Structure Sensitivity of CO2 Hydrogenation on Ni Revisited.

Despite the large number of studies on the catalytic hydrogenation of CO2 to CO and hydrocarbons by metal nanoparticles, the nature of the active sites and the reaction mechanism have remained unresolved. This hampers the development of effective catalysts relevant to energy storage. By investigating the structure sensitivity of CO2 hydrogenation on a set of silica-supported Ni nanoparticle catalysts (2-12 nm), we found that the active sites responsible for the conversion of CO2 to CO are different from those for the subsequent hydrogenation of CO to CH4. While the former reaction step is weakly dependent on the nanoparticle size, the latter is strongly structure sensitive with particles below 5 nm losing their methanation activity. Operando X-ray diffraction and X-ray absorption spectroscopy results showed that significant oxidation or restructuring, which could be responsible for the observed differences in CO2 hydrogenation rates, was absent. Instead, the decreased methanation activity and the related higher CO selectivity on small nanoparticles was linked to a lower availability of step edges that are active for CO dissociation. Operando infrared spectroscopy coupled with (isotopic) transient experiments revealed the dynamics of surface species on the Ni surface during CO2 hydrogenation and demonstrated that direct dissociation of CO2 to CO is followed by the conversion of strongly bonded carbonyls to CH4. These findings provide essential insights into the much debated structure sensitivity of CO2 hydrogenation reactions and are key for the knowledge-driven design of highly active and selective catalysts.

Carbon dioxide and nitrate co-electroreduction to urea on CuOxZnOy.

Urea is a commonly used nitrogen fertiliser synthesised from ammonia and carbon dioxide using thermal catalysis. This process results in high carbon dioxide emissions associated with the required amounts of ammonia. Electrocatalysis provides an alternative method to urea production with reduced carbon emissions while utilising waste products like nitrate. This manuscript reports on urea synthesis from the electroreduction of nitrate and carbon dioxide using CuOxZnOy electrodes under mild conditions. Catalysts with different ratios of CuO and ZnO, synthesised via flame spray pyrolysis, were explored for the reaction. The results revealed that all the CuOxZnOy electrocatalyst compositions produce urea, but the efficiency strongly depends on the metal ratio composition of the catalysts. The CuO50ZnO50 composition had the best performance in terms of selectivity (41% at -0.8 V vs RHE) and activity (0.27 mA/cm2 at -0.8 V vs RHE) towards urea production. Thus, this material is one of the most efficient electrocatalysts for urea production reported so far. This study systematically evaluates bimetallic catalysts with varying compositions for urea synthesis from carbon dioxide and nitrate.

Improving the performance of ASA in the DAC of 2,5-DMF and ethylene.

A variety of methods are employed to synthesize amorphous silica-alumina (ASA) to resolve the role of Al speciation and surface area in the catalytic performance in the Diels-Alder cycloaddition reaction of 2,5-dimethylfuran and ethylene to p-xylene. ASA was prepared by homogeneous deposition-precipitation (HDP) of Al3+ on ordered mesoporous silica, i.e., SBA-15 and OMS prepared under hydrothermal synthesis conditions using an imidazole-based template, and one-step flame spray pyrolysis (FSP). IR spectroscopy and 27Al MAS NMR showed that the resulting ASA represented a set of materials with distinct textural and acidic properties. ASA prepared by grafting Al to ordered mesoporous silica led to a much higher concentration of Brønsted acid sites (BAS). These samples performed much better in the DAC reaction, with p-xylene yields higher than those obtained with a HBeta zeolite benchmark. Materials with Al partially in the bulk of silica (OMS, FSP) and containing significant alumina domains are less acidic and exhibit much lower p-xylene yields. These findings point to the importance of Brønsted acidity for p-xylene formation. This study shows that careful design of the Al speciation can lead to amorphous silica-alumina with similar DAC performance to microporous zeolites.

Pseudomonas rhizophila S211, a New Plant Growth-Promoting Rhizobacterium with Potential in Pesticide-Bioremediation.

