZnO-NPs (1.0ZNMPC) was the highest (42.9 MPa) among all the composite cements. Furthermore, the ZNMPCs were cultured with mouse bone marrow mesenchymal stem cells (mBMSCs). The results yielded that the ZNMPCs exhibited good cytocompatibility with enhanced differentiation, proliferation, and mineralization on mBMSCs, and it also pronouncedly elevated the expressions of genes and proteins involving osteogenesis. These findings suggested that ZNMPCs could drive the differentiation toward osteogenesis and mineralization of mBMSCs, providing a simple way to the MPC with enhanced osteogenesis for further orthopedic applications.

Double-network composites based on inorganic fillers reinforced dextran-based hydrogel with high strength.

The biodegradable hydrogels with a 3D network structure have potential applications in bone tissue engineering. Here, inspired by natural bone, the novel organic-inorganic composites (GelMPC-x) with high compressive strength are designed via adding magnesium oxide/calcium dihydrogen phosphate (MPC) powders into the oxidized dextran/gelatin (OD/Gel) hydrogel. GelMPC-x composites can trigger the gelation of OD/Gel hydrogel through an acid-alkaline reaction between magnesium oxide and calcium dihydrogen phosphate, thus forming an organic-inorganic double network. The cross-linked network between oxidized dextran and gelatin, and the multiple weak interactions between OD/Gel hydrogel and MPC enable the composites to have remarkable compressive strength (77-652 kPa) at the strain of 44 %. More importantly, the composites with appropriate MPC content possess superior injectability, high porosity, and excellent cytocompatibility. This work provides guidelines for the preparation of oxidized dextran-based composite hydrogels with enhanced mechanical performance.

A Combination of Baicalin and Berberine Hydrochloride Ameliorates Dextran Sulfate Sodium-Induced Colitis by Modulating Colon Gut Microbiota.

Baicalin and berberine hydrochloride are the main chemical compositions of Scutellariae Radix and Coptidis Rhizoma, respectively. S. Radix and C. Rhizoma are two traditional Chinese herbs that are commonly used together in compounded formulations to treat colitis. Therefore, the combination of Baicalin and berberine hydrochloride (BBH) to treat colitis was studied. The results of pharmacological evaluations demonstrated the excellent protective effects of BBH on colitis induced by dextran sulfate sodium (DSS). BBH could improve the morphological condition of colitis in mice and maintain the balance of proinflammation cytokines (IL-6, IL-8, IL-1ß, and TNF-α) and anti-inflammation cytokines (IL-4 and IL-10). The 16s rDNA sequencing revealed that BBH was able to modulate the composition of intestinal microflora, especially the abundances of Eubacterium_brachy_group, Holdemania, Erysipelotrichaceae_UCG_003, Christensenellaceae_R-7_group, and Sellimonas. The results of PICRUSt indicated that the therapeutic effects of BBH were tightly connected with DNA synthesis, replication and repair of gut microbiota. In summary, it was concluded that BBH could protect mice against DSS-induced colitis, and the protective effects were tightly correlated with gut microbiota.

Arg-Gly-Asp peptide functionalized poly-amino acid/ poly (p-benzamide) copolymer with enhanced mechanical properties and osteogenicity.

Poly-amino acid (PAA) is a promising biomaterial in biomedical engineering due to its similar amide bond structure to collagen and excellent biocompatibility, but the lack of osteogenic activity and inferior mechanical strength limit its long-term application in orthopedics. In this study, a poly-amino acid/poly (p-benzamide) (PAA-PBA) copolymer with high mechanical strength was designed and fabricated by the method of solution polymerization. The chain structures, thermal properties and mechanical properties of these polymers were evaluated and results showed that PBA greatly promoted the mechanical properties of PAA, and the copolymer performed the maximum mechanical strengths with compressive strength, bending strength and tensile strength of 123 MPa, 107 MPa and, 95 MPa, respectively. To increase the bioactivity of surface, a bioactive coating that consists of poly-(dopamine) (PDA) nanolayers and tripeptide Arginine-Glycine-Aspartic acid (RGD) on sulfonated PAA-PBA copolymer was created. A porous structure appeared on the surface after modification, the surface roughness and hydrophilicity of copolymer has been improved obviously after introducing PDA and RGD peptide coating. The in vitro bioactivity evaluation demonstrated that the RGD-functionalized sample showed a significantly improved ability to promote bone apatite mineralization, cell adhesion, proliferation and osteogenic differentiation. In a word, such a strategy of material synthesis and surface modification method shows a great potential for broadening the use of PAA in the application of load-bearing bone substitute biomaterials.

Photochemically Enabled, Ni-Catalyzed Cyanation of Aryl Halides.

A light-promoted Ni-catalyzed cyanation of aryl halides employing 1,4-dicyanobenzene as a cyanating agent is reported. A broad array of aryl bromides, chlorides, and druglike molecules could be converted into their corresponding nitriles (65 examples). Mechanistic studies suggest that upon irradiation, the oxidative addition product Ni(II)(dtbbpy)(p-C6H4CN)(CN) undergoes homolytic cleavage of the Ni-aryl bond to generate an aryl radical and a Ni(I)-CN species, the latter of which initiates subsequent cyanation reactions.

The Fate and Intermediary Metabolism of Soyasapogenol in the Rat.

Research suggests that soyasaponins are poorly absorbed in the GI tract and that soyasaponin aglycones or soyasapogenols are absorbed faster and in greater amounts than the corresponding soyasaponins. Therefore, it is important to understand the bioavailability of these compounds for the potential development of functional foods containing their components. In this paper, to investigate the metabolic characteristics of soyasapogenols A and B, the pharmacokinetic parameters in rats were determined via oral and intravenous administration. The liver metabolites of soyasapogenols were identified using UPLC-/Q-TOF-MS/MS, and their metabolic pathways were also speculated. The results show that, after oral administration, there was a bimodal phenomenon in the absorption process. Tmax was about 2 h, and soyasapogenol was completely metabolized 24 h later. The bioavailability of soyasapogenol was superior, reaching more than 60%. There were sixteen metabolites of soyasapogenol A and fifteen metabolites of soyasapogenol B detected in rat bile. Both phase I and II metabolic transformation types of soyasapogenols, including oxidation, dehydrogenation, hydrolysis, dehydration, deoxidization, phosphorylation, sulfation, glucoaldehyde acidification, and conjugation with cysteine, were identified. In addition, soyasapogenol A could be converted into soyasapogenols B and E in the metabolic process. These results suggest that it is feasible to use soyasapogenols as functional ingredients in nutraceuticals or food formulations.