Search

Background Functional disability of the finger joints in rheumatoid arthritis (RA) patients could affect their oral hygiene and periodontal status because of poor plaque control. We examined the influence of plaque control on the relationship between the severity of RA and periodontal status in RA patients. Methods This study recruited 89 Japanese RA patients who reported no difficulty in performing oral hygiene. We assessed RA severity using four indices: the Steinbrocker stage and class, the Health Assessment Questionnaire (HAQ) and the Disease Activity Score (DAS). Probing depth (PD), clinical attachment level (CAL), and bleeding on probing (BOP) were taken as parameters of periodontal status. Oral hygiene status was assessed using the plaque index (PlI). We examined the association between the severity of RA and periodontal parameters using multivariable linear regression analyses. Results In multivariable linear regression analyses not including PlI, Steinbrocker stage III-IV patients had significantly higher PlI scores and greater PD compared with those of stage I. The class III-IV patients had significantly higher PlI scores and greater PD. Patients with an HAQ score ≥0.5 had a significantly higher PlI score than those with an HAQ score of 0. However, when PlI was added to each multivariable model as an independent variable, no significant relationship between RA severity and periodontal status was observed. Conclusions This study suggests that it is important to consider the influence of plaque control when assessing the relationship between RA severity and periodontal health status in RA patients.

Urolithiasis is a common urological problem, and its incidence has been increasing worldwide, including in Japan. Relationships between stone etiology and rise in ambient temperature have been reported, but it remains unclear how age and gender affect these relationships.A retrospective examination was conducted of the medical archives of 1005 patients (aged ≥15 years) with acute renal colic diagnosed with urolithiasis upon image examination who consecutively visited emergency departments in three hospitals. The patients were categorized into six groups according to age: younger than 30, 30-39, 40-49, 50-59, 60-69, and 70 years and older. The net difference and fold increase in the number of patients in summer (July to September) versus in winter (December to February) were calculated.Overall, the actual number of the patients varied according to the temperature rise throughout the year and among the age groups. Net increases in the number of patients were observed in all age groups for both genders, apart from 30-39-year-old women. The age group of 50-59 years considerably outnumbered all other groups. A significant statistical correlation was detected between the fold increase and male aging using Spearman's rank correlation analysis (ρ = 0.94, p = 0.017), but not in females (ρ = -0.03, p = 1).These results support a positive association between ambient temperature rise and increase in the incidence of renal colic due to urolithiasis in Japan, and indicate that aging and gender affect the association differently.

Lithium ions were extracted from aqueous solutions into cyclohexane containing di-(2-ethylhexyl)phosphoric acid (D2EHPA) through slug flow in millimeter-diameter glass and polytetrafluoroethylene (PTFE) tubes. The PTFE tube produced a higher initial mass transfer coefficient than the glass tube by increasing internal circulation in the organic phase, and maintained its specific surface area. Slug flow occurred in the PTFE tube when the interfacial tension between the aqueous and organic phases exceeded 50–55 mN/m, which increased the rate of extraction owing to increased circulation in both phases. The addition of tributyl phosphate (TBP) enhanced the extraction efficiency, but did not affect the extraction rate.

We herein report the effects of the following variables on demulsification using an alternating electric field: (1) type and volume fraction of an organic solvent, and (2) type and ionic strength of an electrolyte in water. Ethylbenzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane, and n-hexane were employed as organic solvents. The effect on demulsification of either KCl or CaCl2 addition to the aqueous phase was also examined. We observed that a square waveform alternating electric field was more effective than a sine waveform. In addition, the demulsification rate varied significantly upon altering the volume fraction of the organic solvent and the ionic strength of the electrolyte. Demulsification using an alternating electric field was effective for W/O type emulsions. Demulsification was promoted using an organic solvent with greater relative permittivity.

Extraction by slug flow gives high mass transfer rate and rapid phase separation than the conventional extraction operation. Therefore, there are many advantages such as the volume of the device becomes small and the solvent drastically reduced. The slug flow extraction is expected as a sophisticated separation process. Especially, these advantages become more prominent in the multistage extraction. In this study, the extraction by the slug flow was applied to mutual separation of lithium, cobalt and nickel ions in the mixed aqueous solution. We succeeded in developing a process with lithium, cobalt, nickel ion purity of 85% or more and recovery rate of 90-95%. Furthermore, it was also confirmed that the flow state of the liquid is influenced by the hydrophobicity (PTFE) and hydrophilicity (glass) of the extraction tube. The overall mass transfer volumetric coefficient is affected by (1) the interface area of the oil phase and aqueous phase, (2) the strength of the circulating flow in each segment of the liquid, and (3) the volume flow ratio of the oil phase and the aqueous phase.

