Nickel-Catalyzed Reductive Arylation of α-Bromo Sulfoxide.

A nickel-catalyzed cross-electrophile coupling of aryl iodides with α-bromo sulfoxide to access a diverse array of aryl benzyl sulfoxides has been discovered. These reactions occurred under mild conditions with excellent functional group tolerance so that optically enriched sulfoxides could be coupled with aryl iodides, generating corresponding sulfoxides with excellent stereochemical integrity. Furthermore, the scalability of this transformation was demonstrated. Initial mechanistic studies revealed that the reaction undergoes a radical pathway.

Nickel/photoredox-catalyzed enantioselective arylation of α-chloro thioesters.

The first dual nickel/photoredox-catalyzed enantioselective reductive cross-coupling of racemic α-chloro thioesters with aryl iodides has been developed. This strategy avoids the need for organometallic reagents or stoichiometric metal reductants. This reaction could tolerate a wide range of substrate scope with excellent reactivity and high enantioselectivities (up to 91% ee) to access a variety of chiral α-aryl thioesters. The synthetic utility of the corresponding α-aryl thioesters is demonstrated. Furthermore, we explored the mechanism of such an enantioselective radical cross-coupling process.

Nickel-Catalyzed Cross-Electrophile Coupling of 1,2,3-Benzotriazin-4(3H)-ones with Aryl Bromides.

The nickel-catalyzed cross-electrophile coupling of 1,2,3-benzotriazin-4(3H)-ones with aryl bromides to generate a diverse array of ortho-arylated benzamide derivatives has been developed. The reaction displayed good functional group tolerance with Zn as the reductant. The key to this transformation is the ring opening of benzotriazinones, which undergo a denitrogenative process to obtain various benzamide derivatives (29 examples, 42-93% yield). The scalability of this transformation was demonstrated.

Parametric Effects of Fused Filament Fabrication Approach on Surface Roughness of Acrylonitrile Butadiene Styrene and Nylon-6 Polymer.

This research objective is to optimize the surface roughness of Nylon-6 (PA-6) and Acrylonitrile Butadiene Styrene (ABS) by analyzing the parametric effects of the Fused Filament Fabrication (FFF) technique of Three-Dimensional Printing (3DP) parameters. This article discusses how to optimize the surface roughness using Taguchi analysis by the S/N ratio, ANOVA, and modeling methods. The effects of ABS parameters (initial line thickness, raster width, bed temperature, build pattern, extrusion temperature, print speed, and layer thickness) and PA-6 parameters (layer thickness, print speed, extrusion temperature, and build pattern) were investigated with the average surface roughness (Ra) and root-mean-square average surface roughness (Rq) as response parameters. Validation tests revealed that Ra and Rq decreased significantly. After the optimization, the Ra-ABS and Rq-PA-6 for the fabricated optimized values were 1.75 µm and 21.37 µm, respectively. Taguchi optimization of Ra-ABS, Rq-ABS, Ra-PA-6, and Rq-PA-6 was performed to make one step forward to use them in further research and prototypes.

Nickel/Photoredox-Catalyzed Enantioselective Reductive Cross-Coupling between Vinyl Bromides and Benzyl Chlorides.

A visible-light-promoted nickel/photoredox-catalyzed reductive cross-coupling reaction between vinyl bromides and benzyl chlorides is reported. A diverse array of enantioenriched allylic centers containing products could be achieved in good yields (up to 90%) and high enantioselectivities (up to 95% ee). The mechanistic studies show that this reductive cross-coupling involves a radical pathway.

Nickel-Catalyzed Reductive Coupling of γ-Metalated Ketones with Unactivated Alkyl Bromides.

A nickel-catalyzed reductive cross-coupling reaction of aryl cyclopropyl ketones with easily accessible unactivated alkyl bromides to access aryl alkyl ketones has been developed. This strategy facilitates access to various of γ-alkyl-substituted ketones via ring opening of cyclopropyl ketones (26 examples, 50-90% yield). Initial mechanistic studies revealed that the reaction proceeds via radical cleavage of the alkyl bromide.

Catalytic enantioselective reductive domino alkyl arylation of acrylates via nickel/photoredox catalysis.

