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SnCl4, a versatile Lewis acid catalyst in the biomass conversion, plays a positive role for the cellulose biomass conversion but negative for chitin biomass conversion as realized in our previous research. In this report, the unexpected effects of SnCl4 on the conversion of d-glucosamine (GlcNH2) to 5-hydroxymethylfurfural (5-HMF) in ZnCl2 molten salt hydrate medium were investigated. The strong interaction between SnCl4 and GlcNH2 in ZnCl2 molten salt hydrate medium was examined by nuclear magnetic resonance (NMR) techniques. Additionally the d-glucose and N-acetyl-d-glucosamine were also utilized in NMR titration experiments to reveal the complexation of amino group with Sn4+ ions during the catalytic process. The observed drifts of chemical shifts and signal broadening of the C2 position of GlcNH2 in 13C NMR spectra indicates that the amino group in GlcNH2 is probably the Sn4+ ion complexation site. The correlations in the 1H-15N HSQC NMR spectra provide the direct evidence and further confirm that the amino group is the complexation site between SnCl4 and GlcNH2. This very specific complex between the amino group and the Sn4+ ion inhibit the conversion of GlcNH2 to 5-HMF in ZnCl2 molten salt hydrate medium.

Lignite showed high capacity for reducing Cr(VI) to Cr(III) and hence removed Cr(VI) from aqueous solution, but the reduced Cr(III) cannot be released from adsorbent afterwards especially under acidic condition. In order to know why Cr(III) ions are immobilized within lignite adsorbent and how to recovery Cr species, the interaction of Cr(III) ions with lignite oxidized by Cr(VI) was studied by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The data obtained from these studies indicate that Cr(III) ions are bonded to oxygenic functional groups in lignite oxidized by Cr(VI) and electrons are delocalized over -O-Cr-O- domain. It is also revealed that the O atoms of C = O and C-O groups in the adsorbent matrix are bonded to Cr(III) ions along with the decrease of electron density, while the O atoms of O -C = O group are along with the increase of electron density. Based on these important structural information, we developed a method to treat Cr-loaded lignite further and to recover the Cr species.

Brown coal-based materials are excellent adsorbents for reducing chromium(VI) to chromium(III) and afterward immobilizing these chromium(III) by the binding of oxygenic functional groups in adsorbents. In the study, the approach of pyrolysis is employed for the treatment of Cr-loaded solid waste. The effects of adsorbed chromium on the pyrolysis of Xilingol brown coal were studied, and the solid char residues were collected to characterize with XPS, XRD and SEM/EDX. For the pyrolysis in Ar, the mass loss rates of Cr-loaded samples were much higher than that of unloaded samples above 750 °C, together with the increase in CO and H2 emission. XPS spectra revealed that the increase in CO could be related to formation of [Cr–O–C]. For the pyrolysis in CO2, the presence of chromium was more favorable for the conversion of char, especially demineralized brown coal and kerogen. The maximum decomposition temperatures for the Cr-loaded samples were about 200 °C lower than that of unloaded samples. The char residue yields of Cr-loaded samples were obviously higher than that of corresponding unloaded samples (at 1200 °C). Finally, the chromium in the solid residue was recovered in the form of Cr2O3. The present study exploits an approach method for both brown coal waste treatment and chromium recovery.

Benzo [a]pyrene (BaP) is a well-known endocrine disruptor. Exposure to BaP is known to impair embryo implantation. The corpus luteum (CL), the primary source of progesterone during early pregnancy, plays a pivotal role in embryo implantation and pregnancy maintenance. The inappropriate luteal function may result in implantation failure and spontaneous abortions. However, the effect of BaP on CL remains unknown. This study investigated the deleterious effects of BaP on the structure and function of CL during early pregnancy. Pregnant rats were dosed with BaP at 0.2 mg.kg-1. d from day 1 (D1) to day 9 (D9) of gestation. We found that BaP reduced the number of CLs, disturbed the secretion of steroid and impacted the luteal vascular networks. BaP significantly decreased the angiogenesis factor (VEGFR, Ang-1 and Tie2) and increased the anti-angiogenic factor THBS1. Inhibited THBS1 function by LSKL partially rescued the angiogenesis defect caused by BaP. In vitro, BaP metabolite BPDE also interfered the expression levels of angiogenesis-related factors in HUVECs and impaired the angiogenesis, whereas supplemented with rAng-1 can alleviate the anti-angiogenic effect of BPDE. Furthermore, Notch signaling molecules, including Notch1, Dll4, Jag1 and Hey2, which are essential for the establishment and maturation of vascular networks, were affected by BaP exposure. Collectively, BaP broke the molecular regulatory balance between luteal angiogenesis and vascular maturation, impaired the construction of luteal vascular networks, and further affected luteal formation and endocrine function during early pregnancy. Our findings might provide new insight into the relationship between BaP and luteal insufficiency in early pregnancy. These data also give a new line of evidence for curtailing BaP emissions and protecting the women of childbearing age from occupational exposure.

Herein, the concept of "inverted" (the mode "molecules mainly interact with cations") deep eutectic solvents (DESs) is proposed. A strategy to form inverted DESs by host-guest interactions was developed, and thus numerous DESs could be designed and formed by a combination of host and guest molecules. These liquids are expected to be used as nonaqueous electrolytes in potassium-ion batteries or other fields for further exploration.

In this article, two kinds of isotactic polypropylene (iPP)/high density molecular weight polyethylene (HDPE) blend samples were prepared by an accessible injection-molding method. These two samples contain iPP shish kebab matrix and HDPE dispersed phase (shish kebab and epitaxy crystal, respectively). The variation of microstructures upon annealing was characterized using scanning electron microscopy, differential scanning calorimetry and small-angle X-ray scattering. It was found that the variations of different crystalline structures were changed by varying annealing parameters. Only the rearrangement of partially melted chains into primary lamellae happened for the sample with epitaxy crystalline structure, which was distinguished from the sample with HDPE shish kebab structure. Moreover, the variation of the crystalline structure, crystallinity and melting point were discussed to account for the changes in mechanical properties. These results revealed the relationship among the morphology, annealing parameters and mechanical properties, which provide a practical method to industrial manufacture.

