Biotinylated thermoresponsive core cross-linked nanoparticles via RAFT polymerization and "click" chemistry

A straightforward approach to the synthesis of "clickable" thermoresponsive core cross-linked (CCL) nanoparticles was developed. This approach was based on reversible addition-fragmentation chain transfer (RAFT) radical cross-linking polymerization of styrene and divinylbenzene with azide-functionalized poly(N-isopropylacrylamide) (PNIPAM-N(3)) as macro chain transfer agent in a selective solvent. Spherical nanoparticles with a diameter of 12nm were obtained after 24h polymerization. When the lyophilized CCL nanoparticles were dispersed in THF, spherical nanoparticles were observed, confirming the stability of CCL nanoparticles. The transmission electron microscopy (TEM) studies demonstrated that spherical nanoparticles and wormlike structure coexisted in the aqueous solution. The CCL nanoparticles have a lower critical solution temperature (LCST) at about 29.6°C, a little lower than that of PNIPAM homopolymer. Biotin molecules were conjugated to the surface of CCL nanoparticles via "click" chemistry in aqueous media. After bioconjugation, the LCST shifted to 28.3°C. The bioavailability of biotin to protein avidin was evaluated by a 4'-hydroxyazobenzene-2-carboxylic acid/avidin (HABA/avidin) binding assay and TEM.     

Electronic and magnetic properties of early transition-metal substituted iron-cyclopentadienyl sandwich molecular wires: parity-dependent half-metallicity

Electronic and magnetic properties of early transition metals (V, Ti, Sc)-Fe(k)Cp(k + 1) sandwich molecular wires (SMWs) are investigated by means of ab initio calculations. It is found that all SMWs favor a ferromagnetic ground state. Significantly, V-Fe(k)Cp(k + 1) SMWs are either half-metallic or semiconducting, dependent upon the parity (even or odd) of the number (k) of Fe atoms in the unit cell of SMWs. This parity oscillation of conductive properties results from the combined effects of the band-folding and gap-opening at the Brillouin-zone boundary of one-dimensional materials. In contrast, Sc-Fe(k)Cp(k + 1) and Ti-Fe(k)Cp(k + 1) SMWs are always semiconducting. Our work may open up the way toward half metal/semiconductor heterostructures with perfect atomic interface.     

Rearrangement of 3-deoxy-D-erythro-hexos-2-ulose in aqueous solution: NMR evidence of intramolecular 1,2-hydrogen transfer

Selective (13)C- and (2)H-labeling, and (13)C NMR spectroscopy, have been used to show that the 1,2-dicarbonyl compound (osone), 3-deoxy-D-erythro-hexos-2-ulose (3-deoxy-D-glucosone) (1; 3DG), degrades to 3-deoxy-D-ribo-hexonic acid 2 and 3-deoxy-D-arabino-hexonic acid 3 exclusively via an intramolecular 1,2-hydrogen transfer mechanism in aqueous phosphate buffer at pH 7.5 at 37 °C. Acids 2 and 3 are produced in significantly different amounts (1:6 ratio) despite the prochiral C3 in 1, and two potential reaction mechanisms are considered to explain the observed stereoselectivity. One mechanism involves acyclic forms of 1 as reactants, whereas the other assumes cyclic pyranose reactants. In the former (2-keto-hydrate or 2KH mechanism), putative transition state structures based on density functional theory (DFT) calculations arise from the C1 hydrate form of acyclic 1 having the C1-H1 bond roughly orthogonal to the C2 carbonyl plane. The relative orientation of the alkoxide oxygen atom at C1 and the C2 carbonyl oxygen, and H-bonding between C(1)OH and the C2 carbonyl oxygen, contribute to the stability of the transition state. DFT calculations of the natural charges on individual atoms in the transition state show the migrating hydrogen to have an almost neutral charge, implying that it may more closely resemble a hydrogen atom than a hydride anion during transfer from C1 to C2. A second mechanism (2-keto-pyranose or 2KP mechanism) involving the cyclic 2-keto-pyranoses of 1 as reactants aligns the C1-H1 bond orthogonal to the C2 carbonyl plane in different ring conformations of both anomers, with the β-pyranose giving 3 and the α-pyranose giving 2. While both the 2KH and 2KP mechanisms are possible, the latter readily leads to a prediction of the reaction stereospecificity that is consistent with the experimental data.     

