Ferromagnetism in Metallocene-Doped Fullerenes

 Ferromagnetism in fullerene-based systems doped with metallocenes is reviewed. These compounds form a ferromagnetic state by spin-coupling between π electrons on fullerene units, while the metallocene molecules do not contribute to the spin ordering. One of these compounds has the highest critical temperature (19 K) for this class of compound. The magnetic properties of these materials are very strongly dependent on the crystallization conditions. Corresponding author. E-mail: Dragan.Mihailovic@ijs.si Received September 4, 2002; accepted September 6, 2002     

An Education in Robustness

A case study is presented of the application of robustness analysis to the choice of examination subjects to be made by a 14-year-old girl. The analysis is conducted in terms of the desirable future career options which may be preserved by different combinations of subjects, and also of the balance with topics selected for their intrinsic interest. The approach, which employs very limited technical apparatus, is justified on a number of grounds-in particular, the crucial importance of uncertainty, and the need for understanding and acceptance by a "client" very unlike the corporate manager. Some tentative conclusions are reached on the extension of such methods to other cases of decision-makers with little, if any, resources to control except their own lives.     

Methods for Determining the Re-order Point of an (<Emphasis Type="Italic">s</Emphasis>, <Emphasis Type="Italic">S</Emphasis>) Ordering Policy when a Service Level is Specified

This paper deals with a periodic review inventory system. Methods are discussed for determining the re-order point s of an (s, S) order policy, when a certain service level is required. The results differ from those presented for a (Q, s) model which is usually considered in literature and implemented in practice. Methods are discussed for determining the re-order point of an (s, S) policy when demand is normal or gamma distributed. A numerical investigation demonstrates the applicability of the described methods. In particular, it is shown that these methods are superior to a formula that is implemented in many inventory control systems.     

Atomic radical—molecule reactions F + CH<Subscript>3</Subscript>C≡CH: mechanistic study

The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions, i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical F attacking on the C≡C triple bond in propyne (CH₃C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H₂CCCHF + H via transition state TS₅/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons. This material is available from author via E-mail.     

Determination of acetaminophen by square wave voltammetry at a gold electrode modified by 4-amino-2-mercaptopyrimidine self-assembled monolayers

A 4-Amino-2-mercaptopyrimidine self-assembled monolayer (AMP SAMs/Au) modified gold electrode was prepared. The electrochemical behavior of acetaminophen on the AMP SAMs/Au was studied in Britton-Robinson (BR) buffer solution. Compared to a bare gold electrode, the modified electrode exhibits a significant enhancement in the oxidation current response for acetaminophen. The modified electrode was used for the determination of acetaminophen by square wave voltammetry. The oxidation current increased linearly with the concentration of acetaminophen in the range of 2.0 × 10⁻⁶−4.0 × 10⁻³ M. The modified electrode made it possible to eliminate the interference of dopamine (DA), brucine, epinephrine (EP), and norepinephrine (NE). The practical analytical utility was illustrated by the determination of acetaminophen in a commercially available drug. The text was submitted by the authors in English.     

Visualisation of interlaboratory comparison results in PomPlots

In this work a novel graphical method is applied to the presentation of intercomparison results. This is demonstrated with the results of a recent intercomparison in measuring the ¹³⁷Cs, ⁴⁰K, and ⁹⁰Sr activity concentration in milk powder. The “PomPlot”, an intuitive graphical method, is used for producing a summary overview of the participants’ results of a common measurand. The “PomPlot” displays (relative) deviations of individual results from the reference value on the horizontal axis and (relative) uncertainties on the vertical axis.     

