A novel biochar composite derived from oil-based drill sludge and cuttings: Structural characterization and electrochemical properties.

How to dispose of large quantities of hazardous shale gas drilling waste is an important worldwide problem facing the oil and gas industry. In this study, we report an environmentally friendly and low energy consumption approach (carbonization followed by activation) to convert oil-based drill sludge (OBDS) and oil-based drill cuttings (OBDCs) into biochar composites and investigate the effect of hydrofluoric acid (HF) acidification on them. The biochar composites were prepared using the OBDS, OBDCs, the mixtures of OBDS and OBDCs, and HF treatment the mixtures were named OS, OC, OSC, and OSC-HF, respectively. The characterization result of synthesized biochar composites indicated that the OSC had a larger specific surface area and a higher degree of graphitization. The composites mainly consisted of SiO2 and BaSO4, except for biochar. The OSC electrode exhibited the highest oxygen evolution potential (1.72 V vs Ag/AgCl) and the lowest charge transfer resistance compared with OS, OC, and OSC-HF electrodes, implying that SiO2 plays an important role in electrochemical performance. Using the OSC electrode as an anode, the chemical oxygen demand removal efficiency of the OBDS supernatant was 79.4 ± 0.95%. Further, the OSC electrode could maintain higher degradation efficiency and stability after the fifth reuse. The study provides a promising route for the proper disposal and resource utilization of OBDS and OBDCs and proposes a novel biochar compound as an electrode for the efficient treatment of wastewater. Moreover, this work highlights the important significance of the simultaneous resource utilization of waste and the treatment of wastewater using waste materials.

Fabrication and Characterization of a Novel Composite Magnetic Photocatalyst ß-Bi2O3/BiVO4/MnxZn1-xFe2O4 for Rhodamine B Degradation under Visible Light.

ß-Bi2O3/BiVO4/MnxZn1-xFe2O4 (BV/MZF) composite magnetic photocatalyst was first synthesized using the hydrothermal and calcination method. BV/MZF was a mesoporous material with most probable pore size and specific surface area of 18 nm and 17.84 m2/g, respectively. Due to its high saturation magnetization (2.67 emu/g), the BV/MZF composite can be easily separated and recovered from solution under an external magnetic field. The results of photo-decomposition experiments show that the decomposition rate of Rhodamine B (RhB) by BV/MZF can reach 92.6% in 3 h under visible light. After three cycles, BV/MZF can still maintain structural stability and excellent pollutant degradation effect. In addition, analysis of the photocatalytic mechanism of BV/MZF for RhB shows that the p-n heterojunction formed in BV/MZF plays a vital role in its photocatalytic performance. This work has potential application in the future for solving environmental pollution.

Preparation of non-sintered lightweight aggregates through co-mechanochemical treatment of oil-contaminated drill cuttings, circulation fluidized bed combustion fly ash, and quicklime.

This work investigates the feasibility of co-mechanochemical treatment of oil-contaminated drill cuttings (OCDC), circulation fluidized bed combustion (CFBC) fly ash, and quicklime to prepare non-sintered lightweight aggregates (NSLWAs). The NSLWAs with high cylinder compressive strength and low water absorption could be obtained under the condition of optimal water addition and appropriate steam-curing temperature, as well as steam-curing time. Co-mechanochemical treatment could enhance the pozzolanic reactivity of CFBC fly ash effectively, which is beneficial to the strength development of NSLWAs. Moreover, co-mechanochemical treatment also can degrade the petroleum hydrocarbon of OCDC, greatly reducing the leaching concentrations of total petroleum hydrocarbons (TPH) of NSLWAs. The final leaching concentrations of TPH are much lower than the requirements of Chinese National Standard GB 31571-2015. Graphical abstract.

Solidification of Municipal Solid Waste Incineration Fly Ash through Co-Mechanical Treatment with Circulation Fluidized Bed Combustion Fly Ash.