Nonsteroidal anti-inflammatory drug derivatives (NSAIDs) are an important class of medications. Here we show a visible-light-promoted photoredox/nickel catalyzed approach to construct enantioenriched NSAIDs via a three-component alkyl arylation of acrylates. This reductive cross-electrophile coupling avoids preformed organometallic reagents and replaces stoichiometric metal reductants by an organic reductant (Hantzsch ester). A broad range of functional groups are well-tolerated under mild conditions with high enantioselectivities (up to 93% ee) and good yields (up to 90%). A study of the reaction mechanism, as well as literature precedence, enabled a working reaction mechanism to be presented. Key steps include a reduction of the alkyl bromide to the radical, Giese addition of the alkyl radical to the acrylate and capture of the α-carbonyl radical by the enantioenriched nickel catalyst. Reductive elimination from the proposed Ni(III) intermediate generates the product and forms Ni(I).

3D-Printed Cold Preservation Device in Renal Autotransplantation for the Treatment of a Patient With Renal Artery Stenosis.

Percutaneous transluminal angioplasty (PTRA) is a common treatment method for renal vascular disease (RVD). However, PTRA may not be effective in patients with abnormal vascular disease. Renal autotransplantation (RAT) has been used as an alternative therapy for these diseases. Restrictions due to intracorporeal kidney cold preservation and the renal function of intracorporeal RAT were not as well protected compared with open operation. We developed this technique of 3D-printed polylactide (PLA) cold jackets for laparoscopic complete intracorporeal RAT for the purpose of better protecting the renal function and determining the feasibility of this novel procedure. The procedure was successfully applied to a 51-year-old woman with bilateral renal artery stenosis. The operation time was 5 hours, and blood loss was 200 ml. The patient's blood pressure remained constant throughout the operation, and the pressure was maintained at 120-140/70-90 mmHg without antihypertensive drugs 1 week after the operation. B-ultrasound showed that the blood flow signal of the transplanted kidney was normal and the boundary between the skin and medulla was clear. The patient was discharged 2 weeks after surgery. One year postoperatively, Doppler ultrasound of the autotransplant showed that the transplanted kidney was normal in size and shape. Radionuclide renal dynamic imaging revealed that the glomerular filtration rate (GFR) of the transplanted kidney was 36.9 ml/min. 3D-printed polylactide (PLA) cold jackets for laparoscopic complete intracorporeal RAT are a safe and effective method for the treatment of renal artery stenosis and represent a feasible method for preserving the renal function of severe renal artery stenosis patients; however, the technology is still at the exploratory stage and has room for further improvements.

State-Of-The-Art and Trends in CO2 Laser Cutting of Polymeric Materials-A Review.

Carbon dioxide (CO2) laser cutting finds one of its most relevant applications in the processing of a wide variety of polymeric materials like thermoplastics and thermosetting plastics. Different types of polymeric materials like polypropylene (PP), polymethyl methacrylate (PMMA), low- and high-density polyethylene (LDPE, HDPE), are processed by laser for different household as well as commercial products in the industry. The reason is their easy availability and economical aspect in the market. The problems associated with laser cutting include heat-affected zone (HAZ) generated on the cut surface, kerf width (KW), surface roughness (SR), dross formation, and striations formation. Furthermore, other related problems include taper cutting for deep parts and high-power consumption. The primary purpose of this work is a comprehensive literature review in CO2 laser cutting of polymeric materials. The influence of parametric variation on the cut quality is also explained. Cut quality in terms of KW, SR, HAZ, dross formation, and striations formation is analyzed by optimizing cutting variables like laser power (PL), cutting speed (CS), assist gas pressure (Pg), pulse frequency, nozzle type and its diameter, and stand-off distance (SOD). The effects of the laser cutting on the properties of different thermoplastics/thermosetting materials are also reported. However, this topic requires further studies on exploring the range of polymeric materials, and their optimal parameters selection to improve the cut quality. Therefore, the research gaps and future research directions are also highlighted in the context of CO2 laser cutting for polymeric materials.

Design and Synthesis of N-phenyl Phthalimides as Potent Protoporphyrinogen Oxidase Inhibitors.

