Total Synthesis of (±)-Simonsol C.

Total synthesis of simonsol C has been achieved, focusing on the postdearomatization transformations. Our methodology integrates an efficient combination of dearomatization and Zn/AcOH reduction to introduce an allyl group, followed by oxo-Michael addition, to construct the 6/5/6 benzofuran skeleton. It offers a novel method for synthesizing allyl-containing quaternary carbon atoms in a straightforward manner.

Synthesis of 2-benzyl N-substituted anilines via imine condensation-isoaromatization of (E)-2-arylidene-3-cyclohexenones and primary amines.

A catalyst- and additive-free synthesis of 2-benzyl N-substituted anilines from (E)-2-arylidene-3-cyclohexenones and primary amines has been reported. The reaction proceeds smoothly through a sequential imine condensation-isoaromatization pathway, affording a series of synthetically useful aniline derivatives in acceptable to high yields. Mild reaction conditions, no requirement of metal catalysts, operational simplicity and the potential for scale-up production are some of the highlighted advantages of this transformation.

Adsorption of methyl orange by porous membranes prepared from deep eutectic supramolecular polymer-modified chitosan.

The fabrication of an adsorbent with excellent performance has been a focus of attention because of the toxicity, mutagenicity and carcinogenicity of methyl orange (MO)-containing wastewater discharged from the textile, tannery and pharmaceutical industries. In this study, chitosan (CS) membranes were modified with a deep eutectic supramolecular polymer (DESP), and adsorbent membranes with porous structures were prepared with polyethylene glycol (PEG). Microstructural characterization of the CS-DESP-PEG composite membranes with FT-IR, XRD and SEM showed that the membranes had amorphous crystalline structures and that hydrogen bonding interactions weakened the crystallinity and formed loose porous structures. Optimization of the chitosan to ß-cyclodextrin ratio, pH, PEG proportion, MO concentration and adsorbent dose significantly improved the adsorption efficiencies of the membranes. The adsorption behaviours of the membranes were fit with pseudo-second-order adsorption kinetics and the Freundlich adsorption isotherm model. Regeneration experiments showed that the membranes were reusable multiple times and maintained good adsorption capacities.

Self-Stirring Microcatalysts: Large-Scale, High-Throughput, and Controllable Preparation and Application.

Herein, we introduce a strategy to develop a kind of unprecedented microcatalyst, which owns self-stirring and catalytic performance based on pneumatic printing and magnetic field induction technology. A spindle-shaped microcatalyst based on metal-organic frameworks (MOFs) with a certain aspect ratio and size can be obtained by tuning the printing parameters and the intensity of the magnetic field. One nozzle can print 18 000 microcatalysts per hour, which provides a prerequisite for the realization of large-scale production in the industrial field. Furthermore, this strategy can be widely applied to a variety of other heterogeneous catalysts, such as mesoporous SiO2, zeolite, metallic oxide, and so on. To demonstrate the superiority of the printed catalyst, the series of printed microcatalysts were evaluated by various catalytic reactions including liquid-phase hydrogenation, microdroplet dye-fading, and photocatalytic degradation in microreactor, all of which exhibited excellent catalytic performance.

Chiral Yolk-Shell MOF as an Efficient Nanoreactor for Asymmetric Catalysis in Organic-Aqueous Two-Phase System.

It remains a great challenge to introduce large and efficient homogeneous asymmetric catalysts into MOFs and other microporous materials as well as retain their degrees of freedom. Herein, a new heterogeneous strategy of homogeneous chiral catalysts is proposed, that is, to construct a yolk-shell MOFs-confined, large-size, and highly efficient homogeneous chiral catalyst, which can be used as a nanoreactor for asymmetric catalytic reactions.

Preparation and Characterization of Bletilla striata Polysaccharide/Polylactic Acid Composite.

