Catalytic MTO-based C–H insertion reactions of hydrogen peroxide: an investigation on the polymeric support role in heterogeneous conditions

Polymer-supported methyltrioxorhenium (MTO) compounds are shown to act as efficient and selective catalysts for the oxy-functionalization of C–H bonds in representative hydrocarbon derivatives (leading to the corresponding alcohols or ketones), using H₂O₂ as oxidant. The different supports used for the heterogenation of MTO, such as poly(4-vinylpyridine), poly(4-vinylpyridine)-N-oxide and polystyrene resins, all showed different catalytic behaviour in terms of substrate conversion and product yield, depending on the experimental conditions used. It is noteworthy that the novel heterogeneous catalysts were found to be stable, it being possible to effect their recover and recycle at least five times without appreciable loss of activity.     

Effect of dietary versus pharmacological correction of hypertriglyceridemia on red blood cell membrane sodium/lithium countertransport activity

An elevated red blood cell Na/Li countertransport (Na/Li CT) is often associated with high blood pressure and metabolic abnormalities. Recent studies suggested that a reduction in serum TG levels is associated with a decrease in Na/Li CT activity. However, it is still unclear if this phenomenon could be originated from systemic metabolic alterations or from modifications of the membrane dynamic properties. Aim of the present study was to investigate whether dietary or pharmacological TG lowering therapy might have a different effect on Na/Li CT activity and related metabolic parameters. Twenty normotensive hyper-TG patients were recruited from the Lipid outpatient Clinic: they had a baseline Na/Li CT activity significantly higher compared with age- and BMI-matched normolipidemic controls (386+/-33 vs 274+/-39 umol/l RBC/h, p<0.05). The patients were randomly prescribed one of the following two-months treatment: Group 1)-triglyceride lowering diet; Group 2)-lipid lowering drug (Gemfibrozil 600 mg b.i.d.). Na/Li CT and metabolic and anthropometric variables were measured at baseline and after 1 and 2 months of treatment. At the end of intervention, there was in both groups a significant and comparable fall in plasma triglyceride (group 1: -2.61+/-0.73 mmol/l p<0.01; group 2: -4.29+/-1.20 mmol/l p<0.01). In the diet-treated group there were, in addition small but significant reductions in body weight (-3.7+/-0.8 kg p<0.01), fasting glucose (-0.36+/-0.14 mmol/l p<0.05) and insulin levels (-2.1+/-0.5 mU/l, p<0.01), while no such changes were observed in the fibrate treated patients. Na/Li CT activity was significantly and comparably reduced at the end of treatment in both groups (group 1: -97+/-28 umol/l cell/h, p<0.01; group 2: -89+/-30 umol/l cell/h, p<0.01). In conclusion, these results indicate that the decrease in Na/Li CT associated with both dietary and drug treatment of hypertriglyceridemia is to be traced to a direct effect of plasma TG concentration on this transport system (probably as a result of modification in the membrane lipid environment) rather than to changes in plasma insulin levels or insulin resistance.     

Long-term follow-up results of alpha-interferon-based regimens in patients with late chronic phase chronic myelogenous leukemia

The aim of this analysis was to evaluate the efficacy of alpha-interferon (alpha-IFN) regimens in late chronic phase (diagnosis >12 months) chronic myelogenous leukemia (CP-CML). Long-term follow-up results were evaluated in 137 patients with Philadelphia chromosome (Ph)-positive late CP-CML. The alpha-IFN programs were sequential studies with human leukocyte alpha-IFN (seven patients), recombinant alpha-IFN alone (15 patients) or with IFN-gamma (29 patients), hydroxyurea (HU) (19 patients), or low-dose cytarabine (Ara-C) (67 patients). Overall, 57% of the patients achieved complete hematological response (CHR), and 7% obtained partial hematological response. Nineteen patients (15% of the 123 evaluable patients) had a cytogenetic response which was major (Ph-positive <35%) in 10 patients (8%). A trend for better responses was observed with shorter disease duration. The median overall survival from start of therapy was 49 months, with an estimated 5-year survival rate of 41%. Some common pretreatment prognostic factors associated with response did not show statistical associations when applied in late CP-CML; however, characteristics such as smaller spleen size, and lower percentages of peripheral blood and marrow blasts and basophils were associated with better survival experience. When patients were subgrouped according to risk, no significant differences in the incidence of cytogenetic response and in survival outcomes were observed among various risk groups. This study confirms that alpha-IFN-based regimens have a modest activity in late CP-CML, and supports the need to develop investigational strategies aimed at improving patient prognosis in this phase.     