A number of Pseudomonas strains function as inoculants for biocontrol, biofertilization, and phytostimulation, avoiding the use of pesticides and chemical fertilizers. Here, we present a new metabolically versatile plant growth-promoting rhizobacterium, Pseudomonas rhizophila S211, isolated from a pesticide contaminated artichoke field that shows biofertilization, biocontrol and bioremediation potentialities. The S211 genome was sequenced, annotated and key genomic elements related to plant growth promotion and biosurfactant (BS) synthesis were elucidated. S211 genome comprises 5,948,515 bp with 60.4% G+C content, 5306 coding genes and 215 RNA genes. The genome sequence analysis confirmed the presence of genes involved in plant-growth promoting and remediation activities such as the synthesis of ACC deaminase, putative dioxygenases, auxin, pyroverdin, exopolysaccharide levan and rhamnolipid BS. BS production by P. rhizophila S211 grown on olive mill wastewater based media was effectively optimized using a central-composite experimental design and response surface methodology (RSM). The optimum conditions for maximum BS production yield (720.80 ± 55.90 mg/L) were: 0.5% (v/v) inoculum size, 15% (v/v) olive oil mill wastewater (OMWW) and 40°C incubation temperature at pH 6.0 for 8 days incubation period. Biochemical and structural characterization of S211 BS by chromatography and spectroscopy studies suggested the glycolipid nature of the BS. P. rhizophila rhamnolipid was stable over a wide range of temperature (40-90°C), pH (6-10), and salt concentration (up to 300 mM NaCl). Due to its low-cost production, emulsification activities and high performance in solubilization enhancement of chemical pesticides, the indigenous BS-producing PGPR S211 could be used as a promising agent for environmental bioremediation of pesticide-contaminated agricultural soils.

The somatostatin receptor SSTR1 is coupled to phosphotyrosine phosphatase activity in CHO-K1 cells.

Somatostatin receptors are abundantly expressed on a variety of human endocrine and epithelial tumors. The ability of these receptors to couple to effector pathways that inhibit the growth of these tumor cells has prompted the use of somatostatin agonists in the treatment of human neoplasms. It has been demonstrated that somatostatin stimulates a phosphotyrosine phosphatase in human tumor cells through a receptor-mediated process. This stimulation may counteract the growth-promoting properties of growth factors and the receptor tyrosine kinases that they activate. The recent cloning and characterization of distinct somatostatin receptor subtypes raise the possibility that different receptor subtypes mediate distinct effector pathways. To determine whether cloned somatostatin receptors could mediate coupling to phosphotyrosine phosphotyrosine phosphatase activity, we examined phosphatase activity after somatotostatin activation of the rat somatostatin receptors SSTR1 and SSTR2 after their stable expression in heterologous Chinese Hamster Ovary (CHO-K1) cells. We found that stimulation of SSTR1 cells was capable of increasing phosphotyrosine phosphatase activity, despite the coupling of both receptors to the inhibition of adenylyl cyclase in these cells. This activation was characterized by an EC50 of 70 nM and was sensitive to pertussis toxin. In addition, we demonstrate that activation of phosphotyrosine phosphatase activity in pituitary cell lines correlates with the endogenous expression of the SSTR1 gene within these cells.

Leptospirosis serology in Korean wild animals.

A study was undertaken on wild animals to determine the seroprevalence of animal leptospirosis in Korea. Using the serum microagglutination test for 19 serogroups, it was shown that two of 26 rats (Rattus rattus) had antibodies to Leptospira canicola. When data for domestic animals were included, the most prevalent (nearly 50%) serogroup was Leptospira canicola.

Fast imaging using subencoding data sets from multiple detectors.

A new fast imaging method using a subencoding data acquisition scheme and a multiple coil receiver system is proposed and demonstrated. In this method, a set of aliased images are produced from receiver coils by using the subencoded data without sacrificing the desired resolution, and resolved to an aliasing-free image by using the distance-dependent sensitivity information of each coil. The reduction rate of data acquisition time is proportional to the number of receiver coils. This method can be easily adapted to conventional imaging methods including fast imaging to further reduce the scan time.

Application of single-shot spiral scanning for volume localization.

A new technique using a spiral scan single-shot RF pulse for localized volume selection has been developed and its experimental results are presented. This technique employs an additional radial-gradient coil in conjunction with the oscillating gradients for the spiral scan to localize the 3D volume. The short selection time in this technique minimizes both signal contamination from unwanted regions and signal attenuation due to T2 decay. We provide both the theoretical background of the technique and the experimental results obtained from a phantom as well as a human volunteer. The proposed method appears simple and accurate in localizing a volume which would be used as either fast imaging or localized spectroscopy.