During pregnancy, there is increased expression of some cytokines at the fetal–maternal interface; and the clarification of their roles in trophoblast–endometrium interactions is crucial to understanding the mechanism of placentation. This review addresses the up-to-date reported mechanisms by which the members of the transforming growth factor beta superfamily regulate trophoblast proliferation, differentiation, and invasion of the decidua, which are the main phases of placentation. The available information shows that these cytokines regulate placentation in somehow a synergistic and an antagonistic manner; and that dysregulation of their levels can lead to aberrant placentation. Nevertheless, prospective studies are needed to reconcile some conflicting reports; and identify some unknown mediators involved in the actions of these cytokines before their detailed mechanistic regulation of human placentation could be fully characterized. The TGF beta superfamily are expressed in the placenta, and regulate the process of placentation through the activation of several signaling pathways.

Thyroid hormones (THs) regulate a number of metabolic processes during pregnancy. After implantation, the placenta forms and enhances embryonic growth and development. Dysregulated maternal THs signaling has been observed in malplacentation-mediated pregnancy complications such as preeclampsia, miscarriage, and intrauterine growth restriction (IUGR), but the molecular mechanisms involved in this association have not been fully characterized. In this review, we have discussed THs signaling and its roles in trophoblast proliferation, trophoblast differentiation, trophoblast invasion of the decidua, and decidual angiogenesis. We have also explored the relationship between specific pregnancy complications and placental THs transporters, deiodinases, and THs receptors. In addition, we have examined the effects of specific endocrine disruptors on placental THs signaling. The available evidence indicates that THs signaling is involved in the formation and functioning of the placenta and serves as the basis for understanding the pathogenesis and pathophysiology of dysthyroidism-associated pregnancy complications such as preeclampsia, miscarriage, and IUGR.

Ethanol is an important bulk chemical with diverse applications. Biomass-derived ethanol is traditionally produced by fermentation. Direct cellulose conversion to ethanol by chemocatalysis is particularly promising but remains a great challenge. Herein, a one-pot hydrogenolysis of cellulose into ethanol was developed by using graphene-layers-encapsulated nickel (Ni@C) catalysts with the aid of H3 PO4 in water. The cellulose was hydrolyzed into glucose, which was activated by forming cyclic di-ester bonds between the OH groups of H3 PO4 and glucose, promoting ethanol formation under the synergistic hydrogenation of Ni@C. A 69.1 % yield of ethanol (carbon mole basis) was obtained, which is comparable to the theoretical value achieved by glucose fermentation. An ethanol concentration of up to 8.9 wt % was obtained at an increased cellulose concentration. This work demonstrates a chemocatalytic approach for the high-yield production of ethanol from renewable cellulosic biomass at high concentration.

Embryo implantation is an essential and complex process in mammalian reproduction. However, little evidence has indicated the involvement of autophagy during embryo implantation. To determine the possible role of autophagy in uterine of pregnant mice during the peri-implantation stage, we first examined the expression of autophagy-related markers ATG5 and LC3 on day 4, 5, and 6 of pregnancy (D4, D5, and D6, respectively). Compared with expression on D4, downregulation of the autophagy-related markers was observed on D5 and D6, the days after the embryo attached to the receptivity endometrium. Further examination showed that autophagy-related markers ATG5, ATG12, LC3, cathepsin B, and P62 at the implantation site were significantly decreased when comparing with the inter-implantation site. Fewer number of autophagosomes at the implantation site were also observed by transmission electron microscopy. To confirm the functional role of autophagy during embryo implantation in mice, we administered the autophagy inhibitor 3-methyladenine and chloroquine to mice. After treated with 3-methyladenine, the expression of decidual markers HOXA10 and progesterone receptor were significantly reduced. Furthermore, a reduction in implantation sites and increase in the HOXA10 and PR protein levels were observed in response to chloroquine treatment. In addition, impaired uterine decidualization and dysregulation of the PR and HOXA10 protein levels was observed after autophagy inhibited by 3-methyladenine and chloroquine in in vivo artificial decidualization mouse model. In the last, LC3 and P62 were also observed in normal human proliferative, secretory, and decidua tissues. In conclusion, endometrial autophagy may be essential for embryo implantation, and it may be associated with endometrial decidualization during early pregnancy. KEY MESSAGE: • Autophagy-related markers were significantly decreased at implantation site. • Autophagy inhibition results in abnormal decidualization. • Autophagy is essential for embryo implantation.

Dibutyl phthalate (DBP), one of the most widely used plasticizers, is a known environmental endocrine disruptor that impairs male and female fertility. In this study, oral administration of DBP was given to pregnant mice on 14.5 days post coitus (dpc) for 3 days; and additionally, DBP was added into the culture of 14.5 dpc fetal ovaries for 3 days. DBP exposure during gestation disturbed the progression of meiotic prophase I of mouse oocytes, specifically from the zygotene to pachytene stages. Meanwhile, the DBP-exposed pachytene oocytes showed increased homologous recombination sites and unrepaired DNA damage. Furthermore, DBP caused DNA damage by increasing oxidative stress, decreased the expression of multiple critical meiotic regulators, and consequently induced oocyte apoptosis. Moreover, the effect of DBP on meiosis I prophase involved estrogen receptors α and β. Collectively, these results demonstrated a set of meiotic defects in DBP-exposed fetal oocytes. As aberrations in homologous recombination can result in aneuploid gametes and embryos, this study provides new support for the deleterious effects of phthalates.

