ABSTRACT
Cp2Fe-mediated electrochemical synthesis of a diverse array of phosphorylated azaspiro[4.5]di/trienones has been developed, which demonstrated broad substrate scope and good diastereoselectivity. It represents the first example of electrochemical synthesis of phosphorylated azaspiro[4.5]di/trienones, circumventing the need for external oxidants and high temperatures. Moreover, a plausible mechanism including radical-initiated dearomative cyclization driven by ferrocenium cations has been provided, which was supported by the related mechanistic study.
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Cp2Fe-mediated electrochemical synthesis of phosphorylated indoles and Trp-containing oligopeptides has been developed, which eliminates the need for external oxidants and yields the desired products in moderate to excellent yields under mild conditions. Importantly, the synthetic applicability was further demonstrated through its easy scalability and the anticancer activity of the product. Remarkably, it presents the first electrochemical protocol to access the phosphorylation of indoles and Trp-containing oligopeptides.
Subject(s)
Indoles , Oligopeptides , Indoles/chemistry , Indoles/chemical synthesis , Phosphorylation , Oligopeptides/chemistry , Oligopeptides/chemical synthesis , Molecular Structure , Tryptophan/chemistry , Electrochemical Techniques , Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , HumansABSTRACT
BACKGROUND: Hypertrophic scars (HS) cause functional impairment and cosmetic deformities following surgeries or burns (30% to 94%). There is no target therapy yet because the pathogenesis of HS progression is not well-known. In tissue fibrosis, Zinc finger E-box binding homeobox 1 (ZEB1) abnormal upregulation is an important cause for extracellular matrix (ECM) overexpression, which is the main molecular change in HS. Therefore, we hypothesized that ZEB1-knockdown inhibits HS formation. METHODS: ZEB1 expression in human HS and TGF-ß1-induced fibroblasts were identified by PCR and western blotting. ZEB1 was knockdown by siRNA in HS fibroblasts (HSFs) and mouse HS model (C57/BL6, male, 8-12 weeks). After 8-hour-transfection, HSFs were subjected to PCR, western blotting and CCK-8, apoptosis, migration and contraction assays. Mice HS were analyzed by HE staining, PCR and western blotting after 56 days. RESULTS: ZEB1 was upregulated in HS tissue (2.0-fold; p < 0.001). ZEB1 knockdown inhibited HSFs activity (0.6 to 0.7-fold; p < 0.001), the expression of fibrotic markers (0.4 to 0.6-fold; p < 0.001) and ß-catenin, cyclinD1 and c-Myc expression (0.5-fold; p < 0.001). In mouse HS models, HS skin thickness was thinner (1.60 ± 0.40 mm vs. 4.04 ± 0.36 mm; p < 0.001) after ZEB1 knockdown. CONCLUSIONS: Knockdown of ZEB1 inhibits HS formation both in vitro and in vivo. However, this is an in vitro/mouse model and more validation is needed. CLINICAL RELEVANCE STATEMENT: The discovery of ZEB1 as a mediator of HS formation might be a potential therapeutic target in HS treatment.
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An efficient and environmentally friendly electrochemical synthesis of phosphorylated oxindoles and indolo[2,1-a]isoquinolin-6(5H)-ones mediated by readily available Cp2Fe has been developed, which illustrated a broad substrate scope and diverse functional group compatibility. This protocol featured an external oxidant-free process and was at room temperature, which was proposed to be driven by the anodic oxidation of Cp2Fe.
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The construction of platinum complexes with high steric hindrance is expected to suppress triple-triplet annihilation and π-π stacking to achieve high-performance organic light-emitting diodes (OLEDs) with low efficiency roll-off. Herein, two large steric hindrance platinum complexes (N-CzPhPtacac and N-CzCF3PhPtacac) were prepared by taking advantage of steric hindrance between the phenyl group on carbazole and the functional group (phenyl and trifluoromethyl substituted phenyl) at the 3-position of a pyridine moiety. Due to the similar electron cloud distribution and gap difference between the HOMO and LUMO, the two complexes showed similar orange-red emission peaks at 590 and 596 nm with high PL quantum yields of 90% and 92% and short excited state lifetimes of 2.77 and 3.08 µs in doped films, respectively. Consequently, OLEDs based on N-CzPhPtacac and N-CzCF3PhPtacac showed maximum external quantum efficiency (EQEmax) values of 15.4% and 18.9%, respectively. Importantly, benefitting from the more stretched spatial configuration from the -CF3 effect, the corresponding OLED exhibited a lower efficiency roll-off, with an EQE of 18.1% at 1000 cd m-2.