Polylactic acid (PLA) is limited in its application due to its high price, high brittleness and low glass-transition temperature. Modification methods are currently used to overcome these shortcomings. In this study, Bletilla striata polysaccharide (BSP) was blended with PLA by a solvent method. DMA data showed that the BSP/PLA film had a higher glass-transition temperature, and the glass-transition temperature of the film showed an extreme value of 68 °C when the proportion of the chalk polysaccharide was 0.8%. TG data indicates that the composite film material has good thermal stability. Tensile tests show that the composite film is improved in rigidity and elasticity compared to the pure PLA film. The blending modification of PLA with white peony polysaccharide not only reduces the cost of PLA, but also improves the thermal and mechanical properties of PLA.

Preparation, In Vivo and In Vitro Release of Polyethylene Glycol Monomethyl Ether-Polymandelic Acid Microspheres Loaded Panax Notoginseng Saponins.

In order to enrich the types of Panax notoginseng saponins (PNS) sustained-release preparations and provide a new research idea for the research and development of traditional Chinese medicine sustained-release formulations, a series of Panax notoginseng saponins microspheres was prepared by a double emulsion method using a series of degradable amphiphilic macromolecule materials polyethylene glycol monomethyl ether-polymandelic acid (mPEG-PMA) as carrier. The structure and molecular weight of the series of mPEG-PMA were determined by nuclear magnetic resonance spectroscopy (1 HNMR) and gel chromatography (GPC). The results of the appearance, particle size, drug loading and encapsulation efficiency of the drug-loaded microspheres show that the mPEG10000-PMA (1:9) material is more suitable as a carrier for loading the total saponins of Panax notoginseng. The particle size was 2.51 ± 0.21 µm, the drug loading and encapsulation efficiency were 8.54 ± 0.16% and 47.25 ± 1.64%, respectively. The drug-loaded microspheres were used for in vitro release and degradation experiments to investigate the degradation and sustained release behaviour of the drug-loaded microspheres. The biocompatibility of the microspheres was studied by haemolytic, anticoagulant and cytotoxicity experiments. The pharmacological activity of the microspheres was studied by anti-inflammatory and anti-tumour experiments. The results showed that the drug-loaded microspheres could be released stably for about 12 days and degraded within 60 days. At the same time, the microspheres had good biocompatibility, anti-inflammatory and anti-tumour activities.

Hysteroscopy after repeated implantation failure of assisted reproductive technology: A meta-analysis.

We conducted this meta-analysis to explore the prognostic value of outpatient (or office) hysteroscopy (OH) preceding in vitro fertilization (IVF) or intracytoplasmic sperm injection (ICSI) cycles in women who had experienced repeated implantation failure (RIF), particularly in regard to the conflicting evidence reported by previous studies. Two reviewers independently searched Pubmed, MEDLINE, Web of Science, Cochrane Library and Embase to identify all publications of clinical trials of hysteroscopy with or without endometrial biopsy in RIF patients. The primary outcome measures were clinical pregnancy rate (CPR) and live birth rate (LBR). Pooled relative ratios (RRs) with 95% confidence intervals (CIs) were calculated. Publication bias was detected using funnel plots and Egger's regression tests. Six eligible studies comprising 4143 patients were included. The CPR and LBR were both significantly higher in RIF patients with OH than RIF patients without OH (CPR: RR 1.34, 95% CI 1.14-1.57, P < 0.05; LBR: RR 1.29, 95% CI 1.03-1.62, P < 0.05). Subgroup analysis revealed a significant association between OH and CPR in Asia (CPR: RR 1.49, 95% CI 1.31-1.69; P < 0.05) rather than in Europe (CPR: RR 1.08, 95% CI 0.93-1.26; P = 0.291). However, there was no evidence of a significant difference in either CPR or LBR between the normal and abnormal OH groups (CPR: RR 0.92, 95% CI 0.83-1.02, P = 0.12; LBR: RR 0.76, 95% CI 0.37-1.56, P = 0.450). Hysteroscopy may potentially improve pregnancy outcomes in patients with RIP.