This study aims to explore the solidification performance of municipal solid waste incineration fly ash (MSWIFA) through co-mechanical treatment with circulation fluidized bed combustion fly ash (CFBCFA). The mineral characterization, physical properties, and leaching resistance of the solidified bodies are investigated by X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FT-IR), Thermogravimetry-differential thermal analysis (TG-DTA), compressive strength, porosity, and leaching test, respectively. C-S-H, ettringite (AFt), and Friedel's salt (FS) are the predominant hydrate products in the CFBCFA based solidified bodies, which are similar to the cement based solidified bodies. However, CFBCFA based solidified bodies exhibit higher compressive strength (36.7 MPa) than cement based solidified bodies (11.28 MPa), attributing to the three reasons: lower porosity and more compact internal structure of CFBCFA based solidified bodies; large amounts of Ca(OH)2 originating from MSWIFA are conducive to promoting the hydration reaction extent and compressive strength of the CFBCFA based solidified bodies; excessive Ca(OH)2 would cause compressive strength deterioration for the cement based solidified bodies. The heavy metals (Zn, Cu, Cr, Cd, and Pb) concentrations in the extraction solution of the CFBCFA based solidified bodies are far below the requirements of Chinese National Standard GB 5085.3-2007. The solidification of MSWIFA through co-mechanical treatment could be an ideal substitute for cement solidification technology.

Chemosynthesis pathway and bioactivities comparison of saponins in radix and flower of Panax notoginseng (Burk.) F.H. Chen.

ETHNOPHARMACOLOGICAL RELEVANCE: Panax notoginseng (Burk.) F.H. Chen is a well known medicinal plant. Its radix is used in the history while its flower is recently used for health care. In this study we compared chemical ingredients and bioactivities in cell culture for radix and flower of Panax notoginseng (Burk.) F.H. Chen. MATERIALS AND METHODS: The liquid chromatography-mass spectrometry system was applied to determine the contents of saponins in flower and radix of Panax notoginseng (Burk.) F.H. Chen. Transcription specific luciferase reporter assay and qPCR method for selected RNA were carried out to assess the impacts of flower and radix extract on the transcription signal pathways. RESULTS: The results of chemical analysis showed that the contents of saponins in flower and radix are very different: the contents of Rg1, Rb1, Re, R1, Rg3-20R, Rh1 and Rf in radix are abundant; in contrast, the contents of Rb3, Fc, Ft1, Rb2 and Rh2-20s in flowers are plentiful. There are substantial variations of those saponin contents from one batch vs another. Based on relative content of saponins, the chemosynthesis pathway of ingredients in radix and flower are proposed: for radix, both PPT (Protopanaxatriol) and PPD (Protopanaxadiol) type triterpenoids are involved, the main pathway is PPT→Rb1→Rg1→R1 or PPD→Rh2 20s→Rg3(20s)→Rd→Rb1; for flowers, only PPD is main passage with PPD→Rh2 (20s)→Rg3(20s)→Rd→Rb2→Fc. The results of signal transcription assays demonstrated that herb water extract of radix and flower had no significant influences on most of transcription activities. However, total saponins of radix and flower which have highly content of saponins were able to inhibit the inflammatory related transcriptional activities and their related mRNA expression of IFNα, TNFα, il-6 and TGFß as well as induce anti-oxygen NrF2 activities. In summary, although chemical ingredients and chemosynthesis pathway of flower and radix for Panax notoginseng (Burk.) F.H. Chen were different, these differences might not result in their differences of pharmacological activities.

A functional variant at miR-520a binding site in PIK3CA alters susceptibility to colorectal cancer in a Chinese Han population.

An increasing body of evidence has indicated that polymorphisms in the miRNA binding site of target gene can alter the ability of miRNAs to bind their target genes and modulate the risk of cancer. We aimed to investigate the association between a miR-520a binding site polymorphism rs141178472 in the PIK3CA 3'-UTR and the risk of colorectal cancer (CRC) in a Chinese Han population. The polymorphism rs141178472 was analyzed in a case-control study, including 386 CRC patients and 394 age- and sex-matched controls; the relationship between the polymorphism and the risk of colorectal cancer was examined. Individuals carrying the rs141178472 CC genotype or C allele had an increased risk of developing CRC (CC versus TT, OR (95% CI): 1.716 (1.084-2.716), P = 0.022; C versus T, OR (95% CI): 1.258 (1.021-1.551), P = 0.033). Furthermore, the expression of PIK3CA was detected in the peripheral blood mononucleated cell of CRC patients, suggesting that mRNA levels of PIK3CA might be associated with SNP rs141178472. These findings provide evidence that a miR-520a binding site polymorphism rs141178472 in the PIK3CA 3'-UTR may play a role in the etiology of CRC.