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Poor compatibility limits the wide application of biodegradable poly (lactic acid)/poly (butylene adipate-terephthalate) (PLA/PBAT) blends in packaging industry. How to prepare compatibilizers with high efficiency and low cost by simple methods is a challenge. In this work, methyl methacrylate-co-glycidyl methacrylate (MG) copolymer with different epoxy group content are synthesized as reactive compatibilizers to resolve this issue. The effects of glycidyl methacrylate and MG contents on phase morphology and physical properties of the PLA/PBAT blends are systematically investigated. During melt blending, MG migrates to the phase interface, and then grafts with PBAT to form PLA-g-MG-g-PBAT terpolymers. When the molar ratio of MMA and GMA in MG is 3:1, the reaction activity of MG with PBAT is the highest and the compatibilization effect is the best. When the M3G1 content is 1 wt%, the tensile strength and the fracture toughness are increased to 37. 1 MPa and 120 MJ/m3, which increase by 34 % and 87 %, respectively. The size of PBAT phase decreases from 3.7 µm to 0.91 µm. Therefore, this work provides a low-cost and simple method to prepare the compatibilizers with high efficiency for the PLA/PBAT blend, and provides a new basis for the design of epoxy compatibilizers.
Subject(s)
Polyesters , Polymers , Epoxy Resins , Adipates , Poly A , Lactic AcidABSTRACT
Application of elicitors can greatly enhance plant immune resistance against pathogens. However, it is still obscure whether elicitor activity is influenced by diverse sources. This study investigated the effect of foliar spraying of 19 batches of Chrysanthemum indicum polysaccharides (CIPs) on the disease resistance of Atractylodes macrocephala Koidz. (A. macrocephala) and explored the main reasons for the differences of inducing activity of CIP elicitors. PCA, OPLS-DA, grey relational analysis and entropy weight method had good predictability for the activity evaluation of CIP elicitors and other plant-derived elicitors. The results showed that 19 batches of CIPs had definite regional differences in inducing activity and monosaccharide content. CIP elicitors with high inducing activity could significantly increase the accumulation of Atractylenolide â ¡ and Atractylenolide â ¢, the mRNA relative transcription level of CAT, POD, PAL genes, the amount of pH change in the medium and effectively reduce the disease index of A. macrocephala. Furthermore, CIP with high inducing activity exhibited the high contents of Rha, Ara and GalA, which might be the main contributor to their high activity. The evaluation procedure developed in this work can be applied for screening CIP elicitors with high inducing activity, and it lays a foundation for identifying more functional elicitors related to plant immune resistance.
Subject(s)
Atractylodes , Chrysanthemum , Monosaccharides , Disease Resistance , Atractylodes/chemistry , Polysaccharides/pharmacologyABSTRACT
In patients with severe blepharoptosis, the function of the levator muscle is usually weak. Even if a large amount of levator is resected, under-correction and recurrence often occur postoperatively. Frontalis suspension is the first choice for severe ptosis; however, the external orbital lifting force of the frontalis causes non-physiological eyelid movement. Conjoint fascial sheath (CFS) is a fibrous tissue which can provide dynamic movement of upper eyelids and has been applied for the treatment of mild and moderate blepharoptosis in recent years. This study aims to assess the efficacy and safety of CFS suspension combined with levator muscle advancement for treating severe blepharoptosis. A retrospective study included 44 patients (60 eyelids) with severe ptosis who underwent the modified technique. Preoperatively, levator muscle function and margin reflex distance 1 (MRD1) were measured. Surgical outcomes, symmetry results and complications were evaluated postoperatively. At the 12-18 months follow-up, adequate or normal correction was achieved in 56 eyelids (93.3%), and 37 patients (84.1%) presented good or fair symmetry results. The most common complication was conjunctival prolapse, which was observed in six eyelids (10.0%), followed by lid fold deformity and under-correction. No exposure keratitis was recorded. In conclusion, the modified technique can physically elevate the eyelid with limited tissue injury and is effective for the correction of severe ptosis. Both satisfactory functional and esthetic results were achieved, and severe complications (such as exposure keratitis) were not observed.
