Global solutions of the compressible navier-stokes equations with larger discontinuous initial data

We prove the global existence of weak solutions to the Navier-Stokes equations for compressible, heat-conducting flow in one space dimension with large, discontinuous initial data, and we obtain apriori estimates for these solutions which are independent of time, sufficient to determine their asymptotic behavior. In particular, we show that, as time goes to infinity, the solution tends to a constant state determined by the initial mass and the initial energy. and that the magnitudes of singularities in the solution decay to zero.     

Solving restricted open-shell equations in excited state molecular dynamics simulations

Different approaches to the solution of restricted open-shell equations are summarized and a general implementation for the first excited singlet state in the Car–Parrinello molecular dynamics code (CPMD) is presented. For molecular dynamics simulations where energy conservation is an important criterion, different choices of parameters are necessary depending on the particular chemical situation.     

Synthesis, characterization, and remarkable biological properties of cyclodextrins bearing guanidinoalkylamino and aminoalkylamino groups on their primary side

The introduction of aminoalkylamino and guanidinoalkylamino substituents on the primary side of beta- and gamma-cyclodextrin (CDs) resulted in a series of novel compounds that were extensively characterized by NMR spectroscopy and mass spectrometry. Bromination of the primary side of beta- and gamma-CD, and reaction with neat alkylene diamines at a pressure of 7 atm afforded aminoalkylamino derivatives that were then guanylated at the primary amino group to give the corresponding guanidinoalkylamino-CDs. These compounds are water soluble and display pK(a) values that allow them to be mostly protonated at neutral pH; for example, pK(a(1)) approximately 6.4 and pK(a(2)) approximately 9.5 for the aminoethylamino-beta-CD and pK(a(1)) approximately 7.8 and pK(a(2)) approximately 11.0 for the guanidinoethylamino-beta-CD. The title CDs are rigid, cyclic alpha-D-glucopyranose oligomers (heptamers or octamers) with branches that resemble lysine and arginine side chains that enable multiple interactions with suitable substrates. Thus, they bear similarities to known cell-penetrating peptides. Indeed, the compounds were found to cross the membranes of HeLa cells and penetrate inside the cytoplasm quickly, the guadinylated ones within 15 min, as shown by fluorescence microscopy using fluorescein-labeled derivatives. The toxicity of the compounds, measured by performing MTT tests, ranged from 50 to 300 microM. Furthermore, some of the aminated CDs could facilitate the transfection of DNA expressing the green fluorescent protein (GFP) in HEK 293T cells, with effectiveness comparable to the commercial agent Lipofectamine 2000. Circular dichroism, atomic force microscopy and electrophoresis experiments confirmed the strong interaction of the compounds with DNA. Because of their carbohydrate, non-peptide nature the title compounds are not anticipated to be enzymatically labile or immunogenic, and thus they fulfill many of the criteria for non-hazardous transport vectors in biological and pharmaceutical applications.     

Straightforward route to the adamantane clusters [Sn4Q10]4- (Q = S, Se, Te) and use in the assembly of open-framework chalcogenides (Me4N)2M[Sn4Se10] (M = Mn(II), Fe(II), Co(II), Zn(II)) including the first telluride member (Me4N)2Mn[Ge4Te10

The reaction of K(2)Sn(2)Q(5) (Q = S, Se, Te) with stoichiometric amounts of alkyl-ammonium bromides R(4)NBr (R = methyl or ethyl) in ethylenediamine (en) afforded the corresponding salts (R(4)N)(4)[Sn(4)Q(10)] (Q = S, Se, Te) in high yield. Although the compound K(2)Sn(2)Te(5) is not known, this reaction is also applicable to solids with a nominal composition "K(2)Sn(2)Te(5)" which in the presence of R(4)NBr in en are quantitatively converted to the salts (R(4)N)(4)[Sn(4)Te(10)] on a multigram scale. These salts contain the molecular adamantane clusters [Sn(4)Q(10)](4-) and can serve as soluble precursors in simple metathesis reactions with transition metal salts to synthesize the large family of open-framework compounds (Me(4)N)(2)M[Sn(4)Se(10)] (M = Mn(2+), Fe(2+), Co(2+), Zn(2+)). Full structural characterization of these materials as well as their magnetic and optical properties is reported. Depending on the transition metal in (Me(4)N)(2)M[Sn(4)Se(10)], the energy band gaps of these compounds lie in the range of 1.27-2.23 eV. (Me(4)N)(2)Mn[Ge(4)Te(10)] is the first telluride analogue to be reported in this family. This material is a narrow band gap semiconductor with an optical absorption energy of 0.69 eV. Ab initio electronic band structure calculations validate the semiconductor nature of these chalcogenides and indicate a nearly direct band gap.     

