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An efficient process is proposed for recovery of waste LiMn2O4 cathode material, which is one of the most commonly used cathode materials in LIBs. This report constitutes the precipitation thermodynamic analysis and separation experiments based on the water-leaching solutions during the processes of low-temperature calcination with (NH4)2SO4 and water-leaching. Precipitation thermodynamic analysis is undertaken to investigate the effects of initial concentration of the target solution, [N]T1, excess precipitant, and addition of (NH4)2SO4 on the manganese precipitation in the Mn2+–Li+–SO42−–NH3–NH4+–CO32−–H2O system. Moreover, the effects of initial concentration of the target solution, [N]T2, and excess precipitant on the lithium precipitation in the Li+–SO42−–NH3–NH4+–CO32−–H2O system are investigated. All these factors clearly influence the manganese and lithium precipitation, particularly the [N]T and the presence of excess precipitant in the system. The precipitation experimental results demonstrate that the optimal conditions are: a precipitation temperature of 35 °C; an excess coefficient of the precipitant of 2.4; the use of NHC-3 to precipitate the ML-3 solution; a maximum precipitation percentage of manganese of 99.96%; and an absence of Li2CO3 precipitation. The double-sulfate salts (Li(NH4)SO4 & (NH4)2SO4) evaporated and crystallised from the Li+/NH4+ solution are mixed with the waste LiMn2O4 cathode material for calcination and water leaching, for which the efficiencies of Li and Mn are 100% and 96.89%, respectively. The double-sulfate salts are calcined at 550 °C for 45 min to obtain the Li2SO4 product. Finally, the complete recovery and separation of Mn and Li in the waste LiMn2O4 cathode material are achieved.

An efficient process for recycling waste LiMn2O4 cathode material is proposed in this research. This report constitutes low-temperature (NH4)2SO4 calcination mechanisms and water-leaching characteristics of the calcined samples. A calcination temperature range of 420.65–634.12 °C is determined by analysis of the TG-DSC curve under the conditions of heating from 25 to 1000 °C, with a molar ratio of n(2Li + Mn):n(NH4)2SO4 = 1:1 in air atmosphere. The sample calcined at 600 °C for 45 min when the excess coefficient of the (NH4)2SO4 was 1.1 exhibits optimal water-leaching efficiencies of the Li and Mn elements, which are approximately 100% and 96.73%, respectively. The macro-reaction mechanism of the waste LiMn2O4 cathode material calcined with (NH4)2SO4 is determined as the liquid-solid reaction by analysing the apparent morphologies of the calcined samples and their water-leaching residues under different calcination conditions. Moreover, the micro-reaction mechanism is investigated by analysing the phases of the calcined samples and their water-leaching residues under different calcination conditions. The free high-energy H+ released by the decomposition of the NH4+ generated by the molten (NH4)2SO4 play a key role in the entire calcination process. The spinel structure of the LiMn2O4 is broken and Li+ is released owing to the H+ bombarding the Mn O bonds. Finally, the LiMn2O4 is converted into soluble sulphate salts, such as Li2Mn2(SO4)3 and MnSO4.

Photosynthetic bacteria (PSB) technology is a promising method for biomass, protein, pigments, and other value-added substances generation from wastewater. However, the above bioresources production efficiency is relatively low. In this work, a static magnetic field (SMF) was used to promote bioresources production. Results showed that SMF had positive effects on value-added substances production. With 0.35 Tesla (T) SMF, the PSB biomass, protein, carotenoids, and bacteriochlorophyll concentration were promoted by 31.1%, 22.6%, 56.7%, and 73.1% compared with the control group, respectively. Biomass yield finally reached 0.58 g biomass/g COD removal, which was promoted by 37.1%. The doubling time was shortened by 37.9% in 0.35 T group, showing that SMF can promote cell growth. With 0.35 T SMF, the intracellular NADH dehydrogenase and ATP synthase activities concentration increased by 23.4% and 29.1%, respectively, thus increased the ATP content by 38.0%. Succinic dehydrogenase activity concentration greatly increased by 609.0% at 48 hr, which potentially accelerated the tricarboxylic acid cycle and COD degradation as well as enhanced biomass production. PRACTITIONER POINTS: SMF promoted PSB bioresource production during wastewater treatment processing. Biomass, protein, carotenoids, and Bchl concentration were promoted by 31.1%, 22.6%, 56.7%, and 73.1%, respectively. PSB yield of 0.35 T group was promoted by 37.1% compared with the control group. SDH concentration of 0.35 T was promoted by 609.0% compared with the control group. Increased NADH and ATP synthase activity concentration by SMF enhanced energy metabolism.