Subject(s)
Blepharoplasty , Blepharoptosis , Keratitis , Humans , Blepharoptosis/surgery , Blepharoplasty/methods , Retrospective Studies , Oculomotor Muscles/surgery , Keratitis/surgery , Treatment OutcomeABSTRACT
INTRODUCTION: Fat grafting is an efficient and safe procedure for the correction of upper eyelid sulcus deepening. Stromal vascular fraction (SVF) gel has been proven to be an ideal fat derivative and can be widely used for facial augmentation. We aimed to determine the efficacy of SVF gel for the correction of a mild-to-moderate sunken superior sulcus among Asian patients. METHODS: Patients with a mild-to-moderate sunken superior sulcus underwent SVF gel grafting of the sunken upper periorbital area. The primary result was the quantitative volume difference in the superior sulcus region before and after grafting. This was evaluated through three-dimensional VECTRA® imaging. The secondary results included the aesthetic quantitative evaluation results (upper lid area and pretarsal space ratio), global aesthetic improvement scale (GAIS) score, and complications. RESULTS: Thirty-one patients with mild-to-moderate sunken upper eyelids were included in this study. The average unilateral injected amount was 1.235 mL (± 0.171 mL). The 1-year delta volume was 0.801 ± 0.086 mL, and the effective survival volume was 65.3% (± 6.1%). The median preoperative pretarsal space and upper lid area ratio was 1.010 (± 0.150). The median postoperative pretarsal space and upper lid area ratio at 1 year was 0.159 (± 0.031) (n = 62; P < 0.0001), indicating a significantly reduced sunken appearance. The average GAIS score was 2.174 (± 0.391). All patients were satisfied with their surgical outcomes. The reoperation rate was 12.9%. CONCLUSIONS: SVF gel is safe and effective for the treatment of a mild-to-moderate sunken superior sulcus and is associated with satisfactory clinical outcomes and short recovery times.
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Hypertrophic scar (HS) is a fibroproliferative disorder that causes cosmetic as well as functional problems; however, to our knowledge, there is no satisfactory treatment for HS to date. Previous studies have indicated that angiogenesis plays a crucial role in HS formation; therefore, anti-angiogenetic therapies are considered effective in improving HS. Although tacrolimus (TAC) has been proven effective in preventing HS formation in vivo and in vitro, its underlying mechanism remains controversial and ambiguous. Because of its anti-angiogenic effects in other diseases, we aimed to determine whether TAC reduces HS by suppressing angiogenesis. Using a rabbit ear HS model that we developed, HS was treated once a week with normal saline, dimethyl sulfoxide, or TAC for 3 weeks. Histological evaluation indicated that TAC significantly reduced collagen deposition and microvessel density in scar tissues. Moreover, immunofluorescence staining for CD31 and vascular endothelial growth factor (VEGF)-A revealed that TAC significantly inhibited HS angiogenesis. In vitro analysis showed that TAC inhibited endothelial cell migration and tubulogenesis as well as the viability and proliferation of human umbilical vascular endothelial cells (HUVECs) and HS fibroblasts (HSFBs). Furthermore, TAC significantly downregulated the expression of the human angiogenetic factors VEGF-A, FGF-2, PDGF-ß, and TGF-ß1 in HUVECs and HSFBs. Additionally, TAC-mediated inhibition of angiogenesis decreased the gene expression of crucial fibrotic markers, including α- smooth muscle actin and collagens 1 and 3, in HSFBs. This is the first study to demonstrate the inhibitory effects of TAC on HS formation mediated by a mechanism involving the suppression of scar angiogenesis.