Protoporphyrinogen oxidase (PPO) has been identified as one of the most promising targets for herbicide discovery. A series of novel phthalimide derivatives were designed by molecular docking studies targeting the crystal structure of mitochondrial PPO from tobacco (mtPPO, PDB: 1SEZ) by using Flumioxazin as a lead, after which the derivatives were synthesized and characterized, and their herbicidal activities were subsequently evaluated. The herbicidal bioassay results showed that compounds such as 3a (2-(4-bromo-2,6-difluorophenyl) isoindoline-1,3-dione), 3d (methyl 2-(4-chloro-1,3-dioxoisoindolin-2-yl)-5-fluorobenzoate), 3g (4-chloro-2-(5-methylisoxazol-3-yl) isoindoline-1,3-dione), 3j (4-chloro-2-(thiophen-2-ylmethyl) isoindoline-1,3-dione) and 3r (2-(4-bromo-2,6-difluorophenyl)-4-fluoroisoindoline-1,3-dione) had good herbicidal activities; among them, 3a showed excellent herbicidal efficacy against A. retroflexus and B. campestris via the small cup method and via pre-emergence and post-emergence spray treatments. The efficacy was comparable to that of the commercial herbicides Flumioxazin, Atrazine, and Chlortoluron. Further, the enzyme activity assay results suggest that the mode of action of compound 3a involves the inhibition of the PPO enzyme, and 3a showed better inhibitory activity against PPO than did Flumioxazin. These results indicate that our molecular design strategy contributes to the development of novel promising PPO inhibitors.

3D fabrication and characterization of phosphoric acid scaffold with a HA/ß-TCP weight ratio of 60:40 for bone tissue engineering applications.

A key requirement for three-dimensional printing (3-DP) at room temperature of medical implants depends on the availability of printable and biocompatible binder-powder systems. Different concentration polyvinyl alcohol (PVA) and phosphoric acid solutions were chosen as the binders to make the artificial stent biocompatible with sufficient compressive strength. In order to achieve an optimum balance between the bioceramic powder and binder solution, the biocompatibility and mechanical properties of these artificial stent samples were tested using two kinds of binder solutions. This study demonstrated the printable binder formulation at room temperature for the 3D artificial bone scaffolds. 0.6 wt% PVA solution was ejected easily via inkjet printing, with a supplementation of 0.25 wt% Tween 80 to reduce the surface tension of the polyvinyl alcohol solution. Compared with the polyvinyl alcohol scaffolds, the phosphoric acid scaffolds had better mechanical properties. Though both scaffolds supported the cell proliferation, the absorbance of the polyvinyl alcohol scaffolds was higher than that of the phosphoric acid scaffolds. The artificial stents with a hydroxyapatite/beta-tricalcium phosphate (HA/ß-TCP) weight ratios of 60:40 depicted good biocompatibility for both scaffolds. Considering the scaffolds' mechanical and biocompatible properties, the phosphoric acid scaffolds with a HA/ß-TCP weight ratio of 60:40 may be the best combination for bone tissue engineering applications.

Triazole-linked fluorescent bisboronic acid capable of selective recognition of the Lewis Y antigen.

Cell surface carbohydrates of the Lewis blood group antigens, Lewis X (Lex), Lewis Y (Ley), Lewis A (Lea), and their sialylated derivatives, such as sialy Lewis X (sLex) and sialy Lewis A (sLea), play important roles in various recognition processes. These cell surface carbohydrates have also been associated with the development and progression of many types of cancers. Recently, we synthesized four anthracene-based fluorescent bisboronic acid sensors (compounds 2a-d) linked by 'click' chemistry with tethers of different lengths to match the epitope of various Lewis group of sugars. Among the four compounds, 2a appears to have both high sensitivity and selectivity for Ley among other carbohydrate antigens.

Bone Morphogenetic Protein-9 Enhances Osteogenic Differentiation of Human Periodontal Ligament Stem Cells via the JNK Pathway.

Bone morphogenetic protein-9 (BMP9) shows great osteoinductive potential in bone regeneration. Periodontal ligament stem cells (PDLSCs) with multi-differentiation capability and low immunogenicity are increasingly used as seed cells for periodontal regenerative therapies. In the present study, we investigated the potent osteogenic activity of BMP9 on human PDLSCs (hPDLSCs), in which the c-Jun N-terminal kinase (JNK) pathway is possibly involved. Our results showed that JNK inhibition by the specific inhibitor SP600125 or adenovirus expressing small interfering RNA (siRNA) targeting JNK (AdR-si-JNK) significantly decreased BMP9-induced gene and protein expression of early and late osteogenic markers, such as runt-related transcription factor 2 (Runx2), alkaline phosphatase (ALP), osteopontin (OPN), and osteocalcin (OCN), in hPDLSCs. We also confirmed the in-vivo positive effect of JNKs on ectopic bone formation induced by hPDLSCs injected into the musculature of athymic nude mice and BMP9 ex vivo gene delivery. For the cellular mechanism, we found that BMP9 activated the phosphorylation of JNKs and Smad2/3, and that JNKs may engage in cross-talk with the Smad2/3 pathway in BMP9-mediated osteogenesis.