Shortage of water, energy, and bioresources in the world has led to the exploration of new technologies that achieve resource recovery from wastewater, which has become a new sustainable trend. Photosynthetic non-sulfur bacteria (PNSB), the most ancient photo microorganism, not only treats different wastewater types, but also generates PNSB cells, which are non-toxic bioresources and containing many value-added products. These bioresources can be used as raw materials in the agricultural, food, and medical industries. Therefore, PNSB or PNSB-based wastewater resource recovery technology can be simultaneously used to treat wastewater and produce useful bioresources. Compared with traditional wastewater treatment, this technology can reduce CO2 emissions, promote the N recovery ratio and prevent residual sludge disposal or generation. After being developed for over half a century, PNSB wastewater resource recovery technology is currently extended towards industrial applications. Here, this technology is comprehensively introduced in terms of (1) PNSB characteristics and metabolism; (2) PNSB wastewater treatment and bioresource recovery efficiency; (3) the relative factors influencing the performance of this technology, including light, oxygen, strains, wastewater types, hydraulic retention time, on wastewater treatment, and resource production; (4) PNSB value-added bioresources and their generation from wastewater; (5) the scale-up history of PNSB technology; (6) Finally, the future perspectives and challenges of this technology were also analysed and summarised.

Periodic oxygen supplementation (A-O) strategy was proposed to improve pollutant removal and enhance bioresource production of photosynthetic bacteria (PSB). The A-O strategy obtained higher COD (91.4%) and NH4+-N (78.6%) removal compared with the non-oxygen supplementation (N-O) strategy, which was similar to the continuous oxygen supplementation (C-O) strategy. A-O strategy achieved the highest biomass concentration of 1338.5 mg/L. Bacteriochlorophyll and carotenoids concentration in the A-O strategy were 24.9–31.1% and 15.1–23.7% higher than those in the other two strategies; coenzyme Q10 concentration and content were 52.5% and 21.3% higher than that in the N-O strategy. The metabolomic analysis showed that the A-O strategy enhanced the tricarboxylic acid cycle after fumaric acid formation and β-alanine metabolism, then caused higher biomass accumulation. The A-O strategy reduced the inhibition of photophosphorylation by oxidative-phosphorylation and maintained both characteristics. Hence, A-O might be an economic strategy for enhancing pollutant removal and bioresource production in PSB-based wastewater treatment.

To overcome drug resistance caused by apoptosis deficiency in patients with non-small cell lung carcinoma (NSCLC), there is a need to identify other means of triggering apoptosis-independent cancer cell death. We are the first to report that isogambogenic acid (iso-GNA) can induce apoptosis-independent autophagic cell death in human NSCLC cells. Several features of the iso-GNA-treated NSCLC cells indicated that iso-GNA induced autophagic cell death. First, there was no evidence of apoptosis or cleaved caspase 3 accumulation and activation. Second, iso-GNA treatment induced the formation of autophagic vacuoles, increased LC3 conversion, caused the appearance of autophagosomes and increased the expression of autophagy-related proteins. These findings provide evidence that iso-GNA induces autophagy in NSCLC cells. Third, iso-GNA-induced cell death was inhibited by autophagic inhibitors or by selective ablation of Atg7 and Beclin 1 genes. Furthermore, the mTOR inhibitor rapamycin increased iso-GNA-induced cell death by enhancing autophagy. Finally, a xenograft model provided additional evidence that iso-GNA exhibited anticancer effect through inducing autophagy-dependent cell death in NSCLC cells. Taken together, our results demonstrated that iso-GNA exhibited an anticancer effect by inducing autophagy-dependent cell death in NSCLC cells, which may be an effective chemotherapeutic agent that can be used against NSCLC in a clinical setting.

A large-pore version of Mg-CUK-1, a water-stable metal-organic framework (MOF) with 1-D channels, was synthesized in basic water. Mg-CUK-1L has a BET surface area of 2896 m2 g-1 and shows stark selectivity for CO2 sorption over N2, O2, H2, and CH4. It displays reversible, multistep gated sorption of CO2 below 0.33 atm. The dehydrated single-crystal structure of Mg-CUK-1L confirms retention of the open-channel structure. The MOF can be loaded with organic molecules by immersion in hot melts, providing single crystals suitable for X-ray diffraction. trans-Azobenzene fills the channels in a 2 × 2 arrangement. Solid-state UV-vis spectroscopy reveals that azobenzene molecules undergo reversible trans-cis isomerization, despite being close-packed; this surprising result is confirmed by DFT-simulated UV-vis spectra.