Radial scanning technique for volume selective 31P spectroscopy.

An interlaced radial scanning method that is ideally suited for 31P spectroscopy with short T2 components and a wide spectral range is presented. The proposed method, which uses an additional radial gradient and radial scans in the k-space, minimizes T2 decay during the selection time and also optimizes the volume selectivity in a given gradient field strength. Simulation and experimental results with a short selection time of 2 ms demonstrate that the proposed method is suitable for volume selective 31P spectroscopy.

Cyclic adenosine monophosphate can convert epidermal growth factor into a differentiating factor in neuronal cells.

The rat pheochromocytoma (PC12) cell line is a model for studying the mechanism of growth factor action. Both epidermal growth factor and nerve growth factor stimulate mitogen-activated protein (MAP) kinase in these cells. Recent data suggest that the transient activation of MAP kinase may trigger proliferation, whereas sustained activation triggers differentiation in these cells. We have tested this model by asking whether agents that stimulate MAP kinase without inducing differentiation can act additively to trigger differentiation. Neither forskolin nor epidermal growth factor can stimulate differentiation, yet both activate MAP kinase in these cells. Together, their actions on MAP kinase are synergistic. Cells treated with both agents differentiate, measured morphologically and by the induction of neural-specific genes. We propose that cellular responses to growth factor action are dependent not only on the activation of growth factor receptors by specific growth factors but on synchronous signals that may elevate MAP kinase levels within the same cells.

A novel mitogen-activated protein kinase phosphatase. Structure, expression, and regulation.

Mitogen-activated protein (MAP) kinase lies at the convergence of various extracellular ligand-mediated signaling pathways. It is activated by the dual-specificity kinase, MAP kinase kinase or MEK. MAP kinase inactivation is mediated by dephosphorylation via specific MAP kinase phosphatases (MKPs). One MKP (MKP-1 (also known as 3CH134, Erp, or CL100)) has been reported to be expressed in a wide range of tissues and cells. We report the identification of a second widely expressed MKP, termed MKP-2, isolated from PC12 cells. MKP-2 showed significant homology with MKP-1 (58.8% at the amino acid level) and, like MKP-1, displayed vanadate-sensitive phosphatase activity against MAP kinase in vitro. Overexpression of MKP-2 in vivo inhibited MAP kinase-dependent gene transcription in PC12 cells. MKP-2 differed from MKP-1 in its tissue distribution and in its extent of induction by growth factors and agents that induce cellular stress, suggesting that these MKPs may have distinct physiological functions.

Cloning and expression of two structurally distinct receptor-linked protein-tyrosine phosphatases generated by RNA processing from a single gene.

We describe here the first example of RNA processing generating two functional receptor-linked protein-tyrosine phosphatases (PTP) (protein-tyrosine-phosphate phosphohydrolase, EC 3.1.3.48) that are structurally distinct within their catalytic domains. Two cDNAs, PTP-P1 and PTP-PS, were isolated from rat pheochromocytoma cells, which encode two receptor-linked protein-tyrosine-phosphatases and are produced by alternative splicing and differential use of polyadenylation sites. Both cDNAs share an identical extracellular domain and a single transmembrane domain, but differ within their cytoplasmic regions: PTP-P1 contains two tandem repeated PTPase catalytic domains, whereas PTP-PS contains only the amino-terminal domain. Bacterial expression of PTPase domains of both cDNAs demonstrates that PTP-P1 and PTP-PS contain tyrosine-phosphatase activity. PTP-P1 is encoded by three transcripts of approximately 8, 6, and 4 kilobases, whereas PTP-PS is encoded by a single 4.8-kilobase transcript. PTP-P1 (6 kilobases) and PTP-PS are mainly expressed within the brain and in neuronal and endocrine cells. These data suggest that PTP-P1 and PTP-PS may be involved in neuronal function.

A comparison of the effectiveness of primidone versus carbamazepine in epileptic outpatients.

