On the semi-empirical mass-formula and alpha-disintegration energy in the region of heavy and medium heavy nuclides

In the present paper it has been shown that Fermi’s semi-empirical atomic mass-formula is inadequate for the estimation of alpha-disintegration energy in the medium heavy and heavy nuclide-regions. A suitable correction-term has been added to the mass-formula based on Duckworth’s new atomic masses and similar to the one proposed by Stern for heavy elements (A?208). It is seen that the calculated alpha-decay energies are in numerical agreement with the observed data except for the magic number nuclei which can be satisfactorily explained on the nuclear shell-structure. But even in the latter case the agreement with the experimental results is better when the correction-term is used.     

Spin-deposited nanocrystalline lithium ferrite thin films: Fabrication and characterization

Thin films of lithium ferrite (with general composition Li_0.5Fe_2.5O₄) were fabricated at low temperatures (up to 650 °C) by citrate-route using spin-deposition technique. Deposited films consisted of nanometer-sized grains as evidenced by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. XRD patterns for annealed films showed broad peaks exhibiting a spinel phase. Size of nanocrystallites is estimated to be 3-7 nm using Scherrer's equation. Average grain size ∼8.5 nm is observed from TEM images of films annealed at 650 °C. Scanning electron micrographs show the formation of spherical aggregates of around 130 nm in diameter. The AFM analysis clearly evidenced the development of nanograins even at low (∼500 °C) annealing temperatures. Significant decrease in complex dielectric permittivity (∈′ − j∈″) with frequency is observed in the low frequency (100 Hz-1 MHz) as well as in X-band microwave frequency (8-12 GHz) region. ∈′ is found to be in the range of 15.7-33.9 in low frequency region, whereas in X-band microwave frequency region, it is found to lie between 3.9 and 4.9. Similarly, ∈″ is found to be 0.16-5.9 in the low frequency region, and 0.002-0.024 in the X-band microwave frequency region. Room temperature dc resistivity of these films is estimated to lie in the range of 10⁶-10⁸ Ω cm. These results strongly suggest that citrate-route processed nanocrystalline lithium ferrite thin films are promising candidates for monolithic microwave integrated circuits (MMICs).     

Fast atom bombardment mass spectra of monosulphonated merocyanine dyestuffs

The FAB mass spectra of four sulphonated merocyanine dyes are investigated. Negative ion spectra are superior to those in the positive ion mode. The special structure of merocyanines with an acidic group at one end of the molecule and a basic group at the other leads to significantly different fragmentation pathways for positive and negative ions.     

Das Verhalten disubstituierter Benzole RC6H4Si(CH3)2F bei Elektronenstoß

The electron impact induced fragmentation of disubstituted benzenes of the formulae RC₆H₄Si(CH₃)₂F (R ? p-N(CH₃)₂, p-OCH₃, p-, m-CH₃, H, p-, m-CI, p-, m-Br and p-NO₂), results mainly in an elimination of a methyl radical from the molecular ion. The activation energies for this fragmentation have been measured. The intensities of the molecular and fragment ions, as well as the activation energy, depend upon the substituent R. The change in the activation energy can be explained by the influence of the substituent on the charge distribution of the molecular ions. The activation energies have been calculated using the approximate quantum chemical method of Pariser, Parr and Pople. Calculated and experimental values agree within an order of magnitude and in the dependence on the substituent. The connection of the activation energy with the peak intensity in the mass spectra has been confirmed by intensity calculations on the basis of the quasi-equilibrium theory.     

Application of the combination of isotope ratio monitoring with isotope dilution mass spectrometry to the determination of glucose in serum

Isotope ratio monitoring combined with n((13)C)/n((12)C) isotope dilution mass spectrometry (IRM/IDMS) provides results of low uncertainty of the order of 0.1% if it is applied to the analysis of simple mixtures as found in organic chemistry, even if only low (13)C spike additives to the sample are used. If the method is applied to the analysis of systems that require large-scale sample preparation prior to the measurement, such as the determination of glucose in serum, the results obtained exhibit a higher uncertainty that is comparable to that of the conventional gas chromatography/isotope dilution mass spectrometry (GC/IDMS) method. The reason for this observation is that the small contribution that the IRM/IDMS method makes to the uncertainty budget of the result is superimposed on a large contribution due to the sample preparation. It appears therefore that the IRM/IDMS method has no advantage over the conventional GC/IDMS method. However, if a series of measurements is carried out, and if a suitable experimental design is chosen, the IRM/IDMS method can provide valuable additional information. The influence of sample preparation on each individual result can be quantified as its deviation from the average value of all results of the series. From these data conclusions can be drawn for an improvement in sample preparation.     

