Self-assembly of [2]rotaxane exploiting reversible Pt(II)- pyridine coordinate bonds

A dinuclear self-assembled cationic macrocycle based on Pt(II)-N(pyridine) coordinative bonds and having competitive triflate anions, as metal counterions, is used in the construction of [2]rotaxane and [2]pseudorotaxane architectures assisted by hydrogen bonding. The kinetic lability of the Pt(II)-N(pyridine) coordinative bond controls the dynamics of the [2]rotaxane.     

Flat vs. Folded Chelate Rings in cis‐PtIIa2 (a = NH3, a2 = en,a2 = 2, 2′‐bpy) Complexes of Twofold Substituted Diazine Ligands

Acid‐base and ligating properties of three bis(substituted)pyrazine (pz) and pyrimidine (pym) ligands (pyrazine‐2, 5‐dicarboxylic acid, 2, 5‐pzdcH2, 2, 3‐bis(pyridine‐2‐yl)pyrazine, 2, 3‐bppz, pyrimidine‐4, 6‐dicarboxylic acid, 4, 6‐pmdcH₂) toward cis‐Pt^IIa₂ (a = NH₃, a₂ = en, a₂ = 2, 2′‐bpy) have been studied. Combinations of pz‐N/pym‐N with donor atoms of the substituents lead to 5‐membered platinum chelates, but exclusive N, N‐coordination through the pyridyl substituents of 2, 3‐bppz can lead to a 7‐membered platinum chelate with a characteristic L‐shape of the resulting cation. It is observed for Pt^II(2, 2′‐bpy), yet not for Pt^II(en), and is a consequence of differences in sterical interactions between the 2, 3‐bppz ligand and the coligands of Pt^II.     

The aqueous cationic system sodium undecenoate-dodecyltrimethylammonium bromide at low concentration

The aqueous sodium undecenoate (SUD) –dodecyltrimethylammonium bromide (DTAB) catanionic system was studied at low concentration. The system did not precipitate, even at a 1:1 SUD:DTAB proportion, but showed the formation of a coacervate in a range of surfactant mixture compositions. Micelles have a preferential composition of 0.37 mole fraction of SUD. This behavior is attributed to the presence of the double bond at the distal extreme of the SUD molecule, which can form hydrogen bonds with water. Consequently, the –CH=CH₂ group is situated at the interface between the hydrocarbon micelle core and water, reducing the interfacial free energy. Structural computations demonstrate that the mentioned SUD proportion produces complete coverage of the micelle surface by the double bonds.     

Solubility of benzil in binary alkane + dibutyl ether solvent mixtures. Comparison of predictive expressions derived from the nearly ideal binary solvent model

Experimental solubilities are reported for benzil dissolved in six binary mixtures containing dibutyl ether with hexane, heptane, octane, cyclohexane, methylcyclohexane, and 2,2,4-trimethylpentane at 25°C. Results of these measurements are compared to the predictions of equations developed previously for solubility in systems of nonspecific interactions. The most successful equation in terms of goodness of fit involved a volume fraction average of the excess Gibbs energies relative to the Flory-Huggins model, and predicted the experimental solubilities in the six systems studied to within an overall average absolute deviation of 3.4% and with a maximum deviation of 6.0%.     

Product distributions, rate constants, and mechanisms of LiH+H reactions

We present a quantum-mechanical investigation of the LiH depletion reaction LiH+H-->Li+H2 and of the H exchange reaction LiH+H'-->LiH'+H. We report product distributions, rate constant, and mechanism of the former, and rate constant and mechanism of the latter reaction. We use the potential-energy surface by Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)], the real-wave-packet method by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)], and the J-shifting approximation. The 1H2 nuclear-spin statistics and progressions of vib-rotational states (v',j') rule both initial-state-resolved and thermal product distributions, which have saw-toothed shapes with odd j' preferred with respect to even j'. At high collision energies and temperatures, we obtain a regular 3-to-1 intensity alternation of rotational states. At low collision energies and temperatures, the degeneracy and density of many H2 levels can, however, give more irregular distributions. During the collision, the energy flows from the reactant translational mode to the product vibration and recoil ones. The rate constants of both reactions are not Arrhenius type because the reactions are barrier-less. The low-temperature, LiH depletion rate constant is larger than the H exchange one, whereas the contrary holds at high temperature. The real-time mechanisms show the nuclear rearrangements of the nonreactive channel and of the reactive ones, and point out that the LiH depletion is preferred over the H exchange at short times. This confirms the rate-constant results.     

Vertical Electronic Spectra of the Isovalent Molecules H2CNH,H2SiNH,H2CPH and H2SiPH on the Basis of MRD-CI Calculations

Abstract

Large-scale multi-reference single and double-excitation configuration interaction (MRD-CI) calculations are employed for the study of the isovalent compounds H₂CNH, HLSiNH, hLCPH and H₂SiPH in their ground state equilibrium geometry. The dipole moments and charge distributions are given. The vertical excitation energies to the intravalence states ^3,1 (n, π*) and ^3,1(π,π*) and to the first members of the Rydberg series originating from n and - MO's respectively are predicted; the first two ionization potentials and the Rydberg term values are also calculated. In H₂CNH, mixing of Rydberg and valence-shell states with CN stretching is analyzed. The trends in relative stability of electronic and ionized states can be directly related to increased orbital stability of n relative to π as soon as a first-row constituent is replaced by a second-row atom. The calculations explain the diffuse character of the uv spectrum of imines; they treat the molecules H₂SiNH and H₂SiPH for the first time and present a large number of data for all four molecules which can serve as a basis for future experimental investigations on these and related compounds.     