A facile one-pot two-stage photochemical synthesis of aromatic azoxy compounds and imines has been developed by coupling the selective reduction of nitroaromatic compounds with the selective oxidation of amines in an aqueous solution. In the first stage (light illumination, Ar atmosphere), the light excited nitroaromatic molecule abstract H from amine to form ArNO2H and amine radical, which then form nitrosoaromatic, hydroxylamine and imine compounds. Water acts as a green solvent for the dispersion of the reactants and facilitates the formation of nitrosoaromatic and hydroxylamine intermediate compounds. In the second stage (no light, air atmosphere), the condensation of nitrosoaromatic and hydroxylamine compounds yields aromatic azoxy product with the aid of molecular oxygen in air. This photochemical synthesis achieved both high conversion and high product selectivity (>99%) at room temperature.

Maternal exposure to endocrine-disrupting chemicals (EDCs) is associated with long-term hormone-dependent effects that are sometimes not revealed until maturity, middle age, or adulthood. The aim of this study was to conduct descriptive reviews on animal experimental and human epidemiological evidence of the adverse health effects of in utero and lactational exposure to selected EDCs on the first generation and subsequent generation of the exposed offspring. PubMed, Web of Science, and Toxline databases were searched for relevant human and experimental animal studies on 29 October 29 2018. Search results were screened for relevance, and studies that met the inclusion criteria were evaluated and qualitative data extracted for analysis. The search yielded 73 relevant human and 113 animal studies. Results from studies show that in utero and lactational exposure to EDCs is associated with impairment of reproductive, immunologic, metabolic, neurobehavioral, and growth physiology of the exposed offspring up to the fourth generation without additional exposure. Little convergence is seen between animal experiments and human studies in terms of the reported adverse health effects which might be associated with methodologic challenges across the studies. Based on the available animal and human evidence, in utero and lactational exposure to EDCs is detrimental to the offspring. However, more human studies are necessary to clarify the toxicological and pathophysiological mechanisms underlying these effects.

In situ microfibrillation and multiflow vibrate injection molding (MFVIM) technologies were combined to control the phase morphology of blended polypropylene (PP) and poly(ethylene terephthalate) (PET), wherein PP is the majority phase. Four kinds of phase structures were formed using different processing methods. As the PET content changes, the best choice of phase structure also changes. When the PP matrix is unoriented, oriented microfibrillar PET can increase the mechanical properties at an appropriate PET content. However, if the PP matrix is an oriented structure (shish-kebab), only the use of unoriented spherical PET can significantly improve the impact strength. Besides this, the compatibilizer polyolefin grafted maleic anhydride (POE-g-MA) can cover the PET in either spherical or microfibrillar shape to form a core&ndash, shell structure, which tends to improve both the yield and impact strength. We focused on the influence of all composing aspects&mdash, fibrillation of the dispersed PET, PP matrix crystalline morphology, and compatibilized interface&mdash, on the mechanical properties of PP/PET blends as well as potential synergies between these components. Overall, we provided a theoretical basis for the mechanical recycling of immiscible blends.

The Fischer-Tropsch (FT) process is a practical approach to convert synthesis gas (CO and H2) into hydrocarbons and oxygenates, and these product mixtures are usually well-characterized. However, the analysis of Fischer-Tropsch waste water (FTW) is still somewhat underdeveloped and the exact composition of FTW remains unclear. Herein, various qualitative NMR techniques, especially diffusion-ordered spectroscopy (DOSY) and one dimension (1D) selective gradient total correlation spectroscopy (SelTOCSY) were strategically applied in the analysis of FTW. The NMR results show that the DOSY technique can pseudo-separate most of components in complex mixtures over the diffusion dimension. The SelTOCSY technique is used as a supporting method in the cases where the DOSY technique cannot clearly distinguish overlapped signals. Moreover, the quantitative 1H NMR (qNMR) was further used to quantify the components of the sample. These routine and advanced qualitative and quantitative NMR technique utilized here provide a fast, effective and feasible method for the identification of complex mixtures in FTW, which might be a powerful and fast alternative to gas chromatography or high performance liquid chromatography for FTW research.

Alzheimer’s disease (AD) is an age-related neurodegenerative disease characterized by the deposition of amyloid-β (Aβ) peptides and neurofibrillary tangles (NFTs) and massive loss of neuronal cells in the brain. Adult hippocampus continuously generates new neurons throughout life to shape brain function and impaired neurogenesis may contribute to a series of cognitive deterioration associated with AD. Enhancing endogenous neurogenesis represents a promising strategy that may ameliorate AD-associated cognitive defects. However, neurogenesis-enhancing approaches and underlying mechanisms are still not well studied. Here, using a mouse model of AD amyloid precursor protein (APP/PS1/Nestin-GFP triple transgenic mice, 3xTgAD), we examined the effects of 4 weeks of valproic acid (VPA) treatment on hippocampal neurogenesis in 2- and 6-month-old mice. VPA treatment promoted cell proliferation and increased the density of immature neurons in the dentate gyrus (DG) of the hippocampus of 3xTgAD mice. Consistent with enhanced neurogenesis, behavioral and morphological analysis showed that VPA treatment improved the learning and memory ability of 3xTgAD mice. Mechanistically, VPA treatment increased β-catenin levels, accumulated the inactive form of glycogen synthase kinase-3β (GSK-3β), and induced the expression of NeuroD1, a Wnt target gene involved in neurogenesis, suggesting the activation of the Wnt signaling pathway in the hippocampus of 3xTgAD mice. This study indicates that VPA stimulates neurogenesis in the adult hippocampus of AD mice model through the Wnt pathway, highlighting VPA as a potential therapeutic for treating AD and related diseases.

