Rotational tunneling dynamics of methyl groups inn-alkane host lattices: An optical investigation of the internal and external isotope effect

We exploited the slow relaxation of methyl group rotational tunneling states to perform optical hole burning inn-alkane crystals. The dye probe used was dimethyl-s-tetrazine and its perdeuterated derivative. We investigatedn-octane, perdeuteratedn-octane andn-hexane as host crystals. By comparing the experimentally observed hole-antihole splitting of the protonated and perdeuterated dye probe, all parameters, i.e. the tunneling splitting in the ground-and in the electronically excited state as well as the respective heights of the potential can be determined, assuming a threefold rotational symmetry axis. We found that matrix deuteration has a severe influence on the potential heights, which increase by a factor of two. With these parameters determined, many features of the complex relaxation behavior of the tunneling states can be qualitatively understood: We found Raman-type conversion processes inn-octane-h ₁₈, Orbach-type processes inn-octane-d ₁₈ and inn-hexane we found, in addition, a relaxation regime governed by a Direct process. The experimental activation energies as well as the cross-over temperatures are in satisfying agreement with current theories.     

New Perspectives in Polyoxometalate Chemistry by isolation of compounds containing very large moieties as transferable building blocks: (NMe4)5[As2Mo8V4AsO40] · 3H2O, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] · 65 H2O, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] · 14 H2O,and (NH4)12[Mo36(NO)4O108(H2O)16] · 33 H2O

The compounds (NMe₄)₅[As₂Mo₈V₄AsO₄₀] · 3 H₂O 2a , (NH₄)₂₁[H₃Mo₅₇V₆(NO)₆O₁₈₃(H₂O)₁₈] · 65 H₂O 3a , (NH₂Me₂)₁₈(NH₄)₆[Mo₅₇V₆(NO)₆O₁₈₃(H₂O)₁₈] · 14 H₂O 3b and (NH₄)₁₂[Mo₃₆(NO)₄O₁₀₈(H₂O)₁₆] · 33 H₂O 4a ( 3a and 4a were not correctly reported in the literature regarding to their composition, structures and the oxidation states of the metal centres) which contain large isolated anionic species, have been prepared (among them 3a, 3b , and 4a in rather high yield) and characterized by complete crystal structure analysis as well as IR/Raman, UV/VIS/NIR, ESR spectroscopy and magnetic susceptibility measurements, redox titrations, bond valence sum calculations, elemental analyses and thermogravimetric studies. Perspectives for polyoxometalate chemistry referring to the synthesis of “extremely” large nanoscaled species are discussed, together with the occurrence of a large transferable {Mo₁₇} building block in the compounds 3a, 3b and 4a which also exists in the corresponding iron compound Na₃(NH₄)₁₂[H₁₅Mo₅₇Fe₆(NO)₆O₁₈₃(H₂O)₁₈] · 76 H₂O 7a .     

Functionalized mesoporous silica films as a matrix for anchoring electrochemically active guests

Mesoporous silica thin films were shown to be an appropriate matrix for immobilization of discrete electroactive moieties, yielding uniform transparent thin film electrodes with defined texture and enhanced electrochemical activity. The mesoporous silica films prepared on conducting FTO-coated glass substrate were postsynthetically functionalized. Alkoxysilanes were used as precursors for subsequent grafting via ionic or covalent bonds of representative electroactive species, such as polyoxometalate PMo12O(40)3-, hexacyanoferrate(III), and ferrocene. The electrochemically active concentration within the silica-based composite electrodes achieves 90, 260, and 60 micromol cm(-3) for polyoxometalate, hexacyanoferrate(III), and ferrocene, respectively. The amount of molecules involved in the charge-transfer sequence is proportional to the film thickness and comparable to the total amount of embedded guests. Thus, eventually the whole bulk volume of the modified silica films is electrochemically accessible. Immobilization in the chemically modified silica matrix alters the redox potential of the electroactive molecules. Electron exchange between the adjacent redox centers (electron hopping) is proposed as a possible charge propagation pathway through the insulating silica matrix, which is supported by the fact that the high charge uptake is observed also for the hybrid electrodes with the covalently anchored redox guests.     