Host–Guest Complexation of <Emphasis Type="Italic">β</Emphasis>-, <Emphasis Type="Italic">γ</Emphasis>-Cyclodextrin with Alkyl Trimethyl Ammonium Bromides in Aqueous Solution

As a continuation of our previous investigation, interactions between cyclodextrin (β-CD), γ-cyclodextrin (γ-CD) and alkyl trimethylammonium bromides in aqueous solutions have been studied with titration calorimetry and ¹H NMR at 298.15 K. The results are discussed in terms of the amphiphilic interaction of CD with surfactants and the iceberg structure formed by water molecules existing around the hydrophobic tail of surfactant molecules. The stoichiometry of the β-CD–surfactant system is 1:1 whereas that of the γ-CD–surfactant system is 1:2. The corresponding formation enthalpy (negative) of the complexes of the two systems decreases with an increase in the number of carbon atoms (n) in hydrophobic chain of surfactant molecule, C _n H_2n+1, whereas the entropy increases with the enlargement of n.     

Polymorphism of paracetamol

The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG _sub²⁹⁸=60.0 kJ mol⁻¹; ΔH _sub²⁹⁸=117.9±0.7 kJ mol⁻¹; ΔS _sub²⁹⁸=190±2 J mol⁻¹ K⁻¹. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition enthalpy at 298 K, ΔH _tr²⁹⁸(I→II)=2.0±0.4 kJ mol⁻¹, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based on ΔH _tr²⁹⁸ (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification II were also estimated (ΔG _sub²⁹⁸=56.1 kJ mol⁻¹; ΔH _sub²⁹⁸=115.9±0.9 kJ mol⁻¹; ΔS _sub²⁹⁸=200±3 J mol⁻¹ K⁻¹). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported found by classical thermochemical methods.     

Reversed-phase liquid chromatography and argentation chromatography of the minor capsaicinoids

An investigation of the liquid chromatography of the minor capsaicinoids in a commercial capsaicinoid mixture is reported. Twelve stationary phases including C₈, C₁₈, C₃₀, phenyl, and cation-exchange chemistries were examined in combination with isocratic aqueous methanol and aqueous acetonitrile mobile phases. A phenyl stationary phase and aqueous acetonitrile mobile phase baseline-resolved 7 of 11 capsaicinoids, and selected ion chromatograms (LC–ESI-MS) demonstrated this was the most effective reversed-phase separation. Argentation chromatography with an alkyl or phenyl column and aqueous silver nitrate–methanol mobile phase revealed the presence of the 6-ene-8-methyl and 6-ene-9-methyl homocapsaicin isomers and the absence of 7-ene-9-methyl homocapsaicin. A mixed phenyl–cation-exchange stationary phase (charged with silver ion) enabled unique and useful separations of the capsaicinoids.     

Photophysics of aromatic molecules with low-lying pi sigma* states: excitation-energy dependence of fluorescence in jet-cooled aromatic nitriles

Excitation-energy dependence of fluorescence intensity and fluorescence lifetime has been measured for 4-dimethylaminobenzonitrile (DMABN), 4-aminobenzonitrile (ABN), 4-diisopropylaminobenzonitrile (DIABN), and 1-naphthonitrile (NN) in a supersonic free jet. In all cases, the fluorescence yield decreases rather dramatically, whereas the fluorescence lifetime decreases only moderately for S1 (pi pi*, L(b)) excess vibrational energy exceeding about 1000 cm(-1). This is confirmed by comparison of the normalized fluorescence excitation spectrum with the absorption spectrum of the compound in the vapor phase. The result indicates that the strong decrease in the relative fluorescence yield at higher energies is due mostly to a decrease in the radiative decay rate of the emitting state. Comparison of the experimental results with the TDDFT potential energy curves for excited states strongly suggests that the decrease in the radiative decay rate of the aminobenzonitriles at higher energies is due to the crossing of the pi pi* singlet state by the lower-lying pi sigma*(C[triple bond]N) singlet state of very small radiative decay rate. The threshold energy for the fluorescence "break-off" is in good agreement with the computed energy barrier for the pi pi*/pi sigma* crossing. For NN, on the other hand, the observed decrease is in fluorescence yield at higher excitation energies can best be attributed to the crossing of the pi pi* singlet state by the pi sigma* triplet state.