Non-chromatographic screening method for the determination of mercury species. Application to the monitoring of mercury levels in Antarctic samples

A simple non-chromatographic method for the determination of mercury (Hg²⁺), methylmercury (MeHg⁺), dimethylmercury (Me₂Hg), and phenylmercury (PhHg⁺) employing atomic fluorescence spectrometry (AFS) as detection technique was developed. Mercury species showed a particular behavior in the presence of several reagents. In a first stage SnCl₂ was employed for Hg²⁺ determination; in a second step, [Hg²⁺ + PhHg⁺] concentration was determined using SnCl₂ and UV radiation. MeHg⁺ decomposition was prevented adding 2-mercaptoethanol. In a third stage, [Hg²⁺ + PhHg⁺ + MeHg⁺] concentration was determined using K₂S₂O₈. Finally, the four species were determined employing NaBH₄. Reagents concentration and flow rates were optimized. The extraction technique of mercury species involved the use of 2-mercaptoethanol as ion-pair reagent. The limits of detection for Hg²⁺, PhHg⁺, MeHg⁺, and Me₂Hg were 1, 40, 68, and 99 ng L⁻¹ with a relative standard deviation of 1.5, 3.1, 4.7 and 5.8%, respectively. Calibration curve was linear with a correlation factor equal to 0.9995. The method was successfully applied to the determination of the mercury species in two Antarctic materials: IRMM 813 (Adamussium colbecki) and MURST-ISS-A2 (Antarctic Krill).     

Single crystal EPR study of the dinuclear Cu(II) complex [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline): influence of weak interdimeric magnetic interactions

We report powder and single crystal EPR measurements of [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline) at 9.7 GHz. This compound consists of centrosymmetric copper(II) ion dimers, weakly ferromagnetically exchange-coupled (J = +3.2 cm(-1)), in which the dimeric units are linked by hydrophobic chemical paths involving the phen molecules. EPR revealed that the triplet spectra are collapsed by interdimeric exchange interactions mediated by that chemical path. Analysis and simulation of the single crystal EPR spectra were performed using Anderson's exchange narrowing model, together with statistical arguments. This approach allowed us to interpret the spectra modulated by the interdimeric interactions in situations of weak, intermediate, and strong exchange. We evaluated an interdimeric exchange constant J' = 0.0070(3) cm(-1), indicating that hydrophobic paths can transmit weak exchange interactions between centers at relatively long distances of the order of ～10 ?.     

Development of a solid phase dispersion-pressurized liquid extraction method for the analysis of suspected fragrance allergens in leave-on cosmetics

A new method based on solid phase dispersion-pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the determination of 26 suspected fragrance allergens (all the regulated in the EU Cosmetics Directive amenable by GC, as well as pinene and methyleugenol) in cosmetic samples. The effects of the temperature, extraction time and solvent, and dispersing sorbent, affecting the whole proposed procedure, have been evaluated using a multifactor strategy. The optima conditions after the analysis of main and second order effects entailed the extraction at 120°C for 15 min, using hexane/acetone as solvent, and florisil as dispersing sorbent. The method performance has been studied, showing good linearity (R≥0.996) as well as good precision (RSD≤10%). Detection limits (S/N=3) ranged from 0.000001 to 0.0002% (w/w), values far below the established restrictions as regard labelling in the European Cosmetics Regulation. Reliability was demonstrated through the quantitative recoveries of all the studied compounds. The absence of matrix effects allowed quantification of the compounds by calibration with standard solutions. The analysis of 10 samples (several moisturizing and anti-wrinkle creams and lotions, hand creams, and sunscreen and after-sun creams), covering very different matrices, showed the presence of suspected allergens in all the analyzed samples; in fact, half of the samples contained an elevated number of them. Although the ubiquity of these compounds was demonstrated, labelling was in all cases in consonance with the European Cosmetics Regulation.     

Candida rugosa lipase Lip1–polyethyleneglycol interaction and the relation with its partition in aqueous two-phase systems

The interaction between a lipase from Candida rugosa (Lip1) and polyethyleneglycols of different molecular masses was studied using fluorescence and circular dichroism approaches in order to be applied to the analysis of the enzyme partition mechanism in aqueous two-phase systems of polyethyleneglycol–potassium phosphate. The decrease of the partition coefficients with the polyethyleneglycol molecular mass showed that the enzyme partition is driven by the excluded volume effect and not by the enzyme–polymer interaction. The polymer did not affect the secondary and tertiary structure of the enzyme nor its biological activity. The lipase from Candida rugosa lyophilizate was partitioned in favour of the polyethyleneglycol rich phase; PEG 2000 being the system which showed the better enzyme recovery (78.26%) with a purification factor of 2.3. This method could be applied as a first step to isolate the enzyme from a culture medium with good recovery and without modifying the enzymatic capacity and the molecular structure.