A combined low-temperature-roasting and water-washing process is investigated as a hazard-free method to treat electrolytic manganese residue (EMR) and recover manganese. In this study, the phase transformation characteristics and a thermodynamics analysis of the low temperature roasting process of EMR are evaluated. In addition, the effects of temperature and time on the phase transformation of EMR in the roasting process and the washing characteristics of roasted EMR samples are also investigated. Results reveal that some unstable phases within EMR are transformed into more stable phases depending on the treatment time/temperature conditions used and EMR roasted for 60 min at 600 °C (R 60min/600°C) exhibit the highest rate of manganese recovery, 67.12 %. After 25 min of deionized water washing, the concentration of manganese in solution from R 60min/600°C material become stable, whereas after 6 washing cycles the concentration of manganese in the solution is < 0.005 g/L. The R 60min/600°C material with three wash cycles results in a manganese-water solution concentration that is suitable for use in electrolytic manganese metal production. Finally, toxicity leaching tests show that the concentrations of ions present in the leaching solution are all lower than the regulatory limits mandated by the Chinese Integrated Wastewater Discharge Standard GB 8978−1996.

Controlled partial decomposition of 2-selenonicotinic acid in the presence of Co2+ or Ni2+ resulted in the in situ formation of an unusual MOF based on triselenane ligands (RSeSeSeR) coordinated to M2+ centers as NSeN-pincers. Post-synthetic oxidation by treatment with aqueous H2O2 facilitates its solid-state conversion into a RSeO2− molecular coordination complex, which was tracked via powder X-ray diffraction studies and by single-crystal structural resolution of the final product.

A process for recycling spent LiCoO2 cathode material doped with Mn from spent LiCoO2 lithium-ion batteries is proposed in this paper. Based on the leachate obtained during calcination and water leaching, this report comprises precipitation thermodynamics analysis and separation experiments results. The results of precipitation thermodynamic analysis demonstrate that NH4HCO3 cannot achieve separation of Mn and Co in the water-leaching solution system, while using (NH4)2S2O8 can induce preferential oxidative precipitation of the Mn in the system at pH

Coenzyme Q10 (CoQ10) is extensively used in the fields of medicine, cosmetics, food, and health care due to its function as an adenosine triphosphate (ATP) synthesis promoter and antioxidant. In recent years, the market demand (about 988–1369 tons/year) and application potential of CoQ10 have expanded, so it is necessary to enhance CoQ10 production. Microbial synthesis has gradually become a promising and commercially viable CoQ10 production method because of microorganisms have a high CoQ10 content, they are widely available, and they are inexpensive to grow. Among the microorganisms able to produce CoQ10, purple non-sulfur bacteria (PNSB) are desirable and preferred because of their ability of resource recovery with high yield from wastewater and the great potential of scaling up. In this review, the pros and cons of CoQ10 production methods are described and compared. The advantages of CoQ10 production from PNSB are detailed and illustrated. The influence factors and corresponding regulation strategies are summarized to effectively increase CoQ10 production from PNSB. Based on production cost benefits and environmental sustainability profiles, a novel, cost-effective, and environmental-friendly conversion route for CoQ10 production from non-toxic wastewater by using PNSB is proposed. By using this novel route, the nutrients from wastewater are converted into PNSB biomass, which contains various value-added products (CoQ10, carotenoids, bacteriochlorophyll, 5-aminolevulinic acid, and protein), carbohydrates and metal elements. The cost of light, medium provisions, and temperature control can be reduced or saved. In addition, no fermentation residual broth was produced, and clean water can be obtained. Moreover, existing problems, such as the purity of CoQ10 products derived from wastewaters and the CoQ10 extraction method are analyzed. The perspectives of future research are also proposed to promote the development of CoQ10 production using PNSB.

China has the largest output of electrolytic manganese metal (EMM), accounting for more than 98% of the world’s total annual production. Meanwhile, it has also caused serious environmental pollution and damage, among which the main pollutant is electrolytic manganese residue (EMR). EMR contains a large amount of NH4+-N, Mn, Mg, and other elements such as soluble sulphate, SeO2, and heavy metal elements. The unmanaged stockpiled EMR generally exposed to open air not only causes serious pollution in the surrounding surface water, groundwater, soil, air, and ecosystems, but also poses a serious threat to the health and survival of the residents in the surrounding area. For the EMM industry to support development and human society, the treatment and disposal of EMR must become more sustainable. This review provides a detail on the origin, main phase compositions, hazardous components of EMR, and status quo of hazard-free treatment and resource utilisation of EMR in the last 30 years. In particular, this study systematically summarizes applicability of different type of technologies to hazard-freely treat and utilize EMR, including valuable elements recovery, stabilisation/solidification and electrokinetic remediation, building materials, wastewater treatment materials, soil amendments, and other functional materials. In addition, the advantages and disadvantages of these technologies have also been scientifically evaluated. At the end of the review, existing challenges as well as future prospects of hazard-free treatment and resource utilisation of EMR are also discussed.