Tillage and Fertilizer Management Effects on Phosphorus Runoff from Minimal Slope Fields.

Phosphorus fertilization can increase P losses in surface runoff, but limited information is available for fields with <2% slopes in the US Midwest. Our objectives were to determine the effects of tillage-fertilizer placement (no-till-broadcast, strip till-broadcast; or strip till-deep placement, -15-cm subsurface band) and fertilizer rate applied in the fall (0, 52, or 90 kg PO ha yr) on runoff P concentrations and loads in fields with <2% slopes near Pesotum, IL, during fall and spring simulation runoff events, and to measure corn ( L.) and soybean [ (L.) Merr.] grain yield. Across four simulated runoff events, deep placement reduced dissolved reactive P (DRP) loads by 69 to 72% compared with the broadcast treatments. A tillage-fertilizer placement × P rate interaction showed that DRP and total P (TP) concentrations remained low when P was deep placed, regardless of P rate, whereas concentrations increased with increasing P rate for the broadcast treatments, but no differences existed for bioavailable P (BAP) (α = 0.05). At one site, rainfall simulation in the spring versus fall increased runoff volumes but sharply decreased BAP concentrations. During fall runoff simulations, deep placement reduced TP loads, and greater TP loads occurred with the 90- than the 52-kg PO ha yr rate. Similarly, when P was broadcast in the fall, DRP and TP concentrations were greater than deep-placed P, but no treatment differences occurred in the spring. Deep banding P and K did not reduce crop yield but reduced runoff losses of P from flat fields compared with broadcast P applications, particularly at high rates of P application.

Poly(Lactic Acid) Blends with Poly(Trimethylene Carbonate) as Biodegradable Medical Adhesive Material.

A novel medical adhesive was prepared by blending poly(lactic acid) (PLA) with poly(trimethylene carbonate) (PTMC) in ethyl acetate, and the two materials were proven to be biodegradable and biocompatible. The medical adhesive was characterized by ¹H nuclear magnetic resonance (¹HNMR), gel permeation chromatography (GPC), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The water vapor transmission rate (WVTR) of this material was measured to be 7.13 g·cm-2·24 h-1. Its degree of comfortability was confirmed by the extensibility (E) and the permanent set (PS), which were approximately 7.83 N·cm-2 and 18.83%, respectively. In vivo tests regarding rabbit immunoglobulin M (IgM), rabbit immunoglobulin G (IgG), rabbit bone alkaline phosphatase (BALP), rabbit interleukin 6 (IL-6), rabbit interleukin 10 (IL-10), rabbit tumor necrosis factor α(TNFα), glutamic-oxaloacetic transaminase (AST/GOT), glutamic-pyruvic transaminase (ALT/GPT), alkaline phosphatase (AKP), blood urea nitrogen (BUN) and creatinine (Cr) indicated that the PLA-PTMC medical adhesive was not harmful to the liver and kidneys. Finally, pathological sections indicated that PLA-PTMC was more effective than the control group. These data suggest that in addition to having a positive effect on hemostasis and no sensibility to wounds, PLA-PTMC can efficiently prevent infections and has great potential as a medical adhesive.

Fabrication and characterization of poly(lactic acid-trimethylene carbonate) based biodegradable composite films.

Two biobased composite films have been prepared with poly (lactic acid-trimethylene carbonate), polylactic acid and Laponite by solvent evaporation method. The 1H NMR and FTIR spectrums illustrate that P (LA-TMC) polymer is successfully synthesized and designed composite films are produced. Morphometric analyses demonstrate that the roughnesses of the film's surface and cross-section are on the increase with higher PLA and Laponite content. Mechanical performances reveal that the rise in tensile strength and modulus while maintaining excellent elongation at break is mainly due to the increase in the content of polylactic acid and Laponite. By utilizing the nano effect of Laponite, the maximum tensile strength of the composite film reaches 34.59 MPa. Thermal property results illustrate that the Tg and initial decomposition temperature are on the growth with the increase of PLA content. However, it is not significant on the effect of Laponite on the initial decomposition temperature. The water vapor permeability measurements prove that the barrier property of P(LA-TMC)/PLA/Laponite composite film is on the ascent with the Laponite addition. Hydrolytic degradation tests indicate that PLA and Laponite play avital part in accelerating the degradation rate of composite films and alkaline media is superior acidic and neutral conditions.