In this study, the in-flow demulsification of a water-in-toluene emulsion by an alternating electric field was investigated. A fluorocarbon tube, chosen for its flexibility and resistance to toluene, was positioned between copper electrodes attached to a voltage supply and a wave generator. With this design, it was possible to apply a strong electric field of 1000 kV/m as the emulsion was not in direct contact with the electrodes. The demulsification rate increased on increasing the frequency of the alternating electric field up to ∼100 Hz, and a square wave was more effective than a sine wave at low frequencies. Furthermore, the demulsification rate increased on increasing the content of the organic phase and intensity of the electric field. We investigated the effects of an electrolyte dissolved in the aqueous phase, and found that it promoted demulsification in relation to the valence of the cation used. Additionally, demulsification was strongly affected by the ionic strength of the aqueous phase. Our results show that demulsification by the application of an alternating electric field can be very useful in the continuous flow treatment of extraction mixtures in organic synthesis.

Introduction We investigated relationships between therapeutic outcomes of patients with emphysematous pyelonephritis (EPN) and changes in the Sequential Organ Failure Assessment (SOFA) score. Materials and methods We retrospectively evaluated EPN patients treated in our hospitals using the SOFA score incorporated in the Sepsis-3 updated in 2016. Results Seventeen typical EPN patients were included in this study, and were treated with medical management with no drainage (n = 3), retrograde stenting (n = 10), or percutaneous drainage (n = 3). One patient without drainage died of sepsis, yielding an overall mortality rate of 5.9%. Twelve patients recovered without increase in the SOFA score during hospitalization. However, the SOFA score deteriorated in the other patients from admission, with the initial scores not significantly different from those of the 12 cases. The changes in the SOFA score were significantly affected by the selected approaches of drainage (100% patients for no drainage, 22% for stenting, and 0% for percutaneous drainage, p = 0.029), but not by other clinical data. Conclusion Most EPN patients can currently be conservatively managed successfully. However, it should be noted that less-invasive management could cause deterioration in SOFA after admission, yielding a risk of septic mortality.

Background: Poor oral health is associated with an increased risk of dementia in the elderly. One possible pathway linking these two phenomena is lacunar infarction, a potential cause of dementia. An association between poor oral health and an increased risk of ischaemic stroke has been recognised through the oral infection-inflammation pathway. However, little is known about whether poor oral health is associated with the progression of lacunar infarction. Objective: We examined the association between variables related to oral health and lacunar infarction, as detected by magnetic resonance imaging (MRI). Methods: A total of 110 subjects (52 men, 58 women), aged 27-76 years, who visited our periodontology clinic participated in this study. The subjects underwent dental radiography, periodontal examinations and brain MRI. One experienced specialist in cardiovascular disease and one experienced neurosurgeon determined the number of lacunar infarctions on brain MRI. Periodontologists performed clinical periodontal examinations. Variables related to oral health were determined from the radiographs by an oral radiologist. Information on the subjects' lifestyles and disease histories were obtained using a structured questionnaire and confirmed by clinical records. Adjacent categories logit regression analysis with backward elimination was used to determine variables associated with three groups based on the number of lacunar infarctions. Results: Of the 110 subjects, 61 had lacunar infarctions. Nineteen had multiple (≥7) lesions. Aging (p = 0.0004), increased time spent in physical activity per day (p = 0.042), the presence of hypertension (p = 0.006), the absence of hyperlipidaemia (p = 0.045), the presence of diabetes mellitus (p = 0.025) and low alveolar bone height (p = 0.026) were significantly associated with an increased number of lacunar infarctions in the final regression model. The significance of hyperlipidaemia and alveolar bone height disappeared in an unadjusted model. An increased pocket depth, which indicates current periodontal disease progression, tended to be associated with an increased number of lacunar infarctions (p = 0.058). This tendency did not disappear in an unadjusted model. Conclusion: Our results suggest that lacunar infarction may be associated with current periodontal disease in Japanese adults.

