Peptide labeling using 188Re, 188Re-MAG3 and 153Sm-H1ETA: A comparison on their in vitro lipophilicity

Lanreotide peptide was labeled with ¹⁵³Sm-H₁ETA and ¹⁸⁸Re-MAG₃ in order to evaluate whether or not their conjugation to the peptide produce significant differences of the in vitro lipophilicity with respect to the ¹⁸⁸Re-lanreotide prepared by the direct labeling method (highly lipophilic). The differences of lipophilicity between the complexes, were evaluated using a reverse phase HPLC system. The measured lipophilicity of ¹⁵³Sm-H₁ETA-lanreotide, ¹⁸⁸Re-MAG₃-lanreotide and ¹⁸⁸Re-lanreotide was taken to be the capacity factor [k" = (t _R-t ₀)/t ₀ where t _R is the retention time and t ₀ is the dead time] for each of the complexes under identical chromatography conditions. Results showed that the in vitro lipophilicity decreased in the order ¹⁸⁸Re-lanreotide (direct labeling), ¹⁸⁸Re-MAG₃-lanreotide and ¹⁵³Sm-H₁ETA-lanreotide. Since the last one has a capacity factor (k") similar to that of ¹⁸⁸Re-MAG₃, some renal elimination for ¹⁵³Sm-H₁ETA-lanreotide could be expected, which probably would reduce the unnecessary radiation dose to normal tissues.     

Mixed C18 and C1 modification on an optical fiber for chromatographic sensing

An optical fiber-chromatographic sensor, aiming at simultaneous and selective response to multiple components following a chromatographic separation, is described. We report an improved approach for immobilization of octadecyl (C(18)) and methyl (C(1)) moieties as stationary phase on an optical fiber suitable as a sensing phase for organic solutes. By this approach, the stability and lifetime of the sensing layer as well as the detectability and retention behavior of the chromatographic sensor could be improved. Infrared spectroscopy was employed to confirm the presence of C(18) and C(1) moieties on the modified surface of the optical fiber. The chromatographic sensor was applied, with good sensitivity and chemical selectivity, to the simultaneous separation and detection of bromobenzene and toluene, using water as the mobile phase.     

Nanoscale organization of the pathogen receptor DC-SIGN mapped by single-molecule high-resolution fluorescence microscopy.

DC-SIGN, a C-type lectin exclusively expressed on dendritic cells (DCs), plays an important role in pathogen recognition by binding with high affinity to a large variety of microorganisms. Recent experimental evidence points to a direct relation between the function of DC-SIGN as a viral receptor and its spatial arrangement on the plasma membrane. We have investigated the nanoscale organization of fluorescently labeled DC-SIGN on intact isolated DCs by means of near-field scanning optical microscopy (NSOM) combined with single-molecule detection. Fluorescence spots of different intensity and size have been directly visualized by optical means with a spatial resolution of less than 100 nm. Intensity- and size-distribution histograms of the DC-SIGN fluorescent spots confirm that approximately 80 % of the receptors are organized in nanosized domains randomly distributed on the cell membrane. Intensity-size correlation analysis revealed remarkable heterogeneity in the molecular packing density of the domains. Furthermore, we have mapped the intermolecular organization within a dense cluster by means of sequential NSOM imaging combined with discrete single-molecule photobleaching. In this way we have determined the spatial coordinates of 13 different individual dyes, with a localization accuracy of 6 nm. Our experimental observations are all consistent with an arrangement of DC-SIGN designed to maximize its chances of binding to a wide range of microorganisms. Our data also illustrate the potential of NSOM as an ultrasensitive, high-resolution technique to probe nanometer-scale organization of molecules on the cell membrane.     