Efficient removal of Chromium(VI) from wastewater based on magnetic multiwalled carbon nanotubes coupled with deep eutectic solvents.

Industrial wastewater containing heavy metal Cr(VI) seriously affects the health of organisms and may even lead to cancer. Developing efficient adsorbents that can quickly separate heavy metals is crucial for treating wastewater. In this study, magnetic multiwalled carbon nanotubes (MMWCNTs) with moderate particle size and abundant surface active sites were prepared by coating multiwalled carbon nanotubes with magnetic nanoparticles. The results of FTIR, XRD, TG, VSM, BET, and EDS showed MWCNTs completely encapsulated on the surface of the magnetic nanoparticles, with a particle size of approximately 30 nm. Oxygenated groups provided abundant surface active sites and formed numerous mesopores. The response surface methodology was used to optimize the adsorbent dose, adsorption contact time and adsorption temperature, and the removal rate of Cr(VI) was more than 95%. The quasi-second order kinetics and Freundlich adsorption isotherm model explained the adsorption process to Cr(VI). MMWCNTs interacted with Cr(VI) through electrostatic attraction, reduction reactions, complexation, and other means. The extensive hydrogen bonding of the green solvent deep eutectic solvent (DES) was employed to desorb the MMWCNTs and desorption rate exceed 90%. Even after five adsorption-regeneration cycles, the adsorbent maintained a high capacity. In conclusion, these novel MMWCNTs, as efficient adsorbents paired with DES desorption, hold broad potential for application in the treatment of Cr(VI)-contaminated wastewater.

Case Report: Pelvic mass and massive ascites as the first symptom in cervical adenocarcinoma: report of two cases and literature review.

Cervical adenocarcinoma accounts for 10%-25% of total cases of cervical carcinoma. But in recent years, the incidence of adenocarcinoma has risen both proportionally and absolutely. Clinically, most cervical adenocarcinoma show no symptom or present with abnormal uterine bleeding or vaginal discharge, similar to squamous cell carcinoma. What different about it is that cervical cytological testing demonstrates a high false-negative rate of cervical adenocarcinoma, potentially leading to the failure in detecting in early stage. This report presents two cases both with pelvic masses, and massive ascites served as the initial symptom, which is similar to the clinical symptom of ovarian cancer, but ultimately diagnosed with cervical adenocarcinoma through surgical specimens. There are few literature reports on this situation. Hence, a literature review also has been performed to improve the recognition for cervical adenocarcinoma presenting with pelvic masses and massive ascites, and to avoid misdiagnosis.

ZnO-PLLA/PLLA Preparation and Application in Air Filtration by Electrospinning Technology.

With the increasing environmental pollution caused by disposable masks, it is crucial to develop new degradable filtration materials for medical masks. ZnO-PLLA/PLLA (L-lactide) copolymers prepared from nano ZnO and L-lactide were used to prepare fiber films for air filtration by electrospinning technology. Structural characterization of ZnO-PLLA by H-NMR, XPS, and XRD demonstrated that ZnO was successfully grafted onto PLLA. An L9(43) standard orthogonal array was employed to evaluate the effects of the ZnO-PLLA concentration, ZnO-PLLA/PLLA content, DCM(dichloromethane) to DMF(N,N-dimethylformamide) ratio, and spinning time on the air filtration capacity of ZnO-PLLA/PLLA nanofiber films. It is noteworthy that the introduction of ZnO is important for the enhancement of the quality factor (QF). The optimal group obtained was sample No. 7, where the QF was 0.1403 Pa-1, the particle filtration efficiency (PFE) was 98.3%, the bacteria filtration efficiency (BFE) was 98.42%, and the airflow resistance (Δp) was 29.2 Pa. Therefore, the as-prepared ZnO-PLLA/PLLA film has potential for the development of degradable masks.