Folate deficiency has been linked to a wide range of pregnancy disorders. Most research about folate-deficiency has focused on the embryo itself, little attention has been paid to possible effects on the placenta. According to our results, the morphology of the placenta, endocrine function, and the expression of genes involved in placental differentiation were all abnormal in folate-deficient mice on days 10, 12, and 14 of pregnancy. Similar results were found in human placenta explants cultured in folate-deficient medium. Autophagy is an inducible catabolic process activated by external nutrients starvation. Here we explored further, whether autophagy was involved in the abnormal placentation caused by folate-deficiency. The aberrant number of autophagosomes measured by transmission electron microscopy and the deviant expression of autophagy-related markers showed a disordered autophagy in placentas under conditions of folate-deficiency in vivo and in vitro dual-fluorescence mRFP-eGFP-LC3 analysis indicated enhanced autophagy was detected in HTR8/SVneo cells incubated in folate-deficient medium. Importantly, the placentation impairment in mice and human placenta explants could be recovered by inhibiting placental autophagy using 3-MA. In addition, the apoptosis and invasive capability of HTR8/SVneo cells were obviously suppressed by folate deficiency but notably elevated by 3-MA. These data suggest that folate deficiency can impair placentation and autophagy is a key factor in this. However, the signal pathway by which folate deficiency causes aberrant autophagy needs to be explored further.

The degradation and recovery of waste rigid polyurethane foam (RPUF) have confronted enormous challenge because of its three-dimensional network. An efficient strategy was developed for chemical recycling of high value-added aromatic polyamines and polyether polyols via selective cleavage of carbamate and urea bonds from RPUF and characterized by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Ray (FT-IR). The carbamate and urea bonds were readily cleaved using (NH2)2CO/CH3CH2OH as degradation system at 180 °C for 10 h. Nevertheless, the C–C bonds and C–O–C of ether linkages as framework structure remained intact in the degradation process. Eventually, the high value-added products including aromatic polyamines and polyether polyols were retrieved. A feasible mechanism for degradation was proposed based on the NMR observations.

Deep eutectic solvents (DESs) have attracted broad attention due to their low cost and toxicity, easy preparation, good biological compatibility and similar characteristics to those of ionic liquids. In this study, a DES system composed of choline chloride and urea has been applied for the controllable degradation of polyurethane (PU). By the combination of Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser analytical ionization time-of-flight mass spectrometer (MALDI-TOF-MS), the selective cleavage of carbamate and urea bonds with little damage on carbonate bonds was achieved in the DES system by the regulation of reaction conditions, which favored the recovery of both valuable polycarbonate diol (PCDL) and 3,3′-Dimethyl-[1,1′-biphenyl]-4,4′-Diamine (o-toluidine). The degradation rate of PU and the yield of PCDL reached 100% and 57.4% respectively under mild conditions (1 atm, 170 °C, 8 h). A possible degradation mechanism was proposed based on the experimental results, in which the synergistic effect of choline chloride and urea activated largely the carbamate bond and thus led to a controlled degradation of PU.

Carbon fiber reinforced bismaleimide resin (CF/BMI) composites were recycled by chemical methods. The degradation of bismaleimide (BMI) resin was achieved in subcritical acetic acid. The C-N bonds of BMI resin were selectively cleaved by Ca(NO3)2. The results show that NO3− presents strong oxidizing ability in subcritical acetic acid and Ca2+ was beneficial to the oxidation of NO3−. The carbon fibers can be totally reclaimed from CF/BMI composites. The degradation products of BMI resin were partly carbonized due to the strong oxidation and high reaction temperature. However, the degradation products can be used to produce nitrogen doped carbon materials. The nitrogen doped carbon materials were used to catalyze the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF). The work developed a promising strategy for the full-component recycling of waste CF/BMI composites.

In this study, different from previous reports focused on removal efficiency of Cr(VI), the structural variations of brown coal and kerogen concerned with Cr(VI) removal were studied. The process conditions of Cr(VI) removal were optimized, and the reduction of Cr(VI) to Cr(III) was evaluated. In addition, the variations of functional groups in brown coal and kerogen before and after Cr(VI) detoxification were characterized by FTIR, XPS, SS-NMR, TEM-EDS, and SEM-EDS. The results indicated that brown coal and kerogen had highly adsorption efficiency for Cr(VI) (maximum 4.67 mmol/g), and 80.1% of adsorbed Cr(VI) was reduced to Cr(III) while 90.4% of them was held on the adsorbents. It also revealed that the content of –CH 3 , –CH 2 , C O and phenolic hydroxyl groups in adsorbents decreased, but the content of C O and O–C O groups increased after Cr(VI) detoxification. Overall, structure identified of brown coal and kerogen in this work could provide important basic data for further application in wastewater treatment.

Various NMR techniques were employed to study the catalytic performance of the Lewis acid SnCl4 and the Bronsted acid HCl in the conversion of inulin to value-added compounds by hydrolysis and subsequent dehydration. The hydrolysis of inulin was examined to reveal the catalytic abilities of SnCl4 besides its intrinsic acidity by in situ 1H and 13C NMR at 25 °C. The dehydration reaction of inulin with SnCl4 as catalyst was followed by high temperature in situ 1H NMR at 80 °C. The fructose moieties were dehydrated to 5-(hydroxymethly)furfural (5-HMF), but the glucose fragment of inulin was inactive for dehydration reaction under this condition. The formation of 5-HMF and its transformation into formic acid and levulinic acid through a rehydration reaction could be monitored by in situ NMR spectroscopy. Moreover, diffusion ordered spectroscopy NMR revealed that the Lewis acid ion, Sn4+ interacts with the inulin model compounds, i.e., sucrose and fructose. The synergistic effects of complexation and acidity f...