Preparation and electrochemical behavior of ordered rh adlayers on Pt(100) electrodes

Rhodium adlayers on Pt(100) substrates have been prepared by electrodeposition from dilute Rh(III) acidic solutions. The initially disordered layer is electrochemically annealed by applying a polarization program consisting of high-sweep-rate multicycle sequences between 0.05 and 0.78 V(RHE) in 0.1 M H(2)SO(4). In this way, a pseudomorphic Rh monolayer can be prepared on Pt(100) substrates. The degree of order of the electrochemically annealed layer has been evidenced not only through voltammetric experiments but also by means of scanning tunneling microscopy with atomic resolution for iodine-protected adlayers, which show a c(2 x 2) structure. The electrochemically induced ordering of the Rh adlayer appears to be a consequence of the repeated cycles of adsorption/desorption of H and, especially, oxygenated species. Voltammetry in sulfuric acid solutions permits examination of the energetics of H/anions and OH/O adsorption as a function of the Rh coverage. The first monolayer adsorbs both hydrogen and oxygenated species more strongly than the second one. This can be explained through an electronic effect caused by the underlying Pt(100) substrate.     

2-Diphenylphosphinoyloxybenzaldehyde 4-Nitrophenyl-, 4-Phenyl-1-phthalazinyl-, and Aroylhydrazones and Thiosemicarbazone

Condensation of aryl- and aroylhydrazines and thiosemicarbazide with 2-diphenylphosphinoyloxybenzaldehyde results in formation of the corresponding hydrazones and thiosemicarbazone. The products give rise to conformational equilibrium between rotational and Z,E isomers, which is strongly displaced toward the E,E',Z' isomer and is determined by the nature of substituent in the hydrazine fragment.     

Mechanical analysis on rocket propellants

The mechanical properties of solid rocket propellants are very important for good functioning of rocket motors. During use and storage the mechanical properties of rocket propellants are changing, due to chemical and mechanical influences such as thermal reactions, oxidation reactions or vibrations. These influences can result in malfunctioning, leading to an unwanted explosion of the rocket motor. Most of modern rocket propellants consist of a polymer matrix (i.e. HTPB) filled with a crystalline material (i.e. AP, AN). However, the more conventional double base propellants consist of a solid gel matrix with additives, such as stabilizers. Both materials show a mechanical behaviour, quite similar to that of general polymers. To describe the material behaviour of both propellants a linear visco-elastic theory is often used to describe the mechanical behaviour for small deformations. Because the time-temperature dependency is also valid for these materials a mastercurve can be constituted. With this mastercurve the response properties (stiffness) under extreme conditions can be determined. At TNO-PML a mastercurve of a double base propellant was constituted using dynamical mechanical analysis (DMA) and compared with a mastercurve reduced from conventional (static) stress relaxation tests. The mechanical properties of this double base propellant determined by DMA were compared with conventional (quasi-static) tensile test results. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of the Presence of CO2 in the Feed of an Indirect Heating TSA Process for VOC Removal

This work deals with an experimental study of an indirect temperature swing adsorption process for VOC removal from air or for gas purification. A 1 m long and 70 mm diameter column with an internal heat exchanger has been filled with Ambersorb 600 carbonaceous adsorbent. This column is equipped with sensors to measure temperature at several points inside the bed, as well as the inlet and outlet gas concentration, pressure, temperature and mass flow. In a first step, CO₂ or ethane/dry nitrogen mixtures were used to simulate a single VOC in air, with different concentrations (350 ppm, 1% and 10%). As a first results very effective gas purification was obtained and an advantage of this process is the high pollutant concentration during the regeneration phase. Experiments were performed with various ethane/CO₂ mixtures. The influence of the presence of CO₂ on the ethane concentration breakthrough curves and on the ethane concentration during regeneration is reported. The IAS theory was used, as a first approach, to predict the adsorbed pollutants amount. Relatively good prediction is obtained with a maximum error in the order of 10%. An energy balance study is reported as well.     

Highly sensitive method for the determination of a new anthracycline: Pirarubicin

Summary A new and highly sensitive HPLC method for the simultaneous determination of pirarubicine (THP-doxorubicin) and its metabolites, adriamycin and adriamycinol, in human plasma, is described. Samples were treated by liquid-liquid extraction, the organic phase removed and the residue dissolved in methanol. Separation was on a Lichrocart Supersher RP 8 column, (250×4 mm) 4 m, with a mobile phase of acetonitrile/methanol/formate-buffer.     

Catalytic nitrobenzene oxidation of lignins

Alkaline nitrobenzene oxidation of hardwood and softwood lignins in the presence of redox and phase-transfer catalysts was studied. The selectivity of oxidation of lignins increased by 1.7 to 1.9 times. A possible mechanism of catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3004–3007, December, 1996.