Synaptic current at the rat ganglionic synapse and its interactions with the neuronal voltage-dependent currents

The membrane current activated by fast nicotinic excitation of intact and mature rat sympathetic neurons was studied at 37 degrees C, by using the two-microelectrode voltage-clamp technique. The excitatory postsynaptic current (EPSC) was modeled as the difference between two exponentials. A fast time constant (tau2; mean value 0.57 ms), which proves to be virtually voltage-independent, governs the current rise phase and a longer time constant (tau1; range 5.2-6.8 ms in 2 mM Ca2+) describes the current decay and shows a small negative voltage dependence. A mean peak synaptic conductance of 0.58 muS per neuron is measured after activation of the whole presynaptic input in 5 mM Ca2+ external solution (0.40 muS in 2 mM Ca2+). The miniature EPSCs also rise and decay with exponential time constants very similar to those of the compound EPSC recorded at the same voltage. A mean peak conductance of 4.04 nS is estimated for the unitary event. Deconvolution procedures were employed to decompose evoked macrocurrents. It is shown that under appropriate conditions the duration of the driving function describing quantal secretion can be reduced to <1 ms. The shape of the EPSC is accurately mimicked by a complete mathematical model of the sympathetic neuron incorporating the kinetic properties of five different voltage-dependent current types, which were characterized in a previous work. We show that IA channels are opened by depolarizing voltage steps or by synaptic potentials in the subthreshold voltage range, provided that the starting holding voltage is sufficiently negative to remove IA steady-state inactivation (less than -50 mV) and the voltage trajectories are sufficiently large to enter the IA activation range (greater than -65 mV). Under current-clamp conditions, this gives rise to an additional fast component in the early phase of membrane repolarization-in response to voltage pulses-and to a consistent distortion of the excitatory postsynaptic potential (EPSP) time course around its peak-in response to the synaptic signal. When the stimulation initiates an action potential, IA is shown to significantly increase the synaptic threshold conductance (up to a factor of 2 when IA is fully deinactivated), compared with that required when IA is omitted. The voltage dependence of this effect is consistent with the IA steady-state inactivation curve. It is concluded that IA, in addition to speeding up the spike repolarization process, also shunts the excitatory drive and delays or prevents the firing of the neuron action potential.     

Early treatment decisions with interferon-alfa therapy in early chronic-phase chronic myelogenous leukemia

PURPOSE: To determine, in patients with Philadelphia chromosome (Ph)-positive chronic myelogenous leukemia (CML) on interferon alfa (IFNalpha), whether combining pretreatment characteristics and early response profiles would distinguish patients with differential benefits that would allow better decisions on subsequent therapy. PATIENTS AND METHODS: A total of 274 patients treated from 1982 through 1990 with IFNalpha regimens were analyzed. A second group of 137 patients treated with IFNalpha and low-dose cytarabine (ara-C) between 1990 and 1994 was later used to confirm the guidelines derived from the original study group analysis. Patients' pretreatment factors and response to IFNalpha therapy at 3, 6, and 12 months were analyzed in relation to subsequent achievement of major cytogenetic response. After univariate analysis of prognostic factors, a multivariate analysis selected, at 6 months, independent pretreatment factors that added to the response status in predicting subsequent outcome. The results were then applied at the 3- and 12-month periods and confirmed in the subsequent population. RESULTS: Response to IFNalpha therapy at 3, 6, and 12 months was a significant predictor of later major cytogenetic response. The presence of splenomegaly > or = 5 cm below the costal margin (BCM) or thrombocytosis > or = 700 x 10(9)/L pretreatment added significant independent prediction to response. At 6 months, patients with a partial hematologic response (PHR) or resistant disease had a less than 10% chance of achieving a later major cytogenetic response, as were those in complete hematologic response (CHR) and who had pretreatment splenomegaly and thrombocytosis. Applying the model at 3 months showed that only patients with < or = PHR and pretreatment splenomegaly or thrombocytosis at 3 months had such a low major cytogenetic response rate. Finally, at 12 months, patients with CHR still had a 15% to 25% chance of having a major cytogenetic response later if they did not have pretreatment splenomegaly and thrombocytosis. CONCLUSION: This analysis allows better selection of patients with Ph-positive CML on IFNalpha therapy for continuation of IFNalpha versus changing therapy early in the course of CML. For treatment programs that choose to change patients to other investigational therapies (eg, intensive chemotherapy and/or autologous stem-cell transplantation [SCT]), baseline outcome expectations are provided for patients continued on IFNalpha therapy, against which the results of new approaches can be compared.     

