Enhanced stability by three-dimensional aromaticity of endohedrally doped clusters X(10)M(0/-) with X = Ge, Sn, Pb and M = Cu, Ag, Au

The group 14 clusters encapsulated by coinage metals in neutral and anionic states X(10)M(0/-) (X = Ge, Sn, Pb and M = Cu, Ag, Au) are investigated using quantum chemical calculations with the DFT/B3LYP functional and coupled-cluster CCSD(T) theory. Addition of transition metals into the empty cages forms high symmetry endohedral structures, except for Ge(10)Ag(0/-). In agreement with experiments available for X(10)Cu, the D(4d) global minima of the anions are calculated to be magic clusters with large frontier orbital gaps, high vertical and adiabatic detachment energies, and large embedding energies and binding energies as compared to those of the empty cages X(10)(2-). The enhanced stability of these magic clusters can be rationalized by the three-dimensional aromaticity.     

Optimum conditions for the water extraction of L-theanine from green tea

Theanine is a unique non-protein amino acid found in tea (Camellia sinensis). It contributes to the favourable umami taste of tea and is linked to various beneficial effects in humans. There is an increasing interest in theanine as an important component of tea, as an ingredient for novel functional foods and as a dietary supplement. Therefore, optimal conditions for extracting theanine from tea are required for the accurate quantification of theanine in tea and as an efficient first step for its purification. This study examined the effects of four different extraction conditions on the yield of theanine from green tea using water and applied response surface methodology to further optimise the extraction conditions. The results showed that temperature, extraction time, ratio of water-to-tea and tea particle sizes had significant impacts on the extraction yield of theanine. The optimal conditions for extracting theanine from green tea using water were found to be extraction at 80 °C for 30 min with a water-to-tea ratio of 20:1 mL/g and a tea particle size of 0.5-1 mm.     

Electronic structures, vibrational and thermochemical properties of neutral and charged niobium clusters Nb(n), n = 7-12

Geometric and electronic structures, vibrational properties, and relative stabilities of niobium clusters Nb(n), n = 7-12, are studied using both DFT (BPW91 and M06 functionals) and CCSD(T) calculations with the cc-pVnZ-PP basis set. In each cluster, various lower-lying states are very close in energy in such a way that the ground state cannot be unambiguously established by DFT computations. Nb clusters tend to prefer the lowest possible spin state as the ground state, except for Nb(12) ((3)A(g)). The optimal structure of the cluster at a certain size does not simply grow from that of the smaller one by adding an atom randomly. Instead, the Nb clusters prefer a close-packed growth behavior. Nb(10) has a spherically aromatic character, high chemical hardness and large HOMO-LUMO gap. Electron affinities, ionization energies, binding energy per atom, and the stepwise dissociation energies are evaluated. Energetic properties exhibit odd-even oscillations. Comparison with experimental values shows that both BPW91 and M06 functionals are reliable in predicting the EA and IE values, but the BPW91 is deficient in predicting the binding and dissociation energies. We re-examine in particular the experimental far IR spectra previously recorded using the IR-MPD and free electron laser spectrometric techniques and propose novel assignments for Nb(7) and Nb(9) systems. The IR spectra of the anions are also predicted.     

Synthesis and characterization of a novel liquid crystal series with tribenzoate cores and monofluoro-substitution on the phenyl ring near the chiral chain

Two new chiral series, with benzoate cores and monofluoro-substitution in positions 2 and 3 of the first phenyl ring near the chiral chain, have been synthesized and characterized. The mesomorphic properties have been analysed by optical microscopy, differential scanning calorimetry and electro-optical measurements. The first series (I_c) displays a very rich polymorphism including SmA, SmC*_α, SmC*, SmC*_FI, SmC*_A phases, whereas the second (I_b) does not exhibit the SmC*_A phase, and moreover only displays the SmA phase for short alkoxy chains. The effect of the position of the fluoro substituent and the influence of the alkoxy chain length on the mesomorphic behaviour are discussed.     

Synthesis of Jasminaldehyde by Solid-Liquid Phase Transfer Catalysis Without Solvent,Under Microwave Irradiation

α-n-amylcinnamaldehyde (jasminaldehyde) was obtained with 82 % yield by solid-liquid phase transfer catalysis without solvent within 3 days at room temperature. By use of domestic microwave irradiation, the same yield was obtained within 1 minute at a power of 600 W.     

Amino acid analysis by using comprehensive two-dimensional gas chromatography

The separation characteristics of alkylchloroformate-derivatised amino acids (AAs) by using comprehensive two-dimensional gas chromatography (GC×GC) is reported. The use of a low-polarity/polar column set did not provide as good a separation performance as that achieved with a polar/non-polar column set, where the latter appeared to provide less correlation over the separation space. The degree of component correlation in each column set was estimated by using the correlation coefficient (r²; for ¹t_R and ²t_R data) with the low-polarity/polar and polar/low-polarity sets returning correlation coefficients of 0.86, and 0.00 respectively, under the respective conditions employed for the experiments. The 1.5-m non-polar ²D column (0.1-mm ID; 0.1-m film thickness) gave peak halfwidths of the order of 50–80 ms. Linearity of detection was good, over a three order of magnitude concentration range, with typical lower detection limit of ca. 0.01 mg L^–1, compared with 0.5 mg L^–1 for normal GC operation with splitless injection. The method was demonstrated for analysis of AAs in a range of food and beverage products, including wine, beer and honey. The major AA in these samples was proline. The Heineken beer sample had a relatively more complex and more abundant AA content compared with the other beer sample. The wine and honey samples also gave a range of AA compounds. Repetition of the sample preparation/analysis procedure for the honey sample gave acceptable reproducibility for individual AAs.     

Synthesis of 4,5-benzotropones by cyclization of 1,3-bis-silyl enol ethers with 1,2-dialdehydes

The cyclization of 1,3-bis-silyl enol ethers or (2,4-dioxobutylidene)triphenylphosphoranes with phthalic dialdehyde allowed a convenient synthesis of a variety of 4,5-benzotropones. The hydrogenation of benzotropones afforded functionalized benzocycloheptanones which were transformed into tricyclic butenolides.