Generating or recycling water and resources from wastewater other than just treating wastewater is one of the most popular trends worldwide. Photosynthetic bacteria (PSB) wastewater treatment and resource recovery technology is one of the most potential methods. PSBs are non-toxic and contain lots of value-added products that can be utilized in the agricultural and food industries. They are effective to degrade pollutants and synthesize useful biomass, thus realizing wastewater treatment, bioresource production, and eliminating waste sludge. If all the nutrients in wastewaters could be bio-converted by PSB, then pollutant reductions and economic benefits would be achieved. This review paper firstly describes and summarizes this technology, including PSBs classification, metabolism, and the market application. The feasibility, technical procedures, bioreactors, pollutant removal, and bioresource production are also summarized, compared and evaluated. Issues that concern the advantages and industrialization of this technologies at the plant scale are also discussed.

LiCoO2 lithium-ion batteries are disposed once their life cycle comes to an end, by which large amounts of extremely harmful heavy metals and organic compounds are released into the environment. Further, the spent LiCoO2 cathode material from spent lithium-ion batteries contains numerous high-grade metals with a high recovery value, such as Li, Co and Mn. Hence, a clean and efficient process is proposed in this research for recovery of spent LiCoO2 cathode material via low-temperature (NH4)2SO4 calcination and water-leaching.The calcination temperature range between 445.87 and 677.48 °C is determined from analysis of the TG-DTA curve obtained with n (2Li + Co + Mn): n (NH4)2SO4 of molar ratio = 1:1. The sample calcined under conditions of calcination temperature of 600 °C, calcination time of 45 min and an (NH4)2SO4 excess of 1.2 exhibits optimal water-leaching efficiencies of the Li, Co and Mn elements, which are 99.50%, 98.53%, and 94.41%, respectively. Reaction mechanisms of the low-temperature calcination process are investigated with both SEM and XRD analyses of the differently prepared samples and their residues following water-leaching. Results show that the calcination of spent LiCoO2 cathode material with (NH4)2SO4 is a liquid-solid reaction with the spent cathode material particles being gradually eroded and consumed from the outer layer. In addition, the presence of free high-energy H+ released by the decomposition of NH4+ generated by molten (NH4)2SO4 plays a leading role in the whole calcination process, the structure of LiCoO2 and LiMn2O4 are broken down before eventually being converted into soluble sulfate salts.

Photosynthetic bacteria (PSB), used as fish feed and as raw materials for producing bio-active substances, are normally cultivated in fermenter using culture medium. This work investigated a novel, cleaner PSB production method using non-toxic organic wastewater as culture medium in photobioreactors (PBRs). The scale was enlarged from lab to bench and finally to pilot scale. Results showed that brewery wastewater with nitrogen supplement could substitute traditional culture medium with a comparable biomass output. At the lab scale, biomass production reached 1886.9 mg/L. Plexiglass cylindrical PBRs with mechanical agitation were selected to ensure good mixing to avoid the biomass wall-attachment. Finally, the scale was successfully enlarged 667-fold and the reactor was steadily operated outdoors for 80 days without temperature control and artificial light at the pilot scale. The biomass, protein, carotenoids, bacteriochlorophyll and Coenzyme Q10 values reached 1786.7, 1014.4, 4.9, 23.0, and 67.3 mg/L with a biomass yield of 0.53 g/g-COD-removal, respectively. PSB cells generated from brewery wastewater exhibited no acute toxicity. Culturing PSB with non-toxic wastewater can reduce the cost of culture medium, eliminate the necessity of fermentation broth treatment, and partially saves the cost of wastewater treatment. The challenges/practical barriers, such as chronic toxicity and management, should be further studied. The findings in this study might lead to the establishment of a cleaner PSB production technology with no residual liquid and wastewater resourcization.

