Regioselective Dichlorination of a Non‐Activated Aliphatic Carbon Atom and Phenolic Bismethylation by a Multifunctional Fungal Flavoenzyme

The regioselective functionalization of non‐activated carbon atoms such as aliphatic halogenation is a major synthetic challenge. A novel multifunctional enzyme catalyzing the geminal dichlorination of a methyl group was discovered in Aspergillus oryzae (Koji mold), an important fungus that is widely used for Asian food fermentation. A biosynthetic pathway encoded on two different chromosomes yields mono‐ and dichlorinated polyketides (diaporthin derivatives), including the cytotoxic dichlorodiaporthin as the main product. Bioinformatic analyses and functional genetics revealed an unprecedented hybrid enzyme (AoiQ) with two functional domains, one for halogenation and one for O‐methylation. AoiQ was successfully reconstituted in vivo and in vitro, unequivocally showing that this FADH₂‐dependent enzyme is uniquely capable of the stepwise gem‐dichlorination of a non‐activated carbon atom on a freestanding substrate. Genome mining indicated that related hybrid enzymes are encoded in cryptic gene clusters in numerous ecologically relevant fungi.     

Dihydrogen trioxide clusters, (HOOOH)n (n = 2-4), and the hydrogen-bonded complexes of HOOOH with acetone and dimethyl ether: implications for the decomposition of HOOOH

Hydrogen-bonded gas-phase molecular clusters of dihydrogen trioxide (HOOOH) have been investigated using DFT (B3LYP/6-311++G(3df,3pd)) and MP2/6-311++G(3df,3pd) methods. The binding energies, vibrational frequencies, and dipole moments for the various dimer, trimer, and tetramer structures, in which HOOOH acts as a proton donor as well as an acceptor, are reported. The stronger binding interaction in the HOOOH dimer, as compared to that in the analogous cyclic structure of the HOOH dimer, indicates that dihydrogen trioxide is a stronger acid than hydrogen peroxide. A new decomposition pathway for HOOOH was explored. Decomposition occurs via an eight-membered ring transition state for the intermolecular (slightly asynchronous) transfer of two protons between the HOOOH molecules, which form a cyclic dimer, to produce water and singlet oxygen (Delta (1)O 2). This autocatalytic decomposition appears to explain a relatively fast decomposition (Delta H a(298K) = 19.9 kcal/mol, B3LYP/6-311+G(d,p)) of HOOOH in nonpolar (inert) solvents, which might even compete with the water-assisted decomposition of this simplest of polyoxides (Delta H a(298K) = 18.8 kcal/mol for (H 2O) 2-assisted decomposition) in more polar solvents. The formation of relatively strongly hydrogen-bonded complexes between HOOOH and organic oxygen bases, HOOOH-B (B = acetone and dimethyl ether), strongly retards the decomposition in these bases as solvents, most likely by preventing such a proton transfer.     

Selective synthesis combined with chemical separation of single-walled carbon nanotubes for chirality selection

Single-walled carbon nanotubes (SWNTs) are potential materials for future nanoelectronics. Since the electronic and optical properties of SWNTs strongly depend on tube diameter and chirality, obtaining SWNTs with narrow (n,m) chirality distribution by selective growth or chemical separation has been an active area of research. Here, we demonstrate that a new, bimetallic FeRu catalyst affords SWNT growth with narrow diameter and chirality distribution in methane CVD. At 600 degrees C, methane CVD on FeRu catalyst produced predominantly (6,5) SWNTs according to UV-vis-NIR absorption and photoluminescence excitation/emission (PLE) spectroscopic characterization. At 850 degrees C, the dominant semiconducting species produced are (8,4), (7,6), and (7,5) SWNTs, with much narrower distributions in diameter and chirality than materials grown by other catalysts. Further, we show that narrow diameter/chirality growth combined with chemical separation by ion exchange chromatography (IEC) greatly facilitates achieving single (m,n) SWNT samples, as demonstrated by obtaining highly enriched (8,4) SWNTs with near elimination of metallic SWNTs existing in the as-grown material.     