Osteoclasts are derived from the monocyte/macrophage lineage, but little is known about osteoclast precursors in circulation. We previously showed that cell cycle-arrested quiescent osteoclast precursors (QOPs) were detected along bone surfaces as direct osteoclast precursors. Here we show that receptor activator of NF-κB (RANK)-positive cells isolated from bone marrow and peripheral blood possess characteristics of QOPs in mice. RANK-positive cells expressed c-Fms (receptors of macrophage colony-stimulating factor) at various levels, but scarcely expressed other monocyte/granulocyte markers. RANK-positive cells failed to exert phagocytic and proliferating activities, and differentiated into osteoclasts but not into dendritic cells. To identify circulating QOPs, collagen disks containing bone morphogenetic protein-2 (BMP disks) were implanted into mice, which were administered bromodeoxyuridine daily. Most nuclei of osteoclasts detected in BMP-2-induced ectopic bone were bromodeoxyuridine-negative. RANK-positive cells in peripheral blood proliferated more slowly and had a much longer lifespan than F4/80 (a macrophage marker)-positive macrophages. When BMP disks and control disks were implanted in RANK ligand-deficient mice, RANK-positive cells were observed in the BMP disks but not in the controls. F4/80-positive cells were distributed in both disks. Administration of FYT720, a sphingosine 1-phosphate agonist, promoted the egress of RANK-positive cells from hematopoietic tissues into bloodstream. These results suggest that lineage-determined QOPs circulate in the blood and settle in the bone.

The development of slug flow channel microreactors is expected for new chemical production plants. The purpose of this study was to produce a device that could easily generate short steady slug flow. A fine stable slug flow (length ca. 1 mm) of aqueous and organic phases was successfully achieved in a microchannel for a wide range of flow rates (0–100 ml/h). This operation did not require complicated devices or a power source, and was achieved by the simple process of inserting a piece of glass bead into the microchannel. The generated slug flow was stable and ran through the microchannel without changing shape. The slug flow rapidly separated into aqueous and organic phases in a settler attached to the microreactor. The developed microreactor was applied to Cs + extraction and resulted in rapid separation that compared favorably with conventional batch experiments.

In the field of micro chemical process, the research on slug flow chemical process becomes attractive. The slug flow is a flow in which two liquids appear alternately, forming striped pattern on a flow line, and it is effective to realize efficient chemical reaction. The goal of this research is realization of slug flow generation/separation system by three port electro magnetic micro valves. This system will realizes slug flow with desired length without depending on the characteristics of liquids and their flow rates. A new separation process for slug flow is realized. It achieves noncontact detection of switching of liquid phase by using an optical sensor. The copper ion extraction experiment was conducted, and the effectiveness in an actual chemical process has been shown.

Pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br) was performed at 430°C in the presence of 0.1 wt% of polyethylene terephthalate (PET) in a Pyrex glass reactor. Two different types of brominated flame retardants (decabromodiphenyl ether and decabromodiphenyl ethane) with or without antimony trioxide (as synergist) 5 wt% were used. The presence of PET had a significant effect on the material balance, decreasing the gaseous product and increasing the residue. The type of flame retardant had no effect on the yield of liquid product; however, the presence of Sb resulted in a marked difference in the distribution of decomposition products. Analysis by a gas chromatograph equipped with a flame ionization detector showed that the hydrocarbons were distributed in the range n-C7 to n-C25 with major peaks at n-C9 and n-C17. The presence of PET increased the formation of brominated compounds by several times and affected both the type and quantity of polybrominated compounds. The liquid products obtained from the pyrolysis of HIPS-Br/PET have to be treated before they can be used