Exploring intramolecular reactions in complex systems with metadynamics: the case of the malonate anions

We have determined the optimized structures, relative energies and intramolecular reactions for two anionic forms of malonic acid, anion malonate(-1) (HO(2)CCH(2)CO(2)(-)) and malonate(-2) ((-)O(2)CCH(2)CO(2)(-)). For this purpose we employed accurate quantum chemistry calculations using second-order M?ller-Plesset perturbation theory and Density Functional Theory with an aug'-cc-p-VTZ basis set to determine the structures and energies, and a novel metadynamics method based on Car-Parrinello molecular dynamics for the thermal reactions. For both malonates, we found new isomers (keto and enol structures) characterized by CO(2) rotations and intramolecular proton transfers. These proton transfers characterize the keto-enol tautomerism that takes place both in the monoanion and dianion. In all cases, the keto tautomer is the more stable configuration. The metadynamics method allows the system to explore the potential energy surface in a few picoseconds, crossing activation barriers of 20-50 kcal/mol.     

Solubility of 1-Butene in Water and in a Medium for Cultivation of a Bacterial Strain

Solubility measurements of 1-butene in water, from 20 to 50°C and at atmospheric pressure, were carried out using a Ben-Naim/Baer-type apparatus. The experimental results have a precision of about ±0.3%. Using accurate thermodynamic relations, the Ostwald coefficients at the experimental conditions and at infinite dilution, the mole fractions of the dissolved gas at the gas partial pressure of 101.325 kPa and the Henry coefficients at the water vapor pressure were calculated. The mole fraction of dissolved gas were fitted to the Clarke, Glew, and Weiss equation and thermodynamic quantities, standard molar Gibbs energy, entropy, and enthalpy changes, for the process of transferring the 1-butene molecules from the gaseous to the water phase, were computed. Moreover, solubility measurements of 1-butene in an aqueous medium for the cultivation of Xanthobacter Py2 in the same temperature range were also performed at atmospheric pressure. These solubility data are approximately 2.6% lower than those observed in pure water.     

Access to Enantiopure Advanced Intermediates en Route to Madangamines

The synthesis of enantiopure ABCE and ABCD tetracyclic advanced intermediates en route to madangamine alkaloids and studies for the construction of the triunsaturated 15-membered D ring of madangamine B and the saturated 13-membered D ring of madangamine E are reported.     

Sterically congested macrobicycles with heteroatomic bridgehead functionality

A series of cyclophanes composed of two triarylelement caps linked by two-atom bridges has been synthesized. The bridgehead functional groups include phosphines in combination with amines, hydrosilanes, methylsilanes, and ethoxysilanes. Computational studies accurately predicted that when the bridgehead substituents are small (lone pairs or protons), an in_,in bridgehead stereochemistry is strongly favored, but larger bridgehead substituents favor the formations of in_,out stereoisomers. The X-ray structures, spectra, and reactivity of these compounds are discussed, as well as the resolution of one of the cyclophanes into pure enantiomers.     

Chemical Composition and Antioxidant Activity of Essential Oils from Eugenia patrisii Vahl,E. punicifolia (Kunth) DC., and Myrcia tomentosa (Aubl.) DC., Leaf of Family Myrtaceae

Essential oils (EOs) were extracted from Eugenia patrisii, E. punicifolia, and Myrcia tomentosa, specimens A and B, using hydrodistillation. Gas chromatography coupled with mass spectrometry (GC/MS) was used to identify the volatile constituents present, and the antioxidant capacity of EOs was determined using diphenylpicryl-hydrazyl (DPPH) and trolox equivalent antioxidant capacity (TEAC) assays. For E. patrisii, germacrene D (20.03%), bicyclogermacrene (11.82%), and (E)-caryophyllene (11.04%) were identified as the major constituents of the EOs extracted from specimen A, whereas specimen B primarily comprised γ-elemene (25.89%), germacrene B (8.11%), and (E)-caryophyllene (10.76%). The EOs of E. punicifolia specimen A contained β-Elemene (25.12%), (E)-caryophyllene (13.11%), and bicyclogermacrene (9.88%), while specimen B was composed of (E)-caryophyllene (11.47%), bicyclogermacrene (5.86%), β-pinene (5.86%), and γ-muurolene (5.55%). The specimen A of M. tomentosa was characterized by γ-elemene (12.52%), germacrene D (11.45%), and (E)-caryophyllene (10.22%), while specimen B contained spathulenol (40.70%), α-zingiberene (9.58%), and γ-elemene (6.89%). Additionally, the chemical composition of the EOs was qualitatively and quantitatively affected by the collection period. Furthermore, the EOs of the studied specimens, especially specimen A of E. punicifolia, showed a greater antioxidant activity in DPPH rather than TEAC, as represented by a significantly high inhibition percentage (408.0%).