2,5-hexanedione, a valuable platform chemical which is being broadly used in biofuel, medicinal chemistry and drug discovery, was synthesized from biomass derived dimethyl furane using a highly efficient biphasic system. In this biphasic systems, mineral acids (HCl, H2SO4 and H3PO4) dissolved in aqueous phase were used as hydrolysis catalysts. The hydrolysis reaction is suggested to take place at the interface between the aqueous and the organic phase. But more importantly, water-immiscible organic phase could continuously extract the in-situ produced 2,5-hexanedione from the interface to prevent the extended contact between the 2,5-hexanedione and the acids, thereby avoiding the oligomerization side reactions A yield of 99 % could be obtained when methyl isobutyl ketone (MIBK) was the organic phase in the biphasic system.

This research focuses on high-value utilization of the lignin-derived phenol monomer and bioethanol from biorefining process. Supported-heteropolyacid is easily used as an efficient catalyst for the ethylation of phenol with bioethanol to obtain value-added products. Through adjusting the loading amount, different acidity amount and strength can be obtained, leading to the tunable selectivity to the phenol ethylation route and regioselectivity.

Spermatogenesis is a critical process for maintaining male fertility. Sustained spermatogonial stem cell self-renewal and differentiation ensures constant spermatogenesis, and several signalling pathways regulate this process. An increasing number of studies have suggested that the mammalian target of rapamycin (mTOR) signalling pathway plays an important role in spermatogenesis; however, the mechanism remains unknown. Our study showed that mTOR was positively related with spermatogenesis by detecting mTOR expression and the expression of its target p70s6k, rps6 and 4e-bp1 at different developmental stages. Phosphorylated p70s6k, rps6 and 4ebp1 levels were independently and gradually down-regulated with age. Subsequently, we showed in vivo and in vitro that, upon mTOR inactivation by rapamycin, the number of sperm significantly decreased (P < 0.05) and spermatogonia proliferation was blocked. Phosphorylated p70s6k and rps6 levels were down-regulated, but the levels of phosphorylated 4e-bp1 did not change. Spermatogonia were treated with the specific PI3K inhibitor LY294002, and p70s6k, rps6 and 4ebp1 phosphorylation overtly decreased. Therefore, we suggest that mTOR plays an important role in spermatogenesis by regulating p70s6k activation and that 4e-bp1 is either directly or indirectly regulated by PI3K.

A crystalline bisindolylmaleimide (BIM) 3 with strong fluorescence in the solid state was prepared and studied. Its analogous cross-linked polymer 4 with the same BIMs fluorophore was designed and characterized. The investigation of the covalent bonding networking effect on the solid-state fluorescence was carried out by the comparison between 3 and 4.

The diffusion ordered NMR spectroscopy (DOSY) protocol for the analysis of reaction mixture of lignocellulosic biomass conversion has been developed and investigated systematically. Model reaction mixtures from cellulose, hemicellulose and lignin conversion, real reaction mixtures of sucrose and glucose dehydration, were facilely separated and assigned in the diffusion dimension without any prior separation or isolation. The shift reagent, EuFOD, was successfully utilized to increase the difference in diffusion and thereby resolution in lignin degradation model. DOSY NMR offers an easy and robust method for the structure identification and reaction mixture separation in biomass conversion.

A well-defined nitro group functionalized porous aromatic framework (NO2-PAF-1) was synthesized via a bottom-up strategy using a copper-mediated Ullmann reaction. The synthetic route is cost-efficient and robust for large scale preparation. The Brunauer–Emmett–Teller (BET) specific surface area of the obtained NO2-PAF-1 is up to 610 cm2 g−1 with micro/mesoporosity. Its CO2 uptake was measured to be higher than that of PAF-1 due to the strong interaction between the nitro groups and CO2 molecules, proven by the enhanced isosteric heat of CO2 adsorption (38.4 kJ mol−1).

Compared to 5-HMF (C6H6O3), angelica lactone (C5H6O2) is a platform compound that has more potential for biomass-derived high performance bio-alkane fuel production due to a CC bond in the molecular structure, leading to a C–C coupling intermediate (C10 self-aggregation dimer) and higher C:O ratio (2.5), resulting in lower hydrogen consumption for the subsequent hydrodeoxygenation process. Biomass-derived levulinic acid was used as the only starting raw material to produce C10 branched alkanes. First, carboxyl and carbonyl functional groups of levulinic acid under catalysis via intramolecular esterification and dehydration yielded angelica lactone, which included two isomers of angelica lactone (α-angelica lactone and β-angelica lactone). Secondly, angelica lactone di/trimers would be obtained by angelica lactone self-aggregation: α-angelica lactone and β-angelica lactone connecting via C–C bond coupling. Finally, these intermediate products are selectively hydrodeoxygenated over a RANEY® catalyst to obtain C7–C10 branched alkanes. Nearly a 90% yield can be achieved under 483 K and 5 MPa H2 and the C10 branched alkane product, 3-ethyl-4-methyl heptane, accounts for 75% of the same.

Low temperature 1H- and 19F-DOSY have been used for analyzing reactive intermediates in glycosylation reactions, where a glycosyl trichloroacetimidate donor has been activated using different catalysts. The DOSY protocols have been optimized for low temperature experiments and provided new insight into acid catalyzed glycosylation chemistry. From the study a new glycosylation intermediate was characterized.

An efficient strategy is developed for chemical recycling of cured epoxy resin (CEP) from its carbon fiber reinforced polymer composites (CFREP) using AlCl3/CH3COOH as the degradation system. Acetic acid swells the dense structures of CEP, facilitating the penetration of the aluminum ion catalyst into the polymer matrix. The weakly coordinating aluminum ions in CH3COOH solution selectively cleave the C–N bond while leaving the C–C, C–O (aryl alkyl ether) bonds intact. This process recovers valuable oligomers and carbon fibers from CFREP.