A polylactide based multifunctional hydrophobic film for tracking evaluation and maintaining beef freshness by an electrospinning technique.

A nanofiber film was prepared by a facile electrospinning technique using polylactide (PLA), butterfly pea flower extract (BPA) and cinnamaldehyde (CIN). The as-prepared film shows the prominent antioxidative, antibacterial, colorimetric and hydrophobic properties so that the beef freshness can be monitored and maintained up to 6 days at 4 °C simultaneously. Besides, the nanofiber structure endows the film with a fast color responsiveness under acidic-alkaline atmospheres with different concentrations. Moreover, this film exhibits higher tensile strength (9.56 Mpa) than that of the pure PLA electrospinning film (4.40 Mpa). Especially the introduction of the BPA effectively boosts the antimicrobial ability of the CIN. The freshness, sub-freshness and spoilage levels of the beef can be easily testified by observing the color difference change of the film. So the polylactide based multifunctional film as an intelligent packaging has an excellent potential for the sub-freshness detection of meat.

Smart Indicator Film Based on Sodium Alginate/Polyvinyl Alcohol/TiO2 Containing Purple Garlic Peel Extract for Visual Monitoring of Beef Freshness.

The aim of this study was to prepare a novel pH-sensitive smart film based on the addition of purple garlic peel extract (PGE) and TiO2 nanoparticles in a sodium alginate (SA)/polyvinyl alcohol (PVA) matrix to monitor the freshness of beef. FT-IR spectroscopy revealed the formation of stronger interaction forces between PVA/SA, PGE, and TiO2 nanoparticles, which showed good compatibility. In addition, the addition of PGE improved the tensile strength and elongation at break of the composite film, especially in different pH environments, and the color response was obvious. The addition of 1% TiO2 nanoparticles significantly improved the mechanical properties of the film, as well as the light barrier properties of the film. PGE could effectively be uniformly dispersed into the composite film, but it also had a certain slow-release effect on the release of PGE. PGE had high sensitivity under different pH conditions with rich color changes, and the color showed a clear color change from red to yellow-green when the pH increased from 1 to 14. The same change was observed when it was added to the film. In particular, by applying this film to the process of beef preservation, we judged the freshness of beef by monitoring the changes in the TVB-N value and pH value during the storage process of beef and found that the film showed obvious color changes during the storage process of beef, from blue (indicating freshness) to red (indicating non-freshness), and finally to yellow-green (indicating deterioration), which indicated that the color change of the film and the freshness of the beef maintained a highly consistent.

Effects of antimicrobial nanocomposite films packaging on the postharvest quality and spoilage bacterial communities of mushrooms (Chanterelles).

Poly (lactic acid) (PLA) composite films with the addition of mesoporous silica nanoparticles MSN (0, 2, 4 and 6 wt%) loaded with 10 wt% citral (CIT) were prepared for application in Chanterelles packaging. Composite films with added MSN/CIT showed good mechanical properties, especially 4MSN/CIT/PLA. Changes in physicochemical properties and bacterial flora of Chanterelles during packaging and storage were tested. Compared with CIT/PLA, Chanterelles packed with 4MSN/CIT/PLA showed about 1.62-times lower browning value, 1.53-times lower electrolyte permeability, and 1.83- and 1.78-times lower PPO and POD, respectively, at 12 day. Better physicochemical properties of Chanterelles can be maintained. For bacterial flora changes, Chanterelles packaged with 4MSN/CIT/PLA had more stable flora (p < 0.05) and lower species diversity during storage (p < 0.05), effectively controlling the growth and reproduction of their dominant spoilage bacteria (Enterobacteriaceae spp). In conclusion, the composite membranes obtained by the addition of MSN/CIT to PLA have great potential in the storage of Chanterelles.