In this paper, a calcination-leaching method by using CaCl2 and H2SO4 to recover alumina from coal fly ash (CFA) is developed. The process conditions including the parameters of CaCl2 content, calcination temperature and time, acid concentration and leaching time are studied. Heat treatment under 900°C for 1 h of the ash with 80 wt.% CaCl2 significantly enhances the alumina leachability (>96.6%) in comparison with the directing acid-leaching (2.31-4.78%) method. The recovery rate increases dramatically with the increasing of CaCl2 content from 20% to 80%, and a H2SO4 leaching time from 10 minutes to 1 hour as well, but it remains near constantly as the increasing of CaCl2 dosage >80% or acid-leaching time >1 h. The reaction mechanism is studied by X-ray diffraction (XRD) analysis to determine the crystalline phases change. The results indicate that quartz, mullite and amorphous phases have been destroyed after calcination with CaCl2 and transformed to gehlenite, calcium aluminum silicate, andradite, wollastonite and mayenite, which are susceptible to acid leaching. The mineralogical characteristics of roasted clinker indicate that molten CaCl2 can promote the incorporation of Ca into silica and silicates and result in the progressive susceptibility to acid attack. The potential chemical reactions during calcinating and leaching processes are also studied via chemical equations. The reuse and resource of coal fly ash can reduce the environmental impact of ash heap and the heavy metal pollution to the surrounding environment.

Eleven known caged polyprenylated xanthones 1–11 were isolated from the resin of Garcinia hanburyi Hook. f., and their structures were identified by their MS, NMR and UV spectra. These xanthones showed significant cytotoxicities against four human cancer cell lines (HeLa, A549, HCT-116, and HepG-2) and strong inhibition against the proliferation of the HUVEC cell line in vitro by the MTT method. Furthermore, in an in vivo zebrafish model, xanthones 3 (morellic acid), 7 (gambogenin) and 9 (isogambogenic acid) showed comparable antiangiogenic activities with less toxicities than xanthone 1 (gambogic acid), as evaluated by death and heart rates of treated zebrafish. Xanthone 7 exhibited antiangiogenic activity with no toxicity at concentrations ranging from 8 µM to 16 µM. Meanwhile, xanthones 1, 3, 7 and 9 strongly inhibited the migration of HUVEC at a low concentration of 0.5 µM in HUVEC cell migration assay in vitro. Taken together, these findings strongly suggest that xanthone 7 might be a novel angiogenesis inhibitor.

Isogambogenic acid (iso-GNA) is a well-known herbal medicine extracted from Garcinia hanburyi. Although it is thought to have anti-tumour effects, its function is still unknown. This study carried out in vitro and in vivo evaluations of the anti-tumour and anti-angiogenic activity of iso-GNA and underlying mechanisms. A standard methyl thiazolyl tetrazolium assay showed that iso-GNA was more effective in inhibiting the proliferation of human umbilical vascular endothelial cells than A549 cancer cells. Iso-GNA demonstrated potent anti-angiogenic activity and low toxicity at appropriate concentrations in zebrafish embryos. In a xenograft nude mouse model of lung tumour, iso-GNA effectively inhibited tumour growth and tumour angiogenesis. Iso-GNA suppressed neovascularization of implanted matrigel plugs in vivo and inhibited vascular endothelial growth factor (VEGF)-induced microvessel sprouting from mouse aortic rings ex vivo. Iso-GNA inhibited VEGF-induced migration, invasion, and tube formation in vitro and affected cytoskeletal rearrangement in human umbilical vascular endothelial cells. The results show that iso-GNA suppressed angiogenesis-mediated tumour growth by targeting VEGFR2, Akt, mitogen-activated protein kinase, Rho GTPase, vascular endothelium-cadherin, and focal adhesion kinase signalling pathways. Together, these data suggest that iso-GNA inhibits angiogenesis and may be a viable drug candidate in anti-angiogenesis and anti-cancer therapies.

Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 were prepared by the hydrothermal technique with alkali-treated H-ZSM-5 zeolite as the source and characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, N2 adsorption-desorption measurement and NH3 temperature-programmed desorption. The catalytic performances for the methanol dehydration to dimethyl ether over H-ZSM-5/MCM-41 were evaluated. Among these catalysts, H-ZSM-5/MCM-41 prepared with NaOH dosage (nNa/nSi) varying from 0.4 to 0.47 presented excellent catalytic activity with more than 80% methanol conversion and 100% dimethyl ether selectivity in a wide temperature range of 170–300 °C, and H-ZSM-5/MCM-41 prepared with nNa/nSi = 0.47 showed constant methanol conversion of about 88.7%, 100% dimethyl ether selectivity and excellent lifetime at 220 °C. The excellent catalytic performances were due to the highly active and uniform acidic sites and the hierarchical porosity in the micro-mesoporous composite molecular sieves. The catalytic mechanism of H-ZSM-5/MCM-41 for the methanol dehydration to dimethyl ether process was also discussed.