Development of an <Emphasis Type="Italic">Agrobacterium</Emphasis>-Mediated Transformation Method and Evaluation of Two Exogenous Constitutive Promoters in Oleaginous Yeast <Emphasis Type="Italic">Lipomyces starkeyi</Emphasis>

The biogenic iron oxide/hydroxide materials possess useful combination of physicochemical properties and are considered for application in various areas. Their production does not require special investments because these compounds are formed during cultivation of neurophilic iron bacteria. Bacteria from genus Leptothrix develop intensively in the Sphaerotilus-Leptothrix group of bacteria isolation medium and feeding media of Fedorov and Lieske. These media are different in their composition which determined the present study as an attempt to clear up the reasons that define the differences in the composition of the laboratory-obtained biomasses and the natural biomass finds. FTIRS, Mössbauer spectroscopy, and XRD were used in the research. Comparative analysis showed that the biomass and control samples contain iron compounds (α-FeOOH, γ-FeOOH, β-FeOOH, γ-Fe₂O₃) in different ratios. The biomass samples were enriched in oxyhydroxides of higher dispersion. Organic residuals of bacterial origin, SO₄, CO₃, and PO₄ groups were registered in the biogenic materials.     

Indirect detection of nitrogen-14 in solid-state NMR spectroscopy.

NMR spectra of (14)N (spin I=1) are obtained by indirect detection in powders spinning at the magic angle. The method relies on the transfer of coherence from a neighboring "spy" nucleus with S=1/2, such as (13)C or (1)H, to single- or double-quantum transitions of (14)N nuclei. The transfer of coherence can occur through a combination of scalar and residual dipolar splittings (RDS); the latter are also known as second-order quadrupole-dipole cross terms. The two-dimensional NMR spectra reveal powder patterns determined by second- and third-order quadrupolar couplings. These spectra depend on the quadrupolar coupling constant C(Q) (typically a few megahertz), on the asymmetry parameter eta(Q) of the (14)N nucleus, and on the orientation of the internuclear vector r(IS) between the I ((14)N) and S (spy) nuclei with respect to the quadrupolar tensor. These parameters, which can be subject to motional averaging, can reveal valuable information about the structure and dynamics of nitrogen-containing solids. Application of this technique to various amino acids, either enriched in (13)C or with natural carbon isotope abundance, with spectra recorded at various magnetic fields, illustrates the scope of the method.     

Self-assembly of short peptide amphiphiles: the cooperative effect of hydrophobic interaction and hydrogen bonding

The interplay between hydrogen bonding, hydrophobic interaction and the molecular geometry of amino acid side-chains is crucial to the development of nanostructures of short peptide amphiphiles. An important step towards developing their practical use is to understand how different amino acid side-chains tune hydrophobic interaction and hydrogen bonding and how this process leads to the control of the size and shape of the nanostructures. In this study, we have designed and synthesized three sets of short amphiphilic peptides (I(3)K, LI(2)K and L(3)K; L(3)K, L(4)K and L(5)K; I(3)K, I(4)K and I(5)K) and investigated how I and L affected their self-assembly in aqueous solution. The results have demonstrated a strong tendency of I groups to promote the growth of β-sheet hydrogen bonding and the subsequent formation of nanofibrillar shapes. All I(m)K (m = 3-5) peptides assembled into nanofibers with consistent β-sheet conformation, whereas the nanofiber diameters decreased as m increased due to geometrical constraint in peptide chain packing. In contrast, L groups had a weak tendency to promote β-sheet structuring and their hydrophobicity became dominant and resulted in globular micelles in L(3)K assembly. However, increase in the number of hydrophobic sequences to L(5)K induced β-sheet conformation due to the cooperative hydrophobic effect and the consequent formation of long nanofibers. The assembly of L(4)K was, therefore, intermediate between L(3)K and L(5)K, similar to the case of LI(2)K within the set of L(3)K, LI(2)K and I(3)K, with a steady transition from the dominance of hydrophobic interaction to hydrogen bonding. Thus, changes in hydrophobic length and swapping of L and I can alter the size and shape of the self-assembled nanostructures from these simple peptide amphiphiles.     