Effects of thermotherapy on Th1/Th2 cells in esophageal cancer patients treated with radiotherapy.

BACKGROUND: To investigate the effects of double radiofrequency hyperthermia on Th1/Th2 cells in esophageal cancer patients treated with radiotherapy. MATERIALS AND METHODS: 22 patients with esophageal cancer were divided into a radiotherapy group (10 cases) and a combined group (double radiofrequency hyperthermia combined with radiotherapy group, 12 cases). Both groups received conventional radiotherapy using a cobalt-60 therapy apparatus (TD60-66Gy/30-33F). Patients in the combined group also underwent double radiofrequency hyperthermia (2F/W, 8-10F). Before and after treatment, Th1, Th2, Tc1 and Tc2 cells in peripheral blood were determined with flow cytometry. RESULTS: In the radiotherapy group, Th1 cell contents before and after radiotherapy were 17.5 ± 5.26% and 9.69 ± 4.86%, respectively, with a significant difference (p<0.01). The Th1/Th2 ratio was significantly decreased from 28.2 ± 14.3 to 16.5 ± 10.4 (p<0.01). In the combined group, Th1 cell content before radiotherapy was 15.9 ± 8.18%, and it increased to 18.6 ± 8.84 after radiotherapy (p>0.05), the Th1/Th2 ratio decreasing from 38.4 ± 36.3 to 28.1 ± 24.0 (p>0.05). Changes in Th2, Tc1 and Tc2 cell levels were not significant in the two groups before and after therapy (p>0.05). CONCLUSIONS: Double radiofrequency hyperthermia can promote the conversion from Th2 to Th1 cells, and regulate the balance of Th1/Th2 cells.

Antitumor agents 294. Novel E-ring-modified camptothecin-4ß-anilino-4'-O-demethyl-epipodophyllotoxin conjugates as DNA topoisomerase I inhibitors and cytotoxic agents.

Two conjugates (1 and 2) of camptothecin (CPT) and 4ß-anilino-4'-O-demethylepipodophyllotoxin were previously shown to exert antitumor activity through inhibition of topoisomerase I (topo I). In this current study, two novel conjugates (1E and 2E) with an open E-ring in the CPT moiety were first synthesized and evaluated for biological activity in comparison with their intact E-ring congeners. This novel class of CPT-derivatives exhibits its antitumor effect against CPT-sensitive and -resistant cells, in part, by inhibiting topo I-linked DNA (TLD) religation. An intact E-ring was not essential for the inhibition of TLD religation, although conjugates with an open E-ring were less potent than the closed ring analogs. This lower religation potency resulted in decreased formation of protein-linked DNA breaks (PLDBs), and hence, less cell growth inhibition. In addition to their impact on topo I, conjugates 1E, 2, and 2E exhibited a minor inhibitory effect on topo II-induced DNA cleavage. The novel structures of 1E and 2E may present scaffolds for further development of dual function topo I and II inhibitors with improved pharmacological profiles and physicochemical properties.

Cellular damage and apoptosis along with changes in NF-kappa B expression were induced with contrast agent enhanced ultrasound in gastric cancer cells and hepatoma cells.

