Promotion through gas phase induced surface segregation: methanol synthesis from CO, CO2 and H2 over Ni/Cu(100)

We have studied the rate of methanol formation over Cu(100) and Ni/Cu(100) from various mixtures of CO, CO₂ and H₂. It is found that the presence of submonolayer quantities of Ni leads to a strong increase in the rate of methanol formation from mixtures containing all three components whereas Ni does not influence the rate from mixtures of CO₂/H₂ and CO/H₂, respectively. The influence of the partial pressures of CO and CO₂ on the rate indicates that the role of CO is strictly promoting. From temperature-programmed desorption spectra it follows that the surface concentration of Ni depends strongly on the partial pressure of CO. In this way the increase in reactivity is interpreted as a CO-induced structural promotion introduced by the stronger bonding of CO to Ni as compared to Cu. It is suggested that this type of promotional behavior will be of general importance in existent catalysts and perhaps even more relevant in the development of new or improved bimetallic catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Applying Projection‐Based Methods to the Asymmetric Traffic Assignment Problem

This article examines the application of a path‐based algorithm to the static and fixed demand asymmetric traffic assignment problem. The algorithm is of the simplicial decomposition type and it solves the equilibration or master problem step by means of five existing projection methods for variational inequality problems to evaluate their performance on real traffic networks. The projection methods evaluated are: (1) a cost approximation‐based method for minimizing the Fukushima's gap function, (2) the modified descent method of Zhu and Marcotte ( 1988 ), (3) the double projection method of Khobotov ( 1987 ) and three of its recently developed variants (Nadezhkina and Takahashi, 2006 ; Wang et al., 2010 ; and He et al., 2012); (4) the method of Solodov and Svaiter ( 1999 ); and (5) the method of Solodov and Tseng ( 1996 ). These projection methods do not require evaluation of the Jacobians of the path cost functions. The source for asymmetries are link costs with interactions, as in the case of priority ruled junctions. The path‐based algorithm has been computationally tested using the previous projection methods on three medium to large networks under different levels of congestion and the computational results are presented and discussed. Comparisons are also made with the basic projection algorithm for the fixed demand asymmetric traffic assignment problem. Despite the lack of monotonicity properties of the test problems, the only method that failed to converge under heavy congestion levels was the basic projection algorithm. The fastest convergence was obtained in all cases solving the master problem step using the method of He et al. (2012), which is a variant of Khobotov's method.     

Hand arthropathy of professional origin: milkingman hand

OBJECTIVE: The aim of this case-control study was to know possible correlates between distinctive pattern of hand arthrosis and length manual milking. PATIENTS AND METHODS: Between January 1990 and January 1996, we retrospectively reviewed the patients with symptomatic arthrosis in whose hands was identified this pattern: degenerative disease of distal interphalangeal joints with radial deviation and flexion of distal phalanges in association to arthrosis involving metacarpophalangeal and interphalangeal joints of the thumb. The first 88 cases of hand arthrosis without this clinical and radiographic pattern make the control group. Patients suffering inflammatory rheumatic diseases were excluded. RESULTS: 35 patients with this special pattern of hand arthrosis were recruited. The majority of patients were women (94.3%) and coming from rural environment (94.3%). 32 patients had performed daily manual milking over a period of 20 years, but in three patients the pattern was not related to this activity (odds ratio = 928: p < 0.001). Symptoms were more frequent in the control-group (57% versus 26%; p < 0.04), in which no characteristic pattern of alignment abnormality was found. CONCLUSION: A typical pattern of hand arthrosis was associated with prolonged manual milking: degenerative disease of metacarpophalangeal and interphalangeal joints of thumb, radial deviation associated with flexion of distal phalanges of second at fourth fingers and arthrosis involving their distal interphalangeal joints, often linked to sight ulnar deviation of middle phalanges.     

Recovering Bioactive Compounds from Olive Oil Filter Cake by Advanced Extraction Techniques

The potential of by-products generated during extra-virgin olive oil (EVOO) filtration as a natural source of phenolic compounds (with demonstrated bioactivity) has been evaluated using pressurized liquid extraction (PLE) and considering mixtures of two GRAS (generally recognized as safe) solvents (ethanol and water) at temperatures ranging from 40 to 175 °C. The extracts were characterized by high-performance liquid chromatography (HPLC) coupled to diode array detection (DAD) and electrospray time-of-flight mass spectrometry (HPLC-DAD-ESI-TOF/MS) to determine the phenolic-composition of the filter cake. The best isolation procedure to extract the phenolic fraction from the filter cake was accomplished using ethanol and water (50:50, v/v) at 120 °C. The main phenolic compounds identified in the samples were characterized as phenolic alcohols or derivatives (hydroxytyrosol and its oxidation product), secoiridoids (decarboxymethylated and hydroxylated forms of oleuropein and ligstroside aglycones), flavones (luteolin and apigenin) and elenolic acid derivatives. The PLE extraction process can be applied to produce enriched extracts with applications as bioactive food ingredients, as well as nutraceuticals.     

Quantitative HIV-1 RNA as a marker of clinical stability and survival in a cohort of 302 patients with a mean CD4 cell count of 300 x 10(6)/l

OBJECTIVE: To analyse plasma HIV-1 RNA levels as a marker of clinical stability and survival in a cohort of HIV-infected patients whose time of seroconversion is unknown. DESIGN: Retrospective cohort study. SETTING: Retrovirology laboratory and AIDS Unit in a teaching hospital. PATIENTS: A total of 916 samples from 302 patients, most on antiretroviral therapy, were analysed. Mean initial CD4 cell counts and HIV-1 RNA were 299 x 10(6)/l (range: 0-1600) and 134,261 copies/ml (range: < 200-4,300,000), respectively. Sixty-six cases had been diagnosed previously with AIDS. METHODS: Analysis of progression to AIDS and survival, according to initial and longitudinal viral load (VL) and CD4 cell count measurements was performed by Kaplan-Meier test. Relative risks were calculated by Cox's proportional hazards model. RESULTS: During a mean follow-up of 444 +/- 309 days, 29 patients developed AIDS and 21 died. Relative risk (RR) of progression related to the group with VL < 35,000 was: 10.4 when CD4 > or = 250 x 10(6)/l and VL > or = 35,000 (P = 0.001); and 45.3 when CD4 < 250 x 10(6)/l and VL > or = 35,000 (P < 0.0001). Cumulative probability of progression was: 0%, 0% and 12.3%, at the first, second and third year respectively, for patients with all their sequential VL determinations < 60,000; and 13.3%, 34.7% and 79.3% for patients who did not maintain VL values always < 60,000 (RR = 23; P < 0.0001). The minimum value of VL that reached statistical significance for the survival analysis was 100,000 copies/ml (P < 0.0001). CONCLUSIONS: VL > or = or < 35,000 is a better discriminant for progression than a CD4 cell count > or = or < 250 x 10(6)/l. Sequential VL determinations < 60,000 are associated with a better prognosis.