In this study, we reported millepachine (MIL), a novel chalcone compound for the first time isolated from Millettia pachycarpa Benth (Leguminosae), induced cell cycle arrest and apoptosis in human hepatocarcinoma cells in vitro and in vivo. In in vitro screening experiments, MIL showed strong antiproliferation activity in several human cancer cell lines, especially in HepG2 cells with an IC50 of 1.51 µM. Therefore, we chose HepG2 and SK-HEP-1 cells to study MIL's antitumor mechanism. Flow cytometry showed that MIL induced a G2/M arrest and apoptosis in a dose-dependent manner. Western blot demonstrated that MIL-induced G2/M arrest was correlated with the inhibition of cyclin-dependent kinase 1 activity, including a remarkable decrease in cell division cycle (cdc) 2 synthesis, the accumulation of phosphorylated-Thr14 and decrease of phosphorylation at Thr161 of cdc2. This effect was associated with the downregulation of cdc25C and upmodulation of checkpoint kinase 2 in response to DNA damage. MIL also activated caspase 9 and caspase 3, and significantly increased the ratio of Bax/Bcl-2 and stimulated the release of cytochrome c into cytosol, suggesting MIL induced apoptosis via mitochondrial apoptotic pathway. Associated with those effects, MIL also induced the generation of reactive oxygen species. In HepG2 tumor-bearing mice models, MIL remarkably and dose dependently inhibited tumor growth. Treatment of mice with MIL (20mg/kg intravenous [i.v.]) caused more than 65% tumor inhibition without cardiac damage compared with 47.57% tumor reduction by 5mg/kg i.v. doxorubicin with significant cardiac damage. These effects suggested that MIL and its easily modified structural derivative might be a potential lead compound for antitumor drug.

Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 were prepared by the hydrothermal technique with alkali-treated H-ZSM-5 zeolite as source and characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, N 2 adsorption and desorption measurement, and NH 3 temperature-programmed desorption. The effect of SiO 2 /Al 2 O 3 ratio in H-ZSM-5 on the structure, surface acidity and catalytic performances of H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether were investigated. H-ZSM-5/MCM-41 prepared with H-ZSM-5 of different SiO 2 /Al 2 O 3 ratios as source in which H-ZSM-5 nanoparticles were uniformly dispersed in MCM-41 matrix, had well-ordered micropores and mesopores. The acid amount and strength of moderate acid sites ( T P1 ) of H-ZSM-5/MCM-41 can be controlled by the SiO 2 /Al 2 O 3 ratio in H-ZSM-5 during the range from 25 to 50. Among these catalysts, H-ZSM-5/MCM-41 presented a comparable catalytic activity to the corresponding pure H-ZSM-5 and 100% dimethyl ether selectivity in a wider temperature range than the corresponding pure H-ZSM-5. The excellent catalytic performances were due to the highly active and uniform strong acid sites and the hierarchical porosity in the micro-mesoporous composite molecular sieves. The catalytic mechanism of H-ZSM-5/MCM-41 for the methanol dehydration to dimethyl ether was also discussed.

In general, simultaneously separation and purification of components with a broad polarity range from traditional Chinese medicine (TCM) is a challenge by an ordinary high-speed counter-current chromatography (HSCCC) method. In this paper, we describes a rapid and efficient separation method of combining three-step gradient elution and two-step flow-rate gradient elution using high-performance counter-current chromatography (HPCCC) to separate 8 diterpene compounds simultaneously within 80 min in a single run from the alcohol extract of Pseudolarix kaempferi Gordon. This separation process produced 166 mg pseudolaric acid B O-β- d -glucopyranoside (PABGly), 152 mg pseudolaric acid C (PAC), 8 mg deacetylpseudolaric acid A (deacetylPAA), 5 mg pseudolaric acid A O-β- d -glucopyranoside (PAAGly), 484 mg pseudolaric acid B (PAB), 33 mg pseudolaric acid B methyl ester (PAB methyl ester), 10 mg pseudolaric acid A (PAA) and 18 mg pseudolaric acid H (PAH) from 1.0 g crude sample with purities of 98.6%, 99.6%, 92.3%, 92.2%, 99.2%, 99.4%, 98.3%, 91.0%, respectively. Our study indicates that the suitable combination of step-wise gradient elution and flow-rate gradient elution using HPCCC is an effective strategy to separate complex components from natural products.