The thermal degradation of chitin biomass with various molecular structures was investigated by thermogravimetric analysis (TG), and the gaseous products were analyzed by connected mass spectroscopy (MS). The chemical structure and morphology of char residues collected at 750°C using the model substrates GlcNH2 and GlcNAc, were characterized systematically. The experimental results disclosed that one main mass loss stage was observed for each substrate. Chitosan samples with high molecular weight shown the more thermal stability, and chitin showed the highest thermal stability. Additionally, it was found that catalysts play a significant role during the pyrolysis. The gaseous evolution components, including NH3, H2O, CO, and CO2 were observed by on line MS. The experimental results disclosed that the obtained carbonaceous materials had lost the original hydrocarbon structure totally, and transformed into an aromatic structure with high carbon and nitrogen content, which was identified by XPS and solid state NMR.

Activins and inhibins - comprising activin A, B, AB, C and E, and inhibin A and B isoforms - belong to the transforming growth factor beta (TGFβ) superfamily. They regulate several biological processes, including cellular proliferation, differentiation and invasiveness, to enhance the formation and functioning of many human tissues and organs. In this review, we have discussed the role of activin and inhibin signaling in the physiological and female-specific pathological events that occur in the female reproductive system. The up-to-date evidence indicates that these cytokines regulate germ cell development, follicular development, ovulation, uterine receptivity, decidualization and placentation through the activation of several signaling pathways; and that their dysregulated expression is involved in the pathogenesis and pathophysiology of the numerous diseases, including pregnancy complications, that disturb reproduction. Hence, some of the isoforms have been suggested as potential biomarkers and therapeutic targets for the management of some of these diseases. Tackling the research directions highlighted in this review will enhance a detailed comprehension and the clinical utility of these cytokines.

Disentanglement is potentially a feasible method to improve the processability of polymers without any additives. But there still lacks the methods to efficiently prepare “in-pellet” disentangled polymers. To realize the large-scale production of disentangled pellets, we firstly designed a novel Polymer Melt Disentanglement Machine (PMDM), which can uniquely impose complex shear field (superposition of rotational shear and oscillatory shear) on polymer melt to induce disentanglement. Then, the disentangled polycarbonate pellets were prepared by PMDM under rotational shear, oscillatory shear and complex shear respectively. Finally, we compared the disentanglement effect of those three shear modes and the results show that the sample disentangled by complex shear field has a lower zero-shear viscosity and a higher melt flow rate compared with the samples disentangled by other two shear modes. Besides, the processing temperature and pressure of the disentangled pellets can be reduced by 20 °C and 25% respectively compared with the raw pellets. Complex shear field can efficiently disentangle polymer melt, which indicates its application prospect to improve the processability of the engineering plastics with high melt viscosity, such as polycarbonate et al., by a large-scale production of “in-pellet” disentangled materials via PMDM prior to processing.

Oxidation of 5-hydroxymethylfurfural (HMF) with molecular oxygen to maleic acid (MAc) was performed on graphene oxide (V-GO) supported vanadium composite. The solvent effects (γ-valerolatctone (GVL), acetic acid and H2O) on the reaction were investigated by combing the characterizations of X-ray Photoelectron Spectroscopy (XPS), 13C and 1H Nuclear Magnetic Resonance (13C NMR and 1H NMR), Inductive Coupled Plasma Emission Spectrometer (ICP), and Elemental Analysis (EA), and kinetic studies. GVL was the most efficient solvent with the highest yield of MAc, while acetic acid and H2O benefited the C–C cleavage, giving more formic acid (FAc) than GVL. These variation in the solvent effects originated from the different ability of solvents to convert HMF molecules and 5-hydroxyl-2(5H)-furanone (HF) intermediate. Besides, the protons (H+) in graphene oxide were identified to promote HMF oxidation to MAc, whereas the added NaHCO3 caused the catalyst deactivation. By combing the fabrication of model catalyst and XPS analysis, this negative effect of NaHCO3 resulted from both the inhibition in the reduction of V5+ → V4+ and/or V4+ → V3+ and the loss in the H+ sites on the GO support caused by neutralization reaction. Furthermore, the reaction intermediates were identified by NMR. Oxidation of HMF to MAc was a two-step process, i.e., HMF oxidization to HF intermediate and its following oxidation to MAc. Both oxidation steps required the presence of vanadium and O2. A feasible path for HMF oxidation to MAc was proposed based on the NMR observations.

The selective aerobic oxidation of 5-hydroxymehtylfurfural (HMF) to synthesize 2,5-diformylfuran (DFF) using nitrogen-doped porous carbons as catalysts was achieved. The N-doped carbon materials were prepared by pyrolysis of chitosan with K2CO3 as an activator at 600 to 900°C. The N-doped porous carbon activated at 700 °C showed the highest catalytic activity in the conversion from HMF to DFF without any co-catalyst, i.e., the 95.3% HMF conversion and 94.6% selectivity of DFF under optimum reaction conditions (120°C, 7.5 h and 2.0 MPa O2). According to the XPS results graphitic nitrogen on the surface of the catalysts played a critical role in the activation of O2 to form oxygen radicals that facilitated the oxidative dehydrogenation of HMF.

Previous studies have shown that shear-induced disentanglement of polyolefins can realize on line. However, it is difficult to realize “in pellet” disentanglement for linear polyolefins. This work tried to retard the recovery of disentanglement of HDPE by adding small amount of UHMWPE. Results showed that shear can induce HDPE/UHMWPE blends disentanglement to a large extent. The total re-entanglement time of blends was as much as twice than HDPE, the half time of re-entanglement of H/U3 and H/U5 climbed up from 140 to 710 and 633s respectively. It is highly possible to realize “in pellet” disentanglement to meet the post processing. Furthermore, it was interestingly found that the viscosity of blend would be lower than that of HDPE at a certain time range under the conditions of this experiment. The reduced entanglement enabled the higher chain mobility, which facilitated the formation of the more perfect crystals.