Subject(s)
Cicatrix, Hypertrophic , Animals , Humans , Rabbits , Cicatrix, Hypertrophic/drug therapy , Cicatrix, Hypertrophic/prevention & control , Cicatrix, Hypertrophic/metabolism , Vascular Endothelial Growth Factor A/metabolism , Tacrolimus/pharmacology , Tacrolimus/metabolism , Endothelial Cells/metabolism , Angiogenesis Inducing Agents/pharmacology , Fibroblasts/metabolism , Neovascularization, Pathologic/metabolism , Neovascularization, Pathologic/pathologyABSTRACT
Sustainable conversion of CO2 to fuels using solar energy is highly attractive for fuel production. This work focuses on the synthesis of porous graphitic carbon nitride nanobelt catalyst (PN-g-C3N4) and its capability of photocatalytic CO2 reduction. The surface area increased from 6.5 m2·g-1 (graphitic carbon nitride, g-C3N4) to 32.94 m2·g-1 (PN-g-C3N4). C≡N groups and vacant N2C were introduced on the surface. PN-g-C3N4 possessed higher absorbability of visible light and excellent photocatalytic activity, which was 5.7 and 6.3 times of g-C3N4 under visible light and simulated sunlight illumination, respectively. The enhanced photocatalytic activity may be owing to the porous nanobelt structure, enhanced absorbability of visible light, and surface vacant N-sites. It is expected that PN-g-C3N4 would be a promising candidate for CO2 photocatalytic conversion.
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Porous C3N4(PCN) is favored by researchers because it has more surface active sites, higher specific surface area and stronger light absorption ability than traditional g-C3N4. In this study, cerium dioxide nanoparticles (CeO2-NPs) with mixed valence state of Ce3+and Ce4+were doped into the PCN framework by a two-step method. The results indicate that CeO2-NPs are highly dispersed in the PCN framework, which leads to a narrower band gap, a wider range of the light response and an improved the separation efficiency of photogenerated charge in PCN. Moreover, the specific surface area (145.69 m2g-1) of CeO2-NPs doped PCN is a 25.5% enhancement than that of PCN (116.13 m2g-1). In the experiment of photocatalytic selective oxidation of benzyl alcohol, CeO2-NPs doped porous C3N4exhibits excellent photocatalytic activity, especially Ce-PCN-30. The conversion rate of benzyl alcohol reaches 74.9% using Ce-PCN-30 as photocatalyst by 8 h of illumination, which is 25.7% higher than that of pure porous C3N4. Additionally, CeO2-NPs doped porous C3N4also exhibits better photocatalytic efficiency for other aromatic alcohols.
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BACKGROUND: Many people are characterized by a swollen appearance and loose skin of upper eyelids, especially Asians. Retro-orbicularis oculus fat (ROOF) lying in the lateral canthus area is a critical factor of the bulkiness formation. Although several approaches have been reported, most of them intend to remove orbicularis muscle and preaponeurotic fat through a double-eyelid incision, leaving ROOF untreated. Consequently, an unnatural eyelid fold is formed and the lateral supraorbital region remains bloated . METHODS: Sixty-seven patients underwent sub-brow skin excision combined with ROOF resection. The key point was to excise the loose skin and thick ROOF through an incision along with the lower 1/3 of the eyebrow. Surgical outcomes were evaluated 6 months postoperatively by the heights of the designed line from the palpebral margin to the pupil center (HPPC), medial cornea (HPMC), and lateral canthus (HPLC). The pinch test, photographs, and complications were also recorded. RESULTS: The preoperative average HPPC, HPMC, and HPLC were 9.68 ± 1.73, 7.68 ± 1.24, and 6.82 ± 1.12 mm, while the postoperative average measurements were 7.25 ± 0.51, 5.99 ± 0.54, and 5.54 ± 0.61 mm, respectively. The result of the pinch test was improved and postoperative scarring was inconspicuous. Two patients had transient numbness in the eyebrow region that subsided within seven days. Two patients had slight asymmetry of eyebrow position but did not need a second operation. CONCLUSIONS: Sub-brow skin excision combined with ROOF resection is an effective technique for improving upper eyelid bulkiness and skin excess with low revision rates.