Background: Renal cell carcinoma (RCC) is highly resistant to chemotherapy because of a high apoptotic threshold. Recent evidences suggest that GSK-3β positively regulates human pancreatic cancer and leukaemia cell survival in part through regulation of nuclear factor (NF-κB)-mediated expression of anti-apoptotic molecules. Our objectives were to determine the expression pattern of GSK-3β and to assess the anti-cancer effect of GSK-3β inhibition in RCC. Methods: Immunohistochemistry and nuclear/cytosolic fractionation were performed to determine the expression pattern of GSK-3β in human RCCs. We used small molecule inhibitor, RNA interference, western blotting, quantitative RT–PCR, BrDU incorporation and MTS assays to study the effect of GSK-3β inactivation on renal cancer cell proliferation and survival. Results: We detected aberrant nuclear accumulation of GSK-3β in RCC cell lines and in 68 out of 74 (91.89%) human RCCs. We found that pharmacological inhibition of GSK-3 led to a decrease in proliferation and survival of renal cancer cells. We observed that inhibition of GSK-3 results in decreased expression of NF-κB target genes Bcl-2 and XIAP and a subsequent increase in renal cancer cell apoptosis. Moreover, we show that GSK-3 inhibitor and Docetaxel synergistically suppress proliferation and survival of renal cancer cells. Conclusions: Our results show nuclear accumulation of GSK-3β as a new marker of human RCC, identify that GSK-3 positively regulates RCC cell survival and proliferation and suggest inhibition of GSK-3 as a new promising approach in the treatment of human renal cancer.

A composite of a porous carbon with magnetic and photocatalytic potential was prepared by mixing polyvinyl alcohol, titanium oxide and magnetite and heating at 500°C, 600°C and 900°C. Crystalline TiO2, metallic Fe, martensite and ilmenite were found in the composite. Removal of 4-Chlorophenol in the aqueous solution was conducted by a batch test with irradiation of black light. As a result the composite had potential for adsorption and decomposition of organic compounds in water.

The hydrothermal treatment of two different wood biomass samples such as cherry (hard wood) and cypress (soft wood), whose composition is different i.e. lignin, cellulose and hemicellulose were performed at 280 °C for 15 min with aq. K 2 CO 3 with different concentrations (0–1 M). The soft wood biomass contains higher lignin content than hard wood biomass. The cellulose rich cherry wood biomass produced higher proportion of acetic acid than cypress. The lignin rich cypress produced the hydrocarbons with major portion of phenolic hydrocarbons and derivatives than cherry. The total oil yields from both cherry and cypress wood biomass produced 50 wt% of liquid hydrocarbons at 280 °C for 15 min with 0.5 M K 2 CO 3 solution. The volatility distribution of liquid hydrocarbons showed the characteristic features of soft and hard wood biomasses.

Renal cell carcinoma (RCC) is known to be resistant to chemo- and radiotherapy due to a high apoptotic threshold. Smac and XIAP (X-linked inhibitor of apoptosis protein) proteins were detected in all RCC cell lines and tissue samples examined. We modulated the function of XIAP, either through its constitutional downregulation with an shRNA vector or by applying a Smac-mimicking peptide. Among RCC cell lines, Caki1 expresses the highest levels of XIAP. We transfected Caki1 with XIAP-targeting shRNA vector and generated stable clones. XIAP was knocked down by RNA interference in clone no. 14 by 81.6% and in clone no. 19 by 85.3%. Compared to the parental and mock-transfected cells, neither clone was more sensitive to conventional chemotherapeutic agents, but both clones were more susceptible to Fas stimulation (P

A composite of titanium phosphate-porous carbon was prepared from amino phosphate chelate resin by adsorbing Ti (IV) and carbonization at 773K and 873K. The composite had potential for adsorption and decomposition of organic compounds in water. Removal of methylene blue in the aqueous solution was conducted by a batch test with irradiation of black light. Platinum was added into the composite as promotor. Crystalline TiP2O7 and metallic Pt were found in the composite. The diameters of these crystalline particles were less than 30nm. Pt promoted gasification of the polymer chain of the chelate resin.The removal rate of methylene blue was increased by co-existing Pt. The removal rate constant k was expressed by first order kinetics. The removal rate constant per weight of Ti in the composite k' was almost constant even though Pt content was increased.