In situ 13C and 1H NMR and selective 1D TOCSY spectra have been used for analyzing reactive intermediates in fructose conversion, where fructose with diammonium hydrogen phosphate [(NH4)2HPO4] is consumed via a glucosamine (GlcNH2) intermediate. Our data indicate that the nitrogen in (NH4)2HPO4 maps onto the intermediate GlcNH2 and subsequent to the corresponding product deoxyfructosazine (DOF). Pathways leading to isomerization of fructose have furthermore been identified through DFT calculations. The inclusion of solvent effects results in substantial reduction of the fructose ring-opening free energy barrier (19.4 kcal/mol). Interestingly, lower free energy barrier (21.0 kcal/mol) indicating that the formation of intermediate GlcNH2 is both thermodynamically and kinetically accessible in agreement with the experimental results. Yield of DOF reaches 46% under the optimized conditions.

Our previous study found that two novel cancer-related genes, PRR11 and SKA2, constituted a classic gene pair that was regulated by p53 and NF-Y in lung cancer. However, their role and regulatory mechanism in breast cancer remain elusive. In this study, we found that the expression levels of PRR11 and SKA2 were upregulated and have a negative prognotic value in breast cancer. Loss-of-function experiments showed that RNAi-mediated knockdown of PRR11 and/or SKA2 inhibited proliferation, migration, and invasion of breast cancer cells. Mechanistic experiments revealed that knockdown of PRR11 and/or SKA2 caused dysregulation of several downstream genes, including CDK6, TPM3, and USP12, etc. Luciferase reporter assays demonstrated that wild type p53 significantly repressed the PRR11-SKA2 bidirectional promoter activity, but not NF-Y. Interestingly, NF-Y was only essential for and correlated with the expression of PRR11, but not SKA2. Consistently, adriamycin-induced (ADR) activation of endogenous p53 also caused significant repression of the PRR11 and SKA2 gene pair expression. Notably, breast cancer patients with lower expression levels of either PRR11 or SKA2, along with wild type p53, exhibited better disease-free survival compared to others with p53 mutations and/or higher expression levels of either PRR11 or SKA2. Collectively, our study indicates that the PRR11 and SKA2 transcription unit might be an oncogenic contributor and might serve as a novel diagnostic and therapeutic target in breast cancer. [BMB Reports 2019; 52(2): 157-162].

Chemical reactions with products of high reactivity generally suffer from low yields due to the severe side reactions. This is the case for the synthesis of acrolein from glycerol dehydration. To improve the yield of acrolein, fast removal of high reactive acrolein molecules from the reaction system is desirable but remains a major challenge, due to the high viscosity of glycerol. To tackle this problem, the Pickering emulsion was chosen as the reaction system in this work to accelerate the removal of acrolein. A water-in-oil Pickering emulsion was fabricated for the liquid phase dehydration of glycerol to acrolein, which exhibits twice yield of acrolein compared with the homogeneous system. The combination of the transfer experiments and IR analysis confirmed the drastic restrain of the side reactions between acrolein and glycerol, due to the intensified mass transfer of acrolein from the liquid phase by the larger microinterface of emulsion. Furthermore, the transfer rate of acrolein through the water-oil interface can be tuned via a shift in the interfacial properties of the silica emulsifier by silylation treatment. The highest acrolein yield of nearly 50% was obtained with the highest transfer rate of acrolein on the silica silylated by (MeO)3Si(CH2)11CH3.

Embryo implantation is essential for normal pregnancy, and the process of decidualization is critical for embryo implantation. However, the mechanism of decidualization during early pregnancy is still unknown. Forkhead box O3a (FOXO3a) is the most important functional transcription factor of the forkhead box family and is a highly conserved transcription factor of apoptosis-related genes. In the mouse uterus, FOXO3a was found to be expressed regularly from Days 1-7 of early pregnancy. Upon further exploration, it was found that FOXO3a was expressed at significantly higher levels at the implantation site than at the interimplantation site on Days 5-7 of pregnancy. Under artificial decidualization, FOXO3a was highly expressed in the first and second decidual zones. After decidualization, the expression of FOXO3a was significantly increased both in vivo and vitro. In primary stromal cells, apoptosis was reduced by decreased expression of FOXO3a after inducing decidualization. Moreover, when FOXO3a-small interfering RNA was transfected into the uteri of mice, the expression of decidualization- and apoptosis-related factors was impaired. Thus, FOXO3a might play an important role in decidualization during early pregnancy, and cell apoptosis might be one of pathways for FOXO3a-regulated decidualization.

The female reproductive lifespan is largely determined by the size of the primordial follicle pool, which is established early in life. We previously reported that Di (2-ethylhexyl) phthalate (DEHP), an environmental endocrine disruptor and a widely-spreading plasticizer, impairs primordial folliculogenesis. In the present study, we found DEHP significantly altered the number and sex ratio of the offspring of neonatal-exposed mice. Furthermore, by a neonatal exposure model and an ovary culture model, it showed that DEHP activated autophagy in the ovary, with increased autophagy-related gene expression and recognizable autophagosomes, while inhibition of autophagy by 3-MA attenuated the adverse impact of DEHP on primordial folliculogenesis. Moreover, key components of AMPK-SKP2-CARM1 signalling were up-regulated by DEHP in the ovary, and AMPK inhibitor Compound C reduced autophagy-related gene expression and partially recovered primordial follicle assembly. Collectively, this study demonstrates that DEHP induces autophagy by activating AMPK-SKP2-CARM1 signalling in mice perinatal ovaries, which results in disrupted primordial folliculogenesis and reduced female fertility.