Recycling counter-current chromatography (CCC) together with step-gradient CCC and medium-pressure liquid chromatography (MPLC) was employed to separate nine anthraquinone compounds from Cassia obtusifolia L. in this study. The results showed that recycling CCC is a powerful tool for compounds that are difficult to separate with common elution mode. CCC was the better option for crude material while MPLC had advantage for the final tuning. The combination of recycling CCC and MPLC could simplify the method exploring process in the separation process. The structures of these compounds were identified according to their mass spectra, by (1)H-NMR and compared with standard compounds.

Preparative separation of quinolone alkaloids in Evodia rutaecarpa (Juss.) Benth was conducted by high performance counter-current chromatography (HPCCC) with a pair of two solvent systems consisting of n-hexane-methanol-water-acetic acid (2:1:1:0.2, v/v) and (5:4:2:0.1, v/v). Consequently, 31.78 mg 1-methyl-2-nonyl-4 (1H)-quinolone (I), 59.25 mg 1-methyl-2-(6-undecenyl)-4 (1H)-quinolone (II), 333.27 mg evocarpine (III), 101.13 mg 1-methyl-2-(6,9-pentadecadienyl)-4(1H)-quinolone (IV), 132.17 mg dihydroevocarpine (V), and 86.99 mg 1-methyl-2-(10-pentadecenyl)-4(1H)-quinolone (VI) were obtained from 1.3 g of the crude extract. The structures of these compounds were identified by mass spectrometer (MS), nuclear magnetic resonance (1H NMR and 13C NMR).

Aimed at the defect of black spots, hair, bubbles in medical PP infusion, infusion defect detection system based on machine vision is proposed. Firstly, r design the mechanical actuators, electrical control, and image acquisition system, then use reverse PM diffusion algorithm to enhance the defect area, extracting this area by difference after binarization, and filter the image. Secondly, SVM is used to classify defects and the defective area automatically. Meanwhile, in order to improve the performance of the classifier, the paper selected the best classification parameters based cross validation. The results show that the method is high detection accuracy and requires less training samples, applies to different defect types with accuracy rate of 95%.

To overcome drug resistance caused by apoptosis deficiency in patients with non-small cell lung carcinoma (NSCLC), there is a need to identify other means of triggering apoptosis-independent cancer cell death. We are the first to report that isogambogenic acid (iso-GNA) can induce apoptosis-independent autophagic cell death in human NSCLC cells. Several features of the iso-GNA-treated NSCLC cells indicated that iso-GNA induced autophagic cell death. First, there was no evidence of apoptosis or cleaved caspase 3 accumulation and activation. Second, iso-GNA treatment induced the formation of autophagic vacuoles, increased LC3 conversion, caused the appearance of autophagosomes and increased the expression of autophagy-related proteins. These findings provide evidence that iso-GNA induces autophagy in NSCLC cells. Third, iso-GNA-induced cell death was inhibited by autophagic inhibitors or by selective ablation of Atg7 and Beclin 1 genes. Furthermore, the mTOR inhibitor rapamycin increased iso-GNA-induced cell death by enhancing autophagy. Finally, a xenograft model provided additional evidence that iso-GNA exhibited anticancer effect through inducing autophagy-dependent cell death in NSCLC cells. Taken together, our results demonstrated that iso-GNA exhibited an anticancer effect by inducing autophagy-dependent cell death in NSCLC cells, which may be an effective chemotherapeutic agent that can be used against NSCLC in a clinical setting.

Gambogic acid (GA) is in a phase II clinical trial as an antitumor and antiangiogenesis agent. In this study, 36 GA derivatives were synthesized and screened in a zebrafish model to evaluate their antiangiogenic activity and toxicity. Derivatives 4, 32, 35, 36 effectively suppressed the formation of newly grown blood vessels and showed lower toxicities than GA as evaluated by zebrafish heart rates and mortalities. They also exhibited more potent migration and HUVEC tube formation inhibiting activities than GA. Among them, 36 was the most potent one, suggesting that it may serve as a potential new antiangiogenesis candidate with low toxicity. Additionally, 36 showed comparable antiproliferative activity to HUVECs and five tumor cell lines but low cytotoxicity to LO2 cells.