Elektrometrische Untersuchungen über die Komplexbildung von La(III) mit 3.5-Dinitrosalicylsäure

Zusammenfassung Die Komplexbildung zwischen La(III) und 3.5-Dinitrosalicylsäure in 0.1m-KNO₃ wurde potentiometrisch und konduktometrisch untersucht. Wir erforschten die Bildung von 11- und 12-Komplexen oberhalb pH 3.5. Der 11-Komplex bildet sich in Lösung, während der 12-Komplex ausfällt. Die Stabilitätskonstante des 11-Komplexes wurde durch Anwendung der vonCalvin undMelchior erweiterten Methode vonBjerrum bestimmt. Für logK fand man Werte von 4.92, 5.00 und 5.12 bei 25°, 30°, beziehungsweise 35° C. Die Werte für F, H und S wurden für 30° C berechnet und bestimmt zu–6.97 Kcal/Mol,–7.49 Kcal/Mol, beziehungsweise –1.70 cal/Mol/Grad.

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Electromeric studies on the complex formation between La(III) and 3.5-dinitrosalicylic acid

The complex formation between La(III) and 3.5-dinitrosalicylic acid in 0.1m-KNO₃ medium has been studied potentiometrically and conductometrically. The formation of 11 and 12 complexes beyond 3.5 pH was investigated. 11 complex is formed in solution while 12 complex is precipitated. The stability constant of the 11 complex was determined by applying the Calvin and Melchior's extension ofBjerrum's method. The logK values have been found to be 4.92, 5.00, and 5.12 at 25, 30 and 35°C, respectively. The values of F, H, and S have also been evaluated at 30°C and found to be–6.97 Kcal/mole,–7.49 Kcal/mole, and–1.70 Kcal/mole/degree, respectively.

     

LDL-mimetic lipid nanoparticles prepared by surface KAT ligation for in vivo MRI of atherosclerosis

Low-density lipoprotein (LDL)-mimetic lipid nanoparticles (LNPs), decorated with MRI contrast agents and fluorescent dyes, were prepared by the covalent attachment of apolipoprotein-mimetic peptide (P), Gd(iii)-chelate (Gd), and sulforhodamine B (R) moieties on the LNP surface. The functionalized LNPs were prepared using the amide-forming potassium acyltrifluoroborate (KAT) ligation reaction. The KAT groups on the surface of LNPs were allowed to react with the corresponding hydroxylamine (HA) derivatives of P and Gd to provide bi-functionalized LNPs (PGd-LNP). The reaction proceeded with excellent yields, as observed by ICP-MS (for B and Gd amounts) and MALDI-TOF-MS data, and did not alter the morphology of the LNPs (mean diameter: ca. 50 nm), as shown by DLS and cryoTEM analyses. With the help of the efficient KAT ligation, a high payload of Gd(iii)-chelate on the PGd-LNP surface (ca. 2800 Gd atoms per LNP) was successfully achieved and provided a high r₁ relaxivity (r₁ = 22.0 s⁻¹ mM⁻¹ at 1.4 T/60 MHz and 25 °C; r₁ = 8.2 s⁻¹ mM⁻¹ at 9.4 T/400 MHz and 37 °C). This bi-functionalized PGd-LNP was administered to three atherosclerotic apoE^−/− mice to reveal the clear enhancement of atherosclerotic plaques in the brachiocephalic artery (BA) by MRI, in good agreement with the high accumulation of Gd in the aortic arch as shown by ICP-MS. The parallel in vivo MRI and ex vivo studies of whole mouse cryo-imaging were performed using triply functionalized LNPs with P, Gd, and R (PGdR-LNP). The clear presence of atherosclerotic plaques in BA was observed by ex vivo bright field cryo-imaging, and they were also observed by high emission fluorescent imaging. These directly corresponded to the enhanced tissue in the in vivo MRI of the identical mouse.

LDL-mimetic lipid nanoparticles, decorated with MRI contrast agents and fluorescent dyes, were prepared by the covalent attachments of an apoB100-mimetic peptide, Gd(iii)-chelate, and rhodamine to enhance atherosclerosis in the in vivo imaging.     

Deep eutectic solvent-mediated expedient multicomponent synthesis of oxazine scaffolds

A simple, efficient, and eco-friendly protocol for the synthesis of 1,3-oxazine derivatives, viz. 7-aryl-7,8-dihydro-6H-[1,3]dioxolo[4′,5′:4,5]benzo[1,2-e][1,3]oxazines and 3-aryl-3,4-dihydro-2H- naphtho[2,3-e][1,3]oxazine-5,10-diones, involving one-pot multicomponent condensation reaction of various amines and formaldehyde with sesamol/2-hydroxy-1,4-naphthoquinone, respectively, catalyzed by a choline chloride–oxalic acid deep eutectic solvent has been developed. The method offers several advantages, including mild reaction conditions, simple operating procedure, recyclable and biodegradable catalyst, short reaction times, and excellent yields of the target products.