Identification of the chromosome 14 origin of a C-negative marker associated with a 14q32 deletion by chromosome painting

A constitutional chromosome 14 rearrangement was observed in a female with a psychodevelopmental disorder. Karyotype analysis using a variety of chromosome techniques, QFQ, GTG, CBG, Ag-NOR and DA-DAPI, showed a deletion of chromosome 14q32.1-qter region in association with a supernumerary marker chromosome. The marker, resembling a submetacentric, approximately half the size of a G group chromosome is C band and Ag-NOR negative. The heteromorphism of the satellites showed that the deleted chromosome 14 is paternal in origin. Chromosome painting using an Alu-PCR probe specific for the human chromosome 14 and fluorescent in situ hybridization (FISH) showed that the marker contains chromosome 14q32 sequences. It is likely that the marker was generated from the deleted chromosome 14 region through a complex rearrangement.     

Phase separation and gelation of epoxy resin/hyperbranched polymer blends

The structural buildup during reticulation of thermoset systems containing reactive modifiers can strongly influence the final properties of such blends. This was studied by considering the rheological behavior during cure of an epoxy/amine thermoset system blended with reactive dendritic hyperbranched polymers (HBPs). Depending on the chemical structure of the HBP used in the blend, a phase separation could be observed. The onset and offset of the phase separation process could be detected by observing the evolution of the viscoelastic properties. The phase separation onsets obtained by rheological measurements were compared with the values obtained by traditional cloud point observations. Good agreement between the two techniques was observed. Hyperbranched polymers that did not phase separate during the curing process were used to study gelation phenomena and its dependence on the reactivity and functionality of the HBP. The gelation of the homogeneous blend system using the Flory‐Stockmayer theory was also modeled. This highlighted the influence of both functionality and reactivity of the components, and the appearance of co‐operative polymerization mechanisms in homogeneous blends.     

Redundant system of passive markers for ultrasound scanhead tracking

Scanhead tracking by opto-electronic (OE) systems allows high accuracy in three-dimensional (3-D) freehand ultrasound imaging. In this paper, a new set of methods is proposed and compared with the standard approach [Gram-Schmidt method (GS)]. Three redundancy-based algorithms are introduced to compensate for possible loss of markers during data acquisition: regression plane (RP), multiple Gram-Schmidt (MGS), and center of mass least square (CMLS). When combined with the ultrasound instrument, the root-mean-squared (RMS) uncertainty in locating target points, over a working volume of 420 mm x 490 mm x 100 mm, improved by 7% and 24% using MGS and CMLS method respectively, compared to GS. A lower improvement was obtained with RP methods (5%), using the best marker configuration. In conclusion, CMLS method provides a robust and accurate procedure for 3-D freehand ultrasound scanhead tracking, able to manage possible loss of markers, with interesting perspectives for image fusion and body referenced 3-D ultrasound.     

Understanding foods as soft materials

Foods make up some of the most complex examples of soft condensed matter (SCM) with which we interact daily. Their complexity arises from several factors: the intricacy of components, the different aggregation states in which foods are encountered, and the multitude of relevant characteristic time and length scales. Because foodstuffs are governed by the rules of SCM physics but with all the complications related to real systems, the experimental and theoretical approaches of SCM physics have deepened our comprehension of their nature and behaviour, but many questions remain. In this review we discuss the current understanding of food science, by considering established SCM methods as well as emerging techniques and theoretical approaches. With their complexity, heterogeneity and multitude of states, foods provide SCM physics with a challenge of remarkable importance.     

PCBs and selected organochlorine compounds in Italian mountain air: the influence of altitude and forest ecosystem type

Passive air samplers (polyurethane foam disks) were deployed on an altitudinal transect in the rural Italian Alps to investigate the potential influence of forest cover on air concentrations. Samplers were exposed overtwo periods, each of several weeks, either in clearings or in forests. In the first period, there was high leaf coverage (high leaf area index, LAI); in the second, the LAI was low after the autumnal leaf fall. PCBs sequestered in the PUF generally declined with altitude, for example, in the clearings PCBs-28, 52, 90/101, 118, and 138, all showed statistically significant declines (p < 0.05). The mass of HCB sequestered increased with altitude, evidence of cold condensation. Ratios of the forest:clearing concentrations were calculated; this ratio expresses the filtering ability of forests to deplete air concentrations compared to the adjacent clearings. During the high LAI sampling period, these depletion factors ranged between 0.93 and 0.54 and were inversely correlated with temperature-corrected log K0A. This relationship was notobserved during the low LAI sampling period. The depletion factors were normalized using the LAI to give a density independent depletion factor (DIDF). The slopes of the correlations with K0A were comparable for broadleaf or coniferous forests at different altitudes, suggesting that leaf surfaces determine the exchanges with air. Broadleaf forests at 1000 and 1400 m showed similar behavior, while a conifer forest at 1800 m gave depletion factors which were higher by about a factor of 2. It is suggested that DIDF can be used in regional environmental fate models to estimate the contribution of forests to contaminant fate.