Prior to the release of carbamazepine for the treatment of patients with psychomotor and grand mal seizures, primidone was regarded as the drug of choice for these disorders, especially when combined with diphenylhydantoin (DPH). It was, therefore, of interest to compare the effectiveness of carbamazepine against primidone when added to a therapeutic dose of DPH. Forty-five patients completed a 6-month study with each patient serving as his own control. The patients were initially stabilized on therapeutic doses of DPH and one of the test compounds, while all other medications were withdrawn. After 3 months of treatment, they were transferred onto the other drug for a second 3-month period. Extensive laboratory testing, including anticonvulsant levels, electroencephalograms, and neuropsychological evaluations, was performed. For the most part, the patients remained on outpatient status, returning for reports of seizure frequency, side effects, and laboratory studies every 14 days. The study was conducted in a single blind fashion by the treating neurologists; double blind by the electroencephalographer and psychologists. The results indicated that the two drugs did not differ in their effectiveness on seizure control. There were somewhat more side effects--none serious--with carbamazepine than with primidone. The EEG showed increased fast activity with primidone and increased theta activity with carbamazepine. There was no difference in regard to decrease of electroencephalographic seizure discharges. The patients showed more impairment on a repeatable neuropsychological test battery with primidone than with carbamazepine, and they also showed an increase on the psychopathic deviate scale of the Minnesota Multiphasic Inventory. Depressive feelings, when present, lessened while under treatment with carbamazepine. The results suggest that patients with the seizure types under consideration and who do not respond to DPH alone or to a DPH-phenobarbital combination can be placed on either carbamazepine or primidone while phenobarbital is discontinued. A patient who is intellectually and emotionally intact with no past history of behavioral disturbances may do better on primidone than carbamazepine, because this drug gives fewer side effects. On the other hand, those patients who have a past history of emotional and/or intellectual disturbances may profit more from carbamazepine.

cAMP activates MAP kinase and Elk-1 through a B-Raf- and Rap1-dependent pathway.

Cyclic adenosine monophosphate (cAMP) has tissue-specific effects on growth, differentiation, and gene expression. We show here that cAMP can activate the transcription factor Elk-1 and induce neuronal differentiation of PC12 cells via its activation of the MAP kinase cascade. These cell type-specific actions of cAMP require the expression of the serine/threonine kinase B-Raf and activation of the small G protein Rap1. Rap1, activated by mutation or by the cAMP-dependent protein kinase PKA, is a selective activator of B-Raf and an inhibitor of Raf-1. Therefore, in B-Raf-expressing cells, the activation of Rap1 provides a mechanism for tissue-specific regulation of cell growth and differentiation via MAP kinase.

Relationship of MICs to efficacy of cefotaxime in treatment of Streptococcus pneumoniae infections.

In June 1993, the National Committee for Clinical Laboratory Standards (NCCLS) recommended stringent new interpretive guidelines for antibiotics indicated for Streptococcus pneumoniae meningitis. To assess the predictive values of the recommended breakpoints, retrospective data were collected from patients who had S. pneumoniae infections and were treated with cefotaxime monotherapy. Susceptibilities based on the NCCLS interpretative categories were compared with clinical and bacteriologic outcomes. In 76 evaluable patients, the most common infections were bacteremia-septicemia (n = 49), meningitis (n = 37), and lower respiratory tract infection (n = 14). Under the NCCLS breakpoints proposed in 1993, 55 isolates would have been classed as susceptible to cefotaxime (MIC, < or = 0.25 microgram/ml), 18 would have been classed as intermediate (MIC, 0.5 to 1.0 microgram/ml), and 2 would have been classed as resistant (MIC, > or = 2 micrograms/ml). Of 75 cefotaxime-treated patients for whom cefotaxime MICs were recorded, 73 were clinically cured or improved (37 of 37 with meningitis and 36 of 38 with other infections). One case of bacteremia and one case of bone-and-joint infection were scored as therapeutic failures because initial monotherapy had to be modified because of an adverse drug reaction. Excluding these patients, there were 18 patients infected with S. pneumoniae that would have been classed as not fully susceptible (i.e., MICs > or = 0.5 microgram/ml); all of these patients were cured or improved. The results of this analysis demonstrate that successful treatment with cefotaxime did not correlate well with the guidelines for the susceptibility of pneumococcal isolates to either penicillin or cefotaxime established by the 1993 NCCLS breakpoint recommendations. Because of this study and other similar findings, the NCCLS adopted more clinically relevant guidelines in 1994.