The co-pyrolysis of brominated high impact polystyrene (Br-HIPS) with polyolefins using a fixed bed reactor has been investigated, in particular, the effect that different types of brominated aryl compounds and antimony trioxide have on the pyrolysis products. The pyrolysis products were analysed using FT-IR, GC–FID, GC–MS, and GC–ECD. Liquid chromatography was used to separate the oils/waxes so that a more detailed analysis of the aliphatic, aromatic, and polar fractions could be carried out. It was found that interaction occurs between Br-HIPS and polyolefins during co-pyrolysis and that the presence of antimony trioxide influences the pyrolysis mass balance. Analysis of the Br-HIPS + polyolefin co-pyrolysis products showed that the presence of polyolefins led to an increase in the concentration of alkyl and vinyl mono-substituted benzene rings in the pyrolysis oil/wax resulting from Br-HIPS pyrolysis. The presence of Br-HIPS also had an impact on the oil/wax products of polyolefin pyrolysis, particularly on the polyethylene oil/wax composition which converted from being a mixture of 1-alkenes and n-alkanes to mostly n-alkanes. Antimony trioxide had very little impact on the polyolefin wax/oil composition but it did suppress the formation of styrene and alpha-methyl styrene and increase the formation of ethylbenzene and cumene during the pyrolysis of the Br-HIPS.

Degradations of polypropylene (PP) and polyethylene (PE) over pure hexagonal mesoporous silica and aluminum-containing hexagonal mesoporous silica catalysts were studied in a fixed bed catalytic reactor at 380 and 430 °C, respectively. The thermal and catalytic degradations of both PP and PE in liquid-phase-contact and vapor-phase-contact modes over pure hexagonal mesoporous silica had no significant effect on the product yields. The liquid products were widely distributed in hydrocarbons with boiling point ranges of 36–405 °C. By adding a small amount of aluminum to the hexagonal mesoporous material, aluminium-containing hexagonal mesoporous silica exhibited good performance in cracking heavy molecular weight hydrocarbons into light hydrocarbons. High liquid yields and less coke deposits were obtained in liquid-phase-contact reaction with increasing aluminum content. The liquid products were mainly composed of C5–C10 hydrocarbons with boiling points of 36–174 °C, and propene, butene, and butane were main components in gaseous products. The effect of degradation temperature was not observed on product yields though degradation rate of polyolefin into liquid products was faster. Conversely, in vapor-phase-contact reaction, an increase in gaseous yield was observed when increasing the amount of aluminum and temperature of the cracking reactor, while the residue yield remained constant.

Waste DVDs and CDs were thermally degraded at 450°C by a semibatch process. In total, 40–50 wt% was converted into liquid product that consisted of phenol derivatives (∼75 wt%), bisphenol (∼10 wt%) and its derivatives, and small amounts of aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene, methylethylbenzene, diethylbenzene, and methylisopropyl benzene. Degradation of the polycarbonate support from DVDs and CDs was enhanced by coprocessing with vegetable cooking oil, the degradation of which gave a homologue series of hydrocarbons and organic acids with up to 25 and 18 atoms of carbon, respectively. Silver from the reflective coating on DVDs and CDs remained in the solid residue, its concentration increasing about 2.5 times compared to that of the original disks.

Brominated high-impact polystyrene (HIPS-Br), which contained decabromodiphenyl ether flame retardant, and brominated acrylonitrile butadiene styrene (ABS-Br), which contained bromine-containing epoxy-type flame retardant, were degraded at 450°C individually and in a 1/1 mixture by a thermal and catalytic procedure using folded sheet mesoporous (FSM) and ZSM-5 zeolite in liquid phase contact mode. The two polymers produced similar degradation oils but at a higher yield for HIPS-Br. However, the composition and distribution of Br-, N-, and O-containing compounds depended on the type of flame retardant in HIPS-Br and ABS-Br. Multiphase catalytic systems consisting of FSM in liquid phase contact mode and various CaH-, FeO-, CoMo-, and NiMo-based catalysts, or combinations of these catalysts, in vapor phase contact mode were used to decrease the amount of heteroatoms (Br, N, and O) in the degradation oils. Each system gave particular results in terms of mass balance and concentrations of heteroatoms. A FSM (liquid phase contact)/CaHC (vapor phase contact) combination was the best catalytic system to remove Br-, N-, and O-containing compounds from degradation oils.