Subject(s)
Blepharoplasty , Adipose Tissue/surgery , Blepharoplasty/methods , Cicatrix/surgery , Eyebrows , Eyelids/surgery , HumansABSTRACT
INTRODUCTION: Although several surgical methods have been introduced to treat mild-to-moderate blepharoptosis, including levator-based techniques such as Müller muscle-conjunctival resection, few complications and better functional and aesthetic outcomes remain elusive for plastic surgeons. Hence, this study aimed to provide a new technique (bridge technique) using the levator aponeurosis-Müller's muscle flap to achieve optimal blepharoptosis correction for function and aesthetics among Asians. METHODS: From January 2019 to May 2020, this new technique was performed on 157 consecutive patients with mild-to-moderate blepharoptosis. Our technique was based on the anchor of the levator complex to the tarsus using mattress stitches and three-layer fixation, which provided a reliable motion transmitter for elevating the upper eyelid. The patients' medical records and photographs were reviewed 12 months postoperatively to assess the margin reflex distance 1 (MRD1), incidence of complications, and aesthetic outcomes. RESULTS: The average preoperative and postoperative MRD1 measured 1.2 ± 0.31 mm and 3.7 ± 0.34 mm, respectively. A significant difference was observed between the preoperative and postoperative distance values (p < 0.001). In the aesthetic evaluation, the grading was good, fair, and poor for 142 (90.4%) patients, 10 (6.4%) patients, and 5 (3.2%) patients, respectively. Complications included undercorrection in 12 (5.2%) cases and overcorrection in nine (3.9%) cases, and no cases of residual lagophthalmos were recorded. CONCLUSION: Mild-to-moderate blepharoptosis among Asians can be corrected effectively using this new technique. However, the long-term outcomes of this procedure should be explored.
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Atractylodes macrocephala Koidz. (AM), an herb of traditional Chinese medicine, is well-known for anti-oxidant, anti-tumor and immune regulation potential. However, it is low bioactive compound content that restricts the application of this species. Elicitation is considered as an effective method to enhance biomass and bioactive compound in plants. Our precious study found that polysaccharide of Chrysanthemun indicum L. could promote plant growth by triggering plant defense. In the present study, polysaccharide of Chrysanthemun indicum L. is used to stimulate the accumulation of biomass and bioactive compound with different concentration in Atractylodes macrocephala Koidz. during pot, plot and field experiments. The results suggested that polysaccharide of Chrysanthemun indicum L. could significantly enhance the accumulation of biomass, atractylenolides and polysacchrides. Moreover, 2 mg/mL is determined and verified to be the appropriate concentration during field experiments. In addition, RT-qPCR revealed that CIP-induced terpenoid synthesis in AM mainly depended on mevalonate (MVA) pathway. This is the first report on the discovery of polysaccharide of Chrysanthemun indicum L. for the enhanced accumulation of biaomass and bioactive compound and the use of its for agricultural production.
Subject(s)
Atractylodes/metabolism , Chrysanthemum/chemistry , Polysaccharides/pharmacology , Sesquiterpenes/metabolism , Antioxidants/pharmacology , Atractylodes/drug effects , Atractylodes/genetics , Biomass , Gene Expression Regulation, Plant/drug effects , RNA, Messenger/genetics , RNA, Messenger/metabolismABSTRACT
Hydrogel adhesives are attractive for applications in intelligent soft materials and tissue engineering, but conventional hydrogels usually have poor adhesion. In this study, we designed a strategy to synthesize a novel adhesive with a thin hydrogel adhesive layer integrated on a tough substrate hydrogel. The adhesive layer with positive charges of ammonium groups on the polymer backbones strongly bonds to a wide range of nonporous materials' surfaces. The substrate layer with a dual hydrogen bond system consists of (i) weak hydrogen bonds between N,N-dimethyl acrylamide (DMAA) and acrylic acid (AAc) units and (ii) strong multiple hydrogen bonds between 2-ureido-4[1H]-pyrimidinone (UPy) units. The dual hydrogen-bond network endowed the hydrogel adhesives with unique mechanical properties, e.g., toughness, highly stretchability, and insensitivity to notches. The hydrogel adhesion to four types of materials like glass, 316L stainless steel, aluminum, Al2O3 ceramic, and two biological tissues including pig skin and pig kidney was investigated. The hydrogel bonds strongly to dry solid surfaces and wet tissue, which is promising for biomedical applications.