BACKGROUND: The effect of cell injury and apoptosis induced by ultrasound with contrast agent has been verified. Contrast agent enhanced apoptosis and expression of genes that related to apoptosis and are responsive to ultrasound. This effect was associated with reactive oxygen species (ROS) production induced by the sonochemical reaction, as reported in previous studies. NF-kappa B may be one of the factors involved in oxidizing reactions or modulation during the process of ultrasound inducing apoptosis. RESULTS: Ultrasound irradiated gastric cancer cells (SGC7901 cell line) and hepatocellular carcinoma cells (SMMC-771 cell line) cultured in medium containing contrast agent. Significant cellular damage and apoptosis were observed in the bath cells incubated for 24 hours following 120 seconds ultrasonic irradiation. I kappa B alfa expression synchronously increased in the treatment groups of both the cell lines, and the down-regulated expression of NF-kappa B influenced its-regulated expression of genes that related to apoptosis. Production of intracellular ROS and elevation of NF-kappa B level occurred after incubation of the cells for 1 hour following ultrasonic treatment. CONCLUSIONS: Our result suggested that contrast agent enhanced the biological effect of ultrasound. Their reaction might stimulate the transitory expression of NF-kappaB, and subsequent elevation in IκBalfa expression could lead to the apoptosis of SGC7901 cells and SMMC-771 cells.

Physiological response of Cu and Cu mine tailing remediation of Paulownia fortunei (Seem) Hemsl.

The physiological responses and Cu accumulation of Paulownia fortunei (Seem) Hemsl. were studied under 15.7-157 µmol L(-1) Cu treatments in liquid culture for 14 days; the impacts of Cu concentration in the seedlings were evaluated under Cu mine tailing culture with acetic acid and EDTA treatment for 60 days. Results showed that the concentrations of Chl-a, Chl-b and Carotenoids significantly increased (p < 0.05) at 15.7-78.7 µmol L(-1)Cu treatment and significantly decreased at 157 µmol L(-1) treatment after 14 days of Cu exposure. The activities of superoxide dismutase (SOD) and catalase (CAT) significantly increased as Cu levels were enhanced and the activities of both SOD and CAT under 157 µmol L(-1) Cu stress were 2.9 and 1.9 times higher than that of control, respectively. The concentrations of proline and soluble sugars in the leaves of P. fortunei significantly increased as the Cu concentrations were elevated. Cu concentrations in roots, stems and leaves of P. fortunei increased significantly as Cu levels increased and reached 1911, 101 and 93 µg g(-1) dry weights (DW) at 157 µmol L(-1) Cu treatment, respectively. The seedlings of P. fortunei cultivated in Cu tailing experienced unsuccessful growth and loss of leaves in all treatments due to poor nutrition of the Cu tailing. The dry weight of P. fortunei increased under all the treatments of acetic acid after 60 days exposure. However, dry weight significantly decreased under both levels of EDTA. The Cu concentrations increased significantly in roots and decreased in leaves when each was treated with both concentrations of acetic acid. The Cu concentrations in the roots, stems and leaves increased significantly, and the concentrations of Cu in the stems and leaves under the treatment of 2 µmol L(-1) EDTA reached 189.5 and 763.1 µg g(-1) DW, respectively. The result indicated that SOD, CAT, proline and soluble sugars played an important role in coping with the oxidative stress of copper. Acetic acid could promote growth and EDTA at the experimental levels, which could also enhance Cu absorption and translocation into the stems and leaves of P. fortune. Furthermore, acetic acid and EDTA could be rationally utilized in Cu-contaminated soil.

Local effects of retrovirally transduced endostatin-expressing human umbilical cord blood CD34+ cells on transplanted malignancy in a mouse model of hepatic cancer.