Folate deficiency results in abnormal embryonic development, but the underlying mechanisms remain to be comprehensively investigated. Mutation of Vangl genes belonging to the planar cell polarity (PCP) pathway is associated with abnormal embryonic development, but the effect of folate deficiency on the PCP pathway is unclear. In this study, we found that folate deficiency inhibited Vangl gene expression and Vangl protein binding to the ligand Dvl. As a methyl donor, folate can chemically alter the DNA methylation levels of genomic sequences. Here, reduced representation bisulfite sequencing (RRBS) was employed to detect the methylation profiles of mouse embryos. The results confirmed that folate deficiency affected the genomic methylation levels of mouse embryos, which resulted in down-regulation of key genes involved in embryonic development. Gene ontology (GO) analysis suggested that the genes located in the differentially methylated regions (DMRs) are primarily involved in biological regulation, cellular processes, development, metabolism, and signaling pathways. The data revealed that folate deficiency inhibits the PCP pathway and alters genomic methylation profiles, which may be the underlying mechanisms through which folate deficiency impairs embryonic development.

Benzo(a)pyrene (BaP) is a persistent organic pollutant (POP) that is a serious threat to human health. Numerous studies have shown that BaP causes adverse effects in pregnancy, but the mechanism remains unclear. The moderate invasion of trophoblast cells into the endometrium is an important factor during successful embryo implantation. The aim of this study was to investigate the effect and mechanism of BaP on the invasion and migration of trophoblast cells. HTR-8/SVneo cells were treated with different concentrations (1, 5, 10, 25, 50 and 100 μM) of BaP. The invasion and migration of HTR-8/SVneo cells were observed after BaP treatment. The protein levels related to migration and invasion was detected by Western blot. The results confirmed that BaP inhibits the migration and invasion of extravillous trophoblast HTR-8/SVneo cells. Further investigations indicated that the protein levels of MMP-2, MMP-9 and E-cadherin in HTR-8/SVneo cells were changed by BaP treatment. Moreover, the data demonstrated that BaP activated the MAPK signaling pathway. Pretreatment with specific inhibitors of MAPK rescued BaP-induced change in the migration and invasion of HTR-8/SVneo cells. Taken together, our results indicated that BaP inhibits invasion and the migration of HTR-8/SVneo cells, which might cause a failure in early pregnancy. Copyright © 2015 John Wiley & Sons, Ltd.

Aims Neurodegenerative diseases are the leading cause of morbidity and mortality worldwide. Several studies have shown that tetramethylpyrazine (TMP) is an effective therapy for neurodegenerative diseases and that it acts by inhibiting the activation of microglial cells in response to inflammatory stimuli. However, the molecular mechanisms underlying the action of TMP remain unknown. Main methods Proteomic analysis was used to generate novel insights into the mechanism by which TMP inhibits microglial activation, and western blotting was used to validate candidate proteins. Key findings To identify candidate proteins affected by TMP in lipopolysaccharide-activated microglia, we performed proteomic analysis using iTRAQ labelling coupled with LC TRIPLE-TOF, and we identified 5187 unique proteins. Among these, 266 proteins were differentially expressed and considered putative candidate proteins. Protein annotation revealed that the differentially expressed proteins, such as inducible nitric oxide synthase (iNOS) and ERO1-like protein (ERO1L), might be involved in reducing cellular oxidation in response to stress. Ingenuity pathway analysis revealed that the differentially expressed proteins were involved in a variety of signalling pathways, including liver X receptor/retinoid X receptor (LXR/RXR) activation and the production of nitric oxide and reactive oxygen species in macrophages. Furthermore, one of the differentially expressed protein candidates detected by iTRAQ, iNOS, was confirmed by western blotting. Significance Our data suggest that iTRAQ technology is an effective tool to study the mechanism by which TMP inhibits activated microglia. TMP decreased the expression of LXR/RXR-mediated iNOS, which reduced microglial activation in response to inflammatory stimuli.

Vangl1 and Vangl2 are homologous genes belonging to the group of highly conserved planar cell polarity proteins. It has been shown that Vangl1 and Vangl2 are essential for embryonic development, cell adhesion, migration and polarity. We examined the expression of Vangl1 and Vangl2 in the uterus of mice during early pregnancy. They are upregulated in the endometrium of peri-implantation and reached the peak on D5. Vangl1 mRNA is widely distributed in the luminal epithelium, glandular epithelium and stromal cells in the endometrium, while its protein only appeared in the stromal cells. The localization of Vangl2 protein overlapped with its mRNA. In addition, expression of Vangl1 in the endometrium of pseudopregnant mice was lower than that of pregnant mice, whereas the level of Vangl2 was not significantly different, suggesting that expression of Vangl1 is induced by embryo. Further study showed that implantation would be suppressed after silencing expressions of Vangl1 and Vangl2 by uterine injection with antisense oligonucleotides. These findings suggest that Vangl1 and Vangl2 may play a key role in the embryo implantation of mice.

The basic ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) could efficiently catalyze the conversion of 2-amino-2-deoxy-d-glucose (GlcNH2) into deoxyfructosazine (DOF) and fructosazine (FZ). Mechanistic investigation by NMR studies disclosed that [C2C1Im][OAc], exhibiting strong hydrogen bonding basicity, could coordinate with the hydroxyl and amino groups of GlcNH2via the promotion of hydrogen bonding in bifunctional activation of substrates and further catalyzing product formation, based on which a plausible reaction pathway involved in this homogeneous base-catalyzed reaction was proposed. Hydrogen bonding as an activation force, therefore, is responsible for the remarkable selectivity and rate enhancement observed.

An efficient strategy has been developed for chemical recycling of unsaturated polyester resin (UPR) and its glass fibre reinforced polymer composites (GFRP) by selectively cleaving C–O bonds using the AlCl3/CH3COOH system. AlCl3 promotes acyl exchange reaction between CH3COOH and UPR. This process facilitates recovery of valuable oligomers and monomers from UPR, and glass fibres from GFRP.