The pyrolysis of polyethylene(PE)/polypropylene(PP)/polystyrene(PS) mixed with high impact polystyrene (HIPS-Br) containing decabromo diphenylethane (DDE) as a brominated flame retardant with antimony trioxide as a synergist was performed under controlled temperature programmed pyrolysis (two steps) conditions to understand the decomposition behaviour and evolution of brominated hydrocarbons from flame-retardant additives. The liquid products were extensively analyzed by gas chromatographs equipped with FID, ECD, MSD, TCD, AED and FT-IR. The solid residue samples were analyzed by powder X-ray diffraction and combustion followed by ion-chromatography. The controlled pyrolysis of PE/PP/PS/HIPS-Br significantly affected the decomposition behaviour of HIPS-Br and subsequently the formation of decomposition products. GC/ECD analysis confirmed that the brominated hydrocarbons were concentrated in step 1 liquid products leaving less brominated hydrocarbons in the step 2 liquid products, similar to the decabromo diphenyl ether flame retardant containing mixed plastics. The yield of liquid products in step 1 from 3P/DDE-Sb(5) was 5 wt% and from 3P/DDE-Sb(0) was 2.4 wt%. The presence of antimony in the DDE containing plastics affected the yield of liquid, gas and residue products. ECD analysis showed that the presence of antimony increased the Br containing hydrocarbons and step 1 has 3–4 times higher brominated compounds than step 2 hydrocarbons in both the samples.

Standard lymphadenectomy for prostate cancer is limited to the obturator lymph nodes (LNs), although the internal and external iliac LNs represent the primary landing zone for prostatic lymphatic drainage. We performed anatomically semi-extended pelvic lymph node dissection (PLND) to assess the incidence of LN metastasis in cases of clinically localized prostate cancer. A total of 730 consecutive patients underwent radical prostatectomy with either semi-extended PLND, comprising 6 selective fields, namely the external iliac, internal iliac and obturator LNs bilaterally, or standard LND (obturator LNs alone). A total of 131 patients undergoing semi-extended PLND were compared with 599 patients undergoing standard LND. The patients were stratified into high-risk [prostate-specific antigen (PSA)>20 ng/ml, Gleason score (GS)≥8], intermediate-risk (PSA 10-20 ng/ml, GS=4+3) and low-risk (PSA

Pyrolysis of poly(vinylidene chloride) (PVDC), brominated flame retardant containing high impact polystyrene (HIPS-Br), poly(ethylene) (PE), poly(propylene) (PP), poly(styrene) (PS) mixed were performed in the presence and absence of poly(ethylene terephthalate) (PET) under atmospheric pressure at 430 °C using a semi-batch operation. We attempted the dehalogenation (Cl, Br) of chlorinated and brominated liquid hydrocarbons using iron oxide and calcium hydroxide based carbon composites for the production of halogen free liquid hydrocarbons. The presence of PET in the plastics mixture of PP/PE/PS/PVDC/HIPS-Br affected significantly the formation of pyrolysis products and the pyrolysis behavior of plastic mixture. We observed the following effects of PET on the pyrolysis of PP/PE/PS/PVCD/HIPS-Br mixed plastic pyrolysis: (i) The yield of liquid product was decreased and the formation of gaseous products increased during the thermal decomposition, (ii) the waxy residue was observed in addition to the solid carbon residue and (iii) use of calcium hydroxide carbon composite (CaH–C) removed the major portion of chlorine and bromine content from the liquid products from PP/PE/PS/PVDC/HIPS-Br pyrolysis, however in the presence of PET, the combination of calcium hydroxide carbon composite (CaH–C) and iron oxide carbon composites could not dehalogenate the liquid products effectively. X-ray diffraction analysis reveals the presence of antimony compounds in carbon and wax residues.

Catalytic hydrothermal treatment of wood biomass was performed at 280 degrees C for 15 min in the presence of K2CO3 with different concentrations and biomass/water ratio (thermal). Oil products were extracted from both liquid and solid portion by different solvents and analyzed them individually. The biomass to water ratio has an important effect on product distribution and composition of oil products. Oil 1 (ether extract) with K2CO3 contained mainly phenolic compounds. Benzenediol derivatives were observed with 0.94 M K2CO3 concentration and they were not formed at lower concentrations (0.235 and 0.47 M). The decrease of solid residue was achieved to 4% with 0.94 M K2CO3 at 280 degrees C for 15 min. The volatility distribution of hydrocarbons (ether extract) were characterized by using C-NP gram. The distribution of oxygenated hydrocarbons changed depending upon the biomass to water ratio and concentration of K2CO3 solution.