Antiangiogenesis has been exploited as an effective approach to inhibit the growth of solid tumors. This technique has been evaluated using various vectors in several xenograft animal models to demonstrate the efficacy of endostatin gene therapy against cancer growth. However, previous studies have not examined the use of cord blood CD34+ cells as endostatin-producing cells for gene therapy against hepatoma. This exploratory study was done to investigate the local effects of CD34+ cells transduced with the endostatin gene on a mouse xenograft tumor model. The human endostatin gene was transferred into CD34+ cells using the recombinant retrovirus plasmid, pLncx/endo. Expression was verified by RT-PCR and Western blot analyses, confirming the stable expression and secretion of endostatin from the transferred CD34+ cells. The proliferation of vascular endothelial cells was evaluated by MTT assay and found to decrease by about 59.9% when treated with the supernatant of cultured transfected CD34+ cells in vitro. These genetically modified cord blood CD34+ cells were implanted intratumorally and tumor regression was evaluated after 2 weeks. The average size of a xenograft tumor in the CD34+/endo group was reduced 31.39% compared to that in the untreated mice or those transplanted with CD34+ cells transduced with a control vector. The microvascular density of the tumor decreased 62.45% in the treated group. The expression of proliferation cell nuclear antigen (PCNA) also decreased significantly in the treated group. Moreover, the apoptotic index (AI) of tumors, as evaluated by TUNEL staining, was significantly enhanced in the treatment group. Our findings indicate that angiogenesis of the xenograft tumor in mice may be inhibited by local administration of genetically modified CD34+ cells expressing the endostatin gene. This novel approach may lead to a new direction of cell-based gene therapy for malignancy.

Selective inhibition of tumor microvascular permeability by cavtratin blocks tumor progression in mice.

Tumor vasculature is hyperpermeable to macromolecules compared to normal vasculature; however, the relationship between tumor hyperpermeability and tumor progression is poorly understood. Here we show that a cell-permeable peptide derived from caveolin-1, termed cavtratin, reduces microvascular hyperpermeability and delays tumor progression in mice. These antipermeability and antitumor actions of cavtratin occur in the absence of direct cytostatic or antiangiogenic effects. Cavtratin blocks microvascular permeability by inhibiting endothelial nitric oxide synthase (eNOS), as the antipermeability and antitumor actions of cavtratin are markedly diminished in eNOS knockout mice. Our results support the concepts that hyperpermeability of tumor blood vessels contributes to tumor progression and that blockade of eNOS may be exploited as a novel target for antitumor therapy.

Ultrasonic aspiration hepatectomy for 136 patients with hepatocellular carcinoma.

AIM: To study the operative injury, post-operative complications, the hospitalization time, the post-operative survival rate of ultrasonic aspiration hepatectomy with a domestic new type of ultrasonic surgical device in comparison with that of conventional techniques of hepatectomy. METHODS: A total 136 patients with hepatocellular carcinoma (HCC, including 12 patients in 1991 and 124 consecutive patients from July 1995 to December 2000) underwent ultrasonic aspiration in liver resection (group T) and 179 HCC patients received conventional hepatectomy during the corresponding period (group C). The results of the two groups were compared statistically. RESULTS: There was no significant difference in the mean operation time between group T (152+/-11 min) and C (144+/-11 min). No operation or hospital death occurred in both groups. In group T, the mean volumes of bleeding (463+/-15 ml) and blood transfusion (381+/-12 ml) were markedly less than those in group C (557+/-20 ml, and 507+/-18 ml, respectively, P<0.05). The mean hospitalization time of group T (8.9+/-0.6 d) was markedly shorter than that of group C (11.7d+/-0.6 d) (P<0.05). The incidence of complications in group T was markedly lower than in group C, post-operative jaundice occurred in 4/136 and 31/179, respectively (P<0.05), liver failure in 0/136 and 2/179, cholorrhea in 0/136 and 6/179, hydrothorax in 21/136 and 39/179 (P<0.05), ascices in 9/136 and 54/179, respectively (P<0.05 ). There was no significant difference in the 1-year survival rate between the two groups (P>0.05), while the 3-year survival rate of group T (64.2 % ) increased markedly as compared with that of group C (55.7 %) (P<0.01). CONCLUSION: The ultrasonic aspiration hepatectomy with a domestic new type of ultrasonic surgical device could evidently reduce the operative injury and post-operative complications, shorten the hospitalization time and prolong the survivals of HCC patients.

Clinical and experimental study on regional administration of phosphorus 32 glass microspheres in treating hepatic carcinoma.