Determination of catechol in water with deep eutectic supramolecular solvents-assisted magnetic κ-carrageenan nanoparticles.

A combination of magnetic κ-carrageenan nanoparticles and deep eutectic supramolecular solvents used for extraction of catechol from water was evaluated by the magnetic dispersion solid phase extraction method. The magnetic κ-carrageenan nanoparticles (KC@Fe3O4MNPs) and the deep eutectic supramolecular solvent (DESP) were characterised by 1H NMR, FT-IR, XRD, SEM, VSM, TG, and BET. The adsorption kinetics, adsorption isothermal model, adsorption thermodynamics and effects of pH and salt concentration were investigated. Additionally, the factors used in the desorption process, such as the type, dosage, concentration and time, were analysed. Under the optimised conditions, the analytes were linear over the range 5-5000 ng mL-1, with a correlation coefficient greater than 0.999 and detection and quantitation limits of 1.6 and 4.7 ng mL-1, respectively. The procedure was successfully applied to determinations of the analytes of interest in spiked water samples with relative average recoveries ranging from 94.3% to 101.5%. These results indicated that the combination of functionalized magnetic nanoparticles and DESP had high specificity and extraction efficiency for catechol and will be a feasible alternative to conventional analyses of organic phenolic pollutants in water.

Ultrasonic assisted extraction of polyphenols from bayberry by deep eutectic supramolecular polymer and its application in bio-active film.

Ultrasound and deep eutectic supramolecular polymers (DESP) is a novel combination of green extraction method for phytochemicals. In this study, a new type of green extractant was developed: DESP. It is a derivative of deep eutectic solvent (DES) and was prepared by supramolecular polymer unit ß-cyclodextrin (ß-CD) as hydrogen bond acceptor (HBA) and organic acid as hydrogen bond donor (HBD). The current work focuses on the use of ultrasonic-assisted (UAE) DESP extraction of polyphenolic compounds (PCs) from bayberry. The experimental results showed that DESP synthesized with ß-CD and lactic acid (LA) in a ratio of 1:1 (w/w %) had the best extraction effect. And by using a three-level factor experiment and the response surface method, the predicted TPC content is very close to the actual content (28.85 ± 1.27 mg GAE/g). The DESP extract including PCs were further used as plasticizer for chitosan (CS) to prepare highly active green biofilms (DESP-CS). It is possible to reduce the tedious procedures for separating biologically active substances from DESP. The experiment proved that the prepared films have good mechanical properties, plastic deformation resistance, thermal stability and antioxidant activity.

Development of magnetic dispersive micro-solid phase extraction of four phenolic compounds from food samples based on magnetic chitosan nanoparticles and a deep eutectic supramolecular solvent.

A magnetic dispersive micro-solid phase extraction technique (CS@Fe3O4-MD-µSPE-DESP) based on magnetic chitosan nanoparticles and a deep eutectic supramolecular solvent was developed and applied to determinations of four phenolic compounds in food samples. To prevent environmental pollution and the introduction of toxic substances, deep eutectic supramolecular solvents (DESPs), which exhibited greater desorption capacities than conventional organic solvents and deep eutectic solvents, were used as novel green eluents for the first time. Some important parameters were screened by the Plackett-Burman method and then further optimized with response surface methodology (RSM). Under the optimal conditions, the proposed method showed excellent methodological indices with linearity over the range 0.1-200.0 µg·mL-1, R2 > 0.9988, extraction recoveries above 94.8 %, and precision (RSD%) below 2.9 %. The established method finishes the process of adsorption and desorption in approximately 3 min and enhances the efficiency for determination of phenolic compounds.