The first part of this paper deals with the morphology of the MoS2 phase and its oxide precursor, the MoO3 phase, mainly from a geometrical point of view. After giving a brief review of the literature describing the structure of these compounds, Mo densities in both phases were calculated along various crystallographic planes. Further, using structural models recently proposed by others, Mo densities in MoS2 were also calculated in the case of an epitactic growth on γ-Al2O3 and TiO2 model surfaces. Then, the calculated Mo densities were compared with experimental results (Mo density when HDS activity is maximal) previously obtained for catalysts constituted of MoS2 supported on a low SSA TiO2, a high SSA TiO2 and a conventional γ-alumina. It was suggested that either on alumina or titania the MoS2 phase is growing as (100) MoS2 planes. However, while on the alumina the optimal MoS2 phase might be constituted of dispersed MoS2 slabs covering only a part of the alumina surface (2.9–3.9 Mo atoms/nm2), on titania the optimal MoS2 phase might be constituted of a uniform MoS2 monolayer (5.2 atoms/nm2 for the high SSA titania, which is equal to the Mo density of a perfect MoS2 (100) plane). This difference may originate in the creation of a 'TiMoS' phase enhancing the S atoms mobility over Mo/TiO2-sulfided catalysts. Indeed, while in the case of a γ-alumina carrier the active sites (labile S atoms) are located on the edge of MoS2 slabs making the ratio Moedge/Mototal a crucial parameter for the catalytic performances, in the case of a titania carrier the labile sulfur atoms might be statistically distributed all over the TiMoS active phase. Further, the higher Mo density observed over the high SSA titania (5.2 atoms/nm2) when compared to that over the low SSA titania (4.2 atoms/nm2) was supposedly due to the pH-swing method advantageously used to prepare the former carrier. Indeed, this method allows giving a solid with enhanced mechanical properties providing a good stability to the derived catalysts under experimental conditions. In addition, this TiO2 carrier exhibits a great homogeneity, with a surface structure substantially uniform, which might be adequate for a long-range growth of (100) MoS2 slabs.

Three series of CoMo catalysts (MoO 3 : 6, 11, 16 wt.%) with various Co/Mo molar ratios were prepared by successive incipient wetness impregnations of a titania sample previously prepared by the pH swing method, which provides a TiO 2 carrier with a high SSA (134 m 2 g −1 ) and excellent mechanical properties. DBT HDS activity of the catalysts increased with addition of cobalt up to Co/Mo = 0.4 and then decreased for higher ratios, irrespective of the Mo loading. The results of a [ 35 S]DBT HDS method showed that S 0 , the amount of labile sulfur atoms, increased in parallel with the activity when adding Co up to a molar ratio of 0.4. In contrast, unlike on CoMo/Al 2 O 3 catalysts, only a slight increase in k RE , the H 2 S release rate constant, was observed upon Co addition. This was due to formation of the TiMoS phase: while formation of Ti S * Mo bonds favorably induces an increase in sulfur mobility on Mo/TiO 2 catalysts, electronic density on Mo atoms increases, which limits the promoting effect of Co on mobility of S a sulfur atoms bridged between Mo and Co. Further, while the increase in HDS activity upon Co addition on a uniform MoS 2 monolayer on TiO 2 was in rather good agreement with the quantitative and kinetics data of the 35 S tracer method, over MoS 2 slabs on TiO 2 this increase was larger than that expected from the results of the 35 S tracer method. This was attributed to the presence of □ * and □ a CUS, i.e. catalytic sites that are not replenished with sulfur, at the steady state. A larger number of □ * CUS was present at low Mo wt.% or for low Co/Mo. As these particular catalytic sites are in the form of CUS at the steady state, they are not accounted by the [ 35 S] radiotracer method. This explains the differences observed between the experimental DBT HDS promotion and the promotion deduced from the increase in k RE and S 0 .