AIM:To study the therapeutical effectiveness, dosage range and toxic adverse effects of domestic phosphorus 32 glass microsphere and evaluate its clinical significance.METHODS:I.Fifty two BALB/c tumor bearing male nude mice were allocated into treatment group(n = 38) and control group(n = 14). In the former group different doses of (32) P-GMS were injected into the tumor mass, while in the latter (31)P-GMS or no treatment was given. The experimental animals were sacrificed in batches, and then the tumors and their nearby tissues were examined by light and electron microscopy.II. Through selective catheterization of hepatic artery, (32)P-GMS was infused to 5 healthy domestic pigs in a dosage equivalent to the therapeutic dose for human being, and (31)P-GMS was infused to another 5 healthy domestic pigs. Two pigs infused with contrast medium served as whole course blank controls. One pig from each group was surrendered to euthanasia at week 1, 4, 8 and 16 respectively. The ultrastructural histopath ological changes in liver tissues taken from different sites were evaluated semiquan titatively. III. One hundred and twenty seven times of (32)P-GMS intrahepatic artery interventional therapies were performed on 93 patients with hepatic carcinoma, including 79 cases of primary hepatic carcinoma and 14 cases of secondary hepatic carcinoma. (32)P-GMS (n = 30), and group B,(32)P-GMS and half dose of trans hepatic artery embolization (TAE)(n = 49), and 18 patients with HCC by TAE only as control group C. Fourteen patients with secondary hepatic carcinoma were treated in the same way as group B or C.RESULTS:I.Comparing with the control group, the treatment group of tumor bearing nude mice attained the tumor inhibition rates of 59.7%-93.7% (F = 579.62 P < 0.01) at 14d. At an absorbed dose of 7320Gy, the tumor cells were completely destroyed. When the absorbed doses ranged from 1830Gy to 3660Gy, most of the tumor cells showed the evidences of injury or necrosis, but there appeared some well differentiated tumor cells and enhanced effect of the autoimmunocytes. At an absorbed dose of 366Gy or less, some tumor cells still remained active prolix-ferative ability. The definite anticancer effect appeared as early as 3d after intratumoral injection of (32)P-GMS.II. The cumulative amount of (32) P-GMS in the target tissue after trans hepatic artery instillation attained more than 90% of the total dose administrated. Semiquantitative analysis of ultrastructral morphology in the experimental group showed no statistical difference between the nuclear abnormality (N(abn)) and mitochondrial variability (M(var)) at week 1 or 2, but revealed prominent difference (X(2) = 6.70-9.68, P < 0.01, X(2) = 65.09-115.09, P <0.001) as compared with those in the other groups. In the experimental group the N abn in tissues showed no significant difference between week 8 and week 16. No apparent changes were found in the stomach, spleen, kidney and lung tissues of the experimental pigs. III. The therapeutical results of HCC patients in group A were closely approximated to those of group C, no hematological toxic side effects were noted, and the systemic reaction was mild. In some patients 2mos-3mos after treatment some secondary foci appeared around the periphery of the primary lesion. In general better effectiveness was obtained in patients with small lesion. After analyzing by RIDIT method, the therapeutic result in group B was significantly better than that in group C, and secondary foci around the original lesion were rarely seen at 3mos after treatment. In group C the collateral circulation was reestablished along the periphery of primary foci and the secondary foci appeared more frequently, and were required to undergo several courses of treatment. In group B, 4 cases of HCC were treated surgically as their mass decreased in size after (32)P-GMS treatment.Resected specimens showed that the tumor was encapsulated by fibrotic tissue and most of the tumor cells necrosed. The 3 year survival rates were 43.3%-51.0% after A and B regimen treatment. In 14 cases of secondary HCC, the foci were well controled within one year after treatment.CONCLUSION:When the experimental model of implanted human liver cancer cells received (32)P-GMS of 1830Gy-3660Gy, it produced excellent anticancer effect without any injury to the normal neighboring tissues and the prominent anticancer effect was shown within 3d after intratumoral injection. Intrahepatic arterial administration of (32)P-GMS at the macro-cosmic absorbed dosage less than 190 Gy/dose exerted reversible sub lethal injury to domestic pig liver tissues. It took more than 8 weeks to repair the injured liver tissue and restore its function.(32)P-GMS trans hepatic artery embolization is an effective and safe regimen in treating hepatic carcinoma.