Subject(s)
Hydrogels/chemistry , Acrylamides/chemistry , Acrylates/chemistry , Adhesiveness , Animals , Hydrogen Bonding , SwineABSTRACT
Polymeric carbon nitride (C3N4) is currently the most potential nonmetallic photocatalyst, but it suffers from low catalytic activity due to rapid electron-hole recombination behavior and low specific surface area. The morphology control of C3N4is one of the effective methods used to achieve higher photocatalytic performance. Here, bulk, lamellar and coralloid C3N4were synthesized using different chemical methods. The as-prepared coralloid C3N4has a higher specific surface area (123.7 m2 · g-1) than bulk (5.4 m2 · g-1) and lamellar C3N4(2.8 m2 · g-1), thus exhibiting a 3.15- and 2.59-fold higher photocatalytic efficiency for the selective oxidation of benzyl alcohol than bulk and lamellar C3N4, respectively. Optical characterizations of the photocatalysts suggest that coralloid C3N4can effectively capture electrons and accelerate carrier separation, which is caused by the presence of more nitrogen vacancies. Furthermore, it is demonstrated that superoxide radicals (·O2-) and holes (h+) play major roles in the photocatalytic selective oxidation of benzyl alcohol using C3N4as a photocatalyst.
Subject(s)
Blepharoplasty , Blepharoplasty/adverse effects , Eyelids/surgery , Humans , Surgical FlapsABSTRACT
BACKGROUND: Double eyelid blepharoplasty is the most popular cosmetic surgery among Asian populations. Although various surgical procedures have been reported, certain complications still arise, including asymmetry or the disappearance of the double eyelid crease, an unnatural double eyelid crease curve, and distinct scars. OBJECTIVES: The aim of this study was to describe a new blepharoplasty technique intended to reduce the various complications and create dynamic, natural-looking double eyelids. METHODS: From September 2018 to June 2019, the new technique was performed on 92 Chinese patients. The core of our technique was to construct a reliable motion transmitter, the orbital septum-levator aponeurosis flap, which was sutured to the tarsus. The outcomes were assessed 6 months after the surgery by reviewing medical records and photographs to assess the aesthetic outcomes, the relapse rate, and the incidence of complications. RESULTS: In the aesthetic outcome assessment, 86 patients were graded as good and 4 were graded as fair; of the latter, 2 had uneven scars and 2 showed showed a slight asymmetry of the double eyelid curve in length or width. Two patients were graded as poor because of the disappearance of the double eyelid crease. The relapse rate was 2.2%. Two patients had temporary hematoma. Six patients had lagophthalmos that subsided within 30 days. No cases of infection or ptosis were observed. CONCLUSIONS: The bridge technique is an effective method for creating dynamic, natural-looking double eyelids. However, the long-term outcome of this new surgical approach requires further study.
Subject(s)
Aponeurosis , Blepharoplasty , Blepharoptosis , Asian People , Blepharoplasty/adverse effects , Blepharoptosis/surgery , Esthetics , Eyelids/surgery , Humans , Retrospective StudiesABSTRACT
Functionalization of vegetable oils (VOs) including edible, non-edible, and waste cooking oil (WCOs) to epoxides (EVOs) is receiving great attention by many researchers from academia and industry because they are renewable, versatile, sustainable, non-toxic, and eco-friendly, and they can partially or totally replace harmful phthalate plasticizers. The epoxidation of VOs on an industrial scale has already been developed by the homogeneous catalytic system using peracids. Due to the drawbacks of this method, other systems including acidic ion exchange resins, polyoxometalates, and enzymes are becoming alternative catalysts for the epoxidation reaction. We have reviewed all these catalytic systems including their benefits and drawbacks, reaction mechanisms, intensification of each system in different ways as well as the physicochemical properties of VOs and EVOs and new findings in recent years. Finally, the current methods including titrimetric methods as well as ATR-FTIR and 1H NMR for determination of conversion, epoxidation, and selectivity of epoxidized vegetable oils (EVOs) are also briefly described.