The aim of this study is to investigate the cytotoxic and apoptotic effects of constituents from the seeds of Millettia pachycarpa Benth. Fourteen compounds (1–14) including one novel chalcone (10) were isolated as active principles from Chinese herbal medicine M. pachycarpa Benth. Their structures were identified by using spectroscopic methods. All isolates were then evaluated for their cytotoxic effects against several cancer cell lines (HepG2, C26, LL2 and B16) with cisplatin as a positive control. And their apoptosis-inducing effects were tested against HeLa-C3 cells with taxol as a positive control. Both studies showed that compounds 1, 2, 7 and 10 demonstrated significant cytotoxic and apoptotic effects against cancer cells. Moreover, in the apoptosis assay the novel chalcone (10) showed strong apoptosis inducing effects at a concentration of 2 μM within 36 h. It was found to be the most potent apoptotic inducer of the compounds isolated from M. pachycarpa Benth.

Recycling counter-current chromatography (CCC) together with step-gradient CCC and medium-pressure liquid chromatography (MPLC) was employed to separate nine anthraquinone compounds from Cassia obtusifolia L. in this study. The results showed that recycling CCC is a powerful tool for compounds that are difficult to separate with common elution mode. CCC was the better option for crude material while MPLC had advantage for the final tuning. The combination of recycling CCC and MPLC could simplify the method exploring process in the separation process. The structures of these compounds were identified according to their mass spectra, by (1)H-NMR and compared with standard compounds.

The elution–extrusion counter-current chromatography (EECCC) method was firstly developed by Berthod in 2003 and has been used in natural products separation in recent years. The advantages of this method have been well documented such as reducing the separation time and solvent consumption. In the EECCC method, the time point of the extrusion step is very important during the whole separation process as it directly affects the resolutions, separation time and solvent consumption. However, how to choose a suitable time point to perform the extrusion step without decreasing the resolution has not been studied yet. In the present study, a strategy for systematically calculating the time point for extrusion was developed in theory and five bioactive compounds from the extract of Dendrobium chrysototxum Lindl. were separated and compared using normal CCC and EECCC method. Our results demonstrated that the accurate time point to perform the extrusion could be calculated and reduced both separation time and solvent consumption without losing separation performance. Using this EECCC method, five bioactive compounds were separated and purified with high purity. The separation time and solvent consumption were decreased from 200 min to 100 min and 5–2.5 L during the separation process while the resolutions were still acceptable. Finally, 63 mg, 48 mg, 97 mg, 162 mg and 43 mg of hydroxyl phenanthrenes and bibenzyls with the purity of 98.7%, 98.0%, 98.2%, 99.0% and 98.7%, respectively were isolated from 1.2 g crude extract of D. chrysototxum Lindl. initially purified by column chromatography in one step separation. The purities of compounds were determined by HPLC. Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and NMR.

Recently, intermittent counter-current extraction (ICcE) has been developed and shown its advantage in improving resolution between targeted compounds. However, how to choose suitable parameters to increase the throughput has not been systematically studied yet. In present work, we first calculated theoretically the conditions to carry out ICcE elution mode. Then, honokiol and magnolol were separated as model compounds using ICcE elution mode to confirm our conclusion. After parameters like sample concentration and sample feed were optimized in analytical high-performance counter-current chromatography (HPCCC), the separation process was scaled up to preparative HPCCC successfully. 12.8 g honokiol and 16.1 g magnolol were separated from 30 g mixture with purities of 98.6% and 93.7%. And the throughput of target isolation of ICcE elution mode was at least 3.75× higher than isocratic elution mode with the same HPCCC instruments. Our results confirmed our theory calculation and demonstrated the enormous potential of ICcE on preparative separation of binary mixture.

This paper describes the application of high-performance counter-current chromatography (HPCCC) as a fast, useful and economic alternative for the separation and purification of seven honokiol derivatives (two of them are isomers), which were synthesized by a one-pot procedure. Five honokiol derivatives were successfully separated by n-hexane-ethyl acetate-methanol-water solvent system at three different volume ratios in a step-gradient elution. Two derivatives were obtained through a cycle elution mode. The whole separation process produced 366.3 mg, 323.6 mg, 242.8 mg, 216.2 mg, 203.5 mg, 185.8 mg and 279.3 mg of 3'-formylhonokiol (1), 2'-methoxy-3'-formylhonokiol (2), 2'-methoxyhonokiol (3), 4-methoxyhonokiol (4), 3',5-diformylhonokiol (5), 2',4-dimethoxy-3'-formylhonokiol (6) and 2',4-dimethoxyhonokiol (7) from crude sample of 3 g with purities of 98.7%, 99.3%, 98.6%, 98.2%, 99.0%, 98.4% and 99.2%, respectively. The purities and structural identification were determined by HPLC, (1)H NMR, (13)C NMR and mass spectroscopy.