The analysis of chlorine distribution in the pyrolysis products of poly(vinylidene chloride) PVDC mixed with polyethylene (PE), polypropylene (PP) or polystyrene (PS) were investigated [PE/PVDC, PP/PVDC, PS/PVDC and 3P/PVDC, where 3P is equal mixture of PE, PP and PS] and reported for the first time. The interaction of degradation products from individual (PE, PP and PS) and mixed (3P) plastics with the PVDC degradation products was investigated and compared with poly(vinyl chloride), PVC. The formation of chlorinated hydrocarbons in the liquid products were in the order of PS/PVDC > 3P/PVDC > PP/PVDC > PE/PVDC. Surprisingly, the quantities of chlorinated hydrocarbons were less compared with the pyrolysis liquid products of PVC mixed plastics even though the chlorine content in PVDC is higher than in PVC. The structurally similar chlorinated hydrocarbons were observed from PVDC or PVC with PE, PP, and PS liquid products. Thermogravimetric analysis results suggest that the decomposition temperature of PVDC is lower than PVC and major portion of chlorine (from PVDC) left the degradation reactor before the degradation of PP, PE, and PS.

The objective of this study is to investigate the distribution of products, i.e. liquid, gas and solid from wood (sawdust) and non-wood biomass (rice husk), and major biomass components, i.e. lignin, cellulose produced by hydrothermal treatment (280 8C for 15 min) and analysis of liquid hydrocarbons (oils) for the differences in the hydrocarbon composition with respect to feed material. Cellulose showed the highest conversion among the four samples investigated in the present study. Sawdust and rice husk has almost similar conversions. Liquid products were recovered with various solvents (ether, acetone, and ethyl acetate) and analyzed by GC–MS. The oil (ether extract) from the hydrothermal treatment of cellulose consisted of furan derivatives whereas lignin-derived oil contained phenolic compounds. The compositions of oils (ether extract) from sawdust and rice husk contained both phenolic compounds and furans, however phenolic compounds were dominant. Rice husk derived oil consists of more benzenediols than sawdust derived oil. The volatility distribution of oxygenated hydrocarbons were carried out by C-NP gram and it showed that the majority of oxygenated hydrocarbons from sawdust, rice husk and lignin were distributed at n-C11, whereas they were distributed at n-C8 and n-C10 in cellulose-derived oil. The gaseous products were carbon dioxide, carbon monoxide, methane in sawdust, rice husk, lignin and cellulose. In addition to this, ethylene, ethane and propane were observed for sawdust, rice husk and lignin. The major gas product was carbon dioxide for all samples. q 2005 Elsevier Ltd. All rights reserved.

Catalytic hydrothermal treatment of wood biomass was performed at 280 °C for 15 min in the presence of alkaline solutions (NaOH, Na 2 CO 3 , KOH and K 2 CO 3 ). Oil products were extracted from both liquid and solid portion by different solvents and analyzed individually. The effect of base solutions on the yield of oil products and composition of oils obtained at different stages were discussed in detail. Based on the conversion and yield of liquid products, the catalytic activity can be ranked as follows: K 2 CO 3 > KOH > Na 2 CO 3 > NaOH. In thermal run, the yield of solid residue was about 42% whereas it was 4.0% in the presence of K 2 CO 3 . Catalytic hydrothermal treatment of biomass produced mainly phenolic compounds. In thermal run, furan derivatives were observed whereas these compounds could not be observed in catalytic runs. The volatility distribution of hydrocarbons (ether extract) was characterized by using C-NP gram and it showed that the majority of hydrocarbons for all runs including thermal were distributed boiling point range of n -C 11 . The products from hydrothermal treatment of wood biomass were analyzed using GC–MS, 1 H NMR, 13 C NMR, TOC and ion chromatograph.

The thermal and catalytic degradation of a complex polymer mixture was performed at 450 °C at atmospheric pressure in a batch process. The mixture contained polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile–butadiene–styrene copolymer with a brominated flame retardant and antimony oxide synergist (ABS–Br) and poly(vinyl chloride) (PVC), in a 3/3/2/1/1 weight ratio. The effect of iron (FeOOH and Fe–C composite) and calcium (CaCO 3 and Ca–C composite) based catalysts for removal of heteroatom- (nitrogen, bromine, and chlorine) containing compounds in oil products was studied. Changes in the amount and distribution of heteroatoms were described using NP gram curves. Iron catalysts give best results for bromine removal from decomposition oil while calcium catalysts have high efficiency for chlorine removal; however, both Fe- and Ca-catalysts have low effect in nitrogen removal. Carbon composite catalysts give three times less chlorine but they produce higher amounts of nitrogen in degradation oils than the corresponding Fe and Ca pure compounds. In bromine removal Ca–C composite shows higher effect compared to CaCO 3 while Fe–C composite has slightly worse effect than FeOOH.