The supramolecular chemistry of metal complexes with heavily substituted imidazoles as ligands: Cobalt(II) and zinc(II) complexes of 1-methyl-4,5-diphenylimidazole

An investigation of the M^II/X⁻/L [M^II = Co, Ni, Cu, Zn; X⁻ = Cl⁻, Br⁻, I⁻, NCS⁻, NO₃⁻, N₃⁻, CH₃COO⁻; L = 1-methyl-4,5-diphenylimidazole] general reaction system towards the detailed study of the intermolecular interactions utilized for controlling the supramolecular organization and the structural consequences on the structures produced has been initiated. Three representative complexes with the formulae [Co(NO₃)₂(L)₂] (1), [Zn(NO₃)₂(L)₂] (2) and [Co(NCS)₂(L)₂]·EtOH (3·EtOH) have been synthesized and characterized by spectroscopic methods and single-crystal X-ray analysis. Compounds 1 and 2 are isomorphous (tetragonal, I4₁cd) with their metal ions in a severely distorted octahedral Co/ZnN₂O₄ environment, while 3·EtOH crystallizes in P2₁/c with a tetrahedral CoN₄ coordination. The structural analysis of 1, 2 and 3·EtOH reveals a common mode of packing among neighbouring ligands (expressed through intramolecular π–π interactions between the 4,5-diphenylimidazole moieties), enhancing thus the rigidity and stability of the complexes. The bent coordination of the two isothiocyanates in 3 [Co–NCS angles of 173.8(2) and 160.8(2)°] seems to be caused by intermolecular hydrogen bonding and crystal packing effects.     

Electronic transport between Au surface and scanning tunnelling microscope tip via a multipodal cyclodextrin host–metallo‐guest supramolecular system

An elementary supramolecular conducting system was constructed using a novel (±)‐thioctic acid‐functionalized β‐cyclodextrin host deposited on a gold (Au) surface and an iridium‐bearing guest molecule with biphenyl tails to insert specifically into the cyclodextrin cavity. The resulting supramolecular system was used to investigate remote electron communication between the flat Au surface and the platinum (Pt)/iridium (Ir) tip of a scanning tunnelling microscope. The morphology of the surfaces after successive deposition of host molecules followed by guest molecules was investigated. Formation of features of 2 nm size was shown on the Au surface functionalised with the supramolecular system. I–V spectroscopic analysis of the tunnelling current through this supramolecular layer revealed the relation between the effective barrier height and tunnelling distance. Thus, in the supramolecular host–metallo‐guest system, a small increase of conductance is observed, compared to the layer without the guest. This can be attributed to the presence of the Ir‐guest, which eventually creates intermediate energy states between the Au substrate and the Pt/Ir tip. Copyright © 2011 John Wiley & Sons, Ltd.     

Ice photolysis of 2,2′,4,4′,6-pentabromodiphenyl ether (BDE-100): Laboratory investigations using solid phase microextraction

Here, we report for the first time a laboratory investigation into the photochemical degradation of 2,2′,4,4′,6-pentabromodiphenyl ether (BDE-100) in ice solid samples using an artificial UV light source. Solid phase microextraction (SPME) was used as a sensitive extraction technique for monitoring trace amounts of the hydrophobic pollutant and its photoproducts. The results showed that ice photolysis kinetics for BDE-100 is similar to the one observed in the aqueous counterpart. The eight photoproducts identified consisted of brominated diphenyl ethers with lower bromine content and polybrominated dibenzofurans, suggesting two important photodegradation pathways for BDE-100 in ice solid samples: (i) stepwise reductive debromination and (ii) intramolecular elimination of HBr. Similarities in photochemical product arrays observed in the ice and water photolysis of BDE-100 were attributed to a similar mechanism for photochemical decomposition for both phases. Possible involvement of the water molecules in the reactions has been excluded by performing photolysis in D₂O ice solid and water samples. Taking advantage of the high preconcentration factor obtained with SPME at low temperatures, a SPME fiber cooled with liquid carbon dioxide down to 0 °C was used as a photoreaction support for BDE-100 allowing the identification of a greater number of photoproducts.     

Social media and sensemaking patterns in new product development: demystifying the customer sentiment

Artificial intelligence by principle is developed to assist but also support decision making processes. In our study, we explore how information retrieved from social media can assist decision-making processes for new product development (NPD). We focus on consumers’ emotions that are expressed through social media and analyse the variations of their sentiments in all the stages of NPD. We collect data from Twitter that reveal consumers’ appreciation of aspects of the design of a newly launched model of an innovative automotive company. We adopt the sensemaking approach coupled with the use of fuzzy logic for text mining. This combinatory methodological approach enables us to retrieve consensus from the data and to explore the variations of sentiments of the customers about the product and define the polarity of these emotions for each of the NPD stages. The analysis identifies sensemaking patterns in Twitter data and explains the NPD process and the associated steps where the social interactions from customers can have an iterative role. We conclude the paper by outlining an agenda for future research in the NPD process and the role of the customer opinion through sensemaking mechanisms.