动态磁涂覆混合固定相开管毛细管电色谱中电渗流的特征

将表面分别被改性成C18和氨基的磁性纳米颗粒按照不同比例混合,制备成具有不同分离选择性的混合固定相,进一步采用动态磁涂覆的方法制备开管毛细管电色谱柱。通过考察这种色谱柱中不同种类固定相表面物理化学性质对电渗流的综合影响,从理论上说明了其电渗流的特征。分别在不同固定相配比及不同涂覆长度条件下进行实验,理论与实验结果相符,证实通过调节固定相配比或磁铁对数可以便捷地调节电渗流的大小。     

A unique approach to development of near-infrared fluorescent sensors for in vivo imaging

Near-infrared (NIR) fluorescent sensors have emerged as promising molecular tools for imaging biomolecules in living systems. However, NIR fluorescent sensors are very challenging to be developed. Herein, we describe the discovery of a new class of NIR fluorescent dyes represented by 1a/1c/1e, which are superior to the traditional 7-hydroxycoumarin and fluorescein with both absorption and emission in the NIR region while retaining an optically tunable hydroxyl group. Quantum chemical calculations with the B3LYP exchange functional employing 6-31G(d) basis sets provide insights into the optical property distinctions between 1a/1c/1e and their alkoxy derivatives. The unique optical properties of the new type of fluorescent dyes can be exploited as a useful strategy for development of NIR fluorescent sensors. Employing this strategy, two different types of NIR fluorescent sensors, NIR-H(2)O(2) and NIR-thiol, for H(2)O(2) and thiols, respectively, were constructed. These novel sensors respond to H(2)O(2) or thiols with a large turn-on NIR fluorescence signal upon excitation in the NIR region. Furthermore, NIR-H(2)O(2) and NIR-thiol are capable of imaging endogenously produced H(2)O(2) and thiols, respectively, not only in living cells but also in living mice, demonstrating the value of the new NIR fluorescent sensor design strategy. The new type of NIR dyes presented herein may open up new opportunities for the development of NIR fluorescent sensors based on the hydroxyl functionalized reactive sites for biological imaging applications in living animals.     

Glycosylation of Volatile Phenols in Grapes following Pre-Harvest (On-Vine) vs. Post-Harvest (Off-Vine) Exposure to Smoke

Taint in grapes and wine following vineyard exposure to bushfire smoke continues to challenge the financial viability of grape and wine producers worldwide. In response, researchers are studying the chemical, sensory and physiological consequences of grapevine smoke exposure. However, studies involving winemaking trials are often limited by the availability of suitable quantities of smoke-affected grapes, either from vineyards exposed to smoke or from field trials involving the application of smoke to grapevines. This study compared the accumulation of volatile phenol glycosides (as compositional markers of smoke taint) in Viognier and Cabernet Sauvignon grapes exposed to smoke pre- vs. post-harvest, and found post-harvest smoke exposure of fruit gave similar levels of volatile phenol glycosides to fruit exposed to smoke pre-harvest. Furthermore, wines made from smoke-affected fruit contained similar levels of smoke-derived volatile phenols and their glycosides, irrespective of whether smoke exposure occurred pre- vs. post-harvest. Post-harvest smoke exposure therefore provides a valid approach to generating smoke-affected grapes in the quantities needed for winemaking trials and/or trials that employ both chemical and sensory analysis of wine.     

Jet spaces in modern Hamiltonian biomechanics

In this paper we propose the time-dependent Hamiltonian form of human biomechanics, as a sequel to our previous work in time-dependent Lagrangian biomechanics [1]. This is the time-dependent generalization of an ‘ordinary’ autonomous human biomechanics, in which total mechanical + biochemical energy is not conserved. In our view, this time-dependent energetic approach is much more realistic than the autonomous one. Starting with the Covariant Force Law, we first develop autonomous Hamiltonian biomechanics. Then we extend it using a powerful geometrical machinery consisting of fibre bundles and jet manifolds associated to the biomechanical configuration manifold. We derive time-dependent, dissipative, Hamiltonian equations and the fitness evolution equation for the general time-dependent human biomechanical system.