Kinetics of the NCCO + NO2 reaction

The kinetics of the NCCO + NO(2) reaction was studied by transient infrared laser absorption spectroscopy. The total rate constant of the reaction was measured to be k = (2.1 ± 0.1) × 10(-11) cm(3) molecule(-1) s(-1) at 298 K. Detection of products and consideration of possible secondary chemistry shows that CO(2) + NO + CN is the primary product channel. The rate constants of the NCCO + CH(4) and NCCO + C(2)H(4) reactions were also measured, obtaining upper limits of k (NCCO + CH(4)) ≤ 7.0 × 10(-14) cm(3) molecule(-1) s(-1) and k (NCCO + C(2)H(4)) ≤ 5.0 × 10(-15) cm(3) molecule(-1) s(-1). Ab initio calculations on the singlet and triplet potential energy surfaces at B3LYP/6-311++G**//CCSD(T)/6-311++G** levels of theory show that the most favorable reaction pathway occurs on the singlet surface, leading to CO(2) + NO + CN products, in agreement with experiment.     

Immunosuppressive activity of 8-gingerol on immune responses in mice

8-gingerol is one of the principal components of ginger, which is widely used in China and elsewhere as a food, spice and herb. It shows immunosuppressive activity on the immune responses to ovalbumin (OVA) in mice. In the present study, we found that 8-gingerol suppressed lipopolysaccharide (LPS) and concanavalin A (ConA)-stimulated splenocyte proliferation in vitro. In vivo, 8-gingerol not only signi?cantly suppressed Con A-, LPS- and OVA-induced splenocyte proliferation (P < 0.05) but also decreased the percentage of CD19+ B cells and CD3+ T cell (P < 0.05) at high doses (50, 100 mg/kg). Moreover, OVA-speci?c IgG, IgG1 and IgG2b levels in OVA-immunized mice were reduced by 8-gingerol at doses of 50, 100 mg/kg. These results suggest that 8-gingerol could suppress humoral and cellular immune responses in mice. The mechanism might be related to direct inhibition of sensitized T and B lymphocytes.     

高压下β-FeOOH纳米固体结构转变的研究

 以化学水解法合成的β-FeOOH纳米微粉（平均粒径在12 nm左右）为原料，分别在0.0~4.5 GPa和200~350 ℃的压力和温度范围进行冷压和热压处理。实验结果表明，冷压对β-FeOOH纳米固体的结构没有明显影响，但却使它的热致相变（从β-FeOOH相到α-Fe₂O₃相）温度从常压下的203.8 ℃提高到4.5 GPa压力下的274 ℃，接近常规体相材料的相变温度。而在一定的热压条件处理下，首次发现了从β-FeOOH相到α-FeOOH相的结构转变，并在4.5 GPa、200 ℃的热压条件下得到了转变过程中的一个新的亚稳相。从压力和温度对纳米微粒的作用角度，对上述实验结果进行了讨论。     

静高压下Al80Mn14Si6合金准晶相形成的研究

 本文首次研究了Al₈₀Mn₁₄Si₆合金在静高压下准晶相得形成。利用静高压熔态淬火方法，在压力2.8和3.1 GPa下得到淬火的Al-Mn-Si样品。电子和X射线衍射实验表明，高压淬火样品中含有准晶二十面体相和非晶相。X射线衍射实验还表明，高压淬火样品经350 ℃退火一小时基本上没有发生变化；而经过500 ℃退火一小时后，准晶相晶化为α-Al₇₃Si₁₀Mn₁₇相。另外，电子衍射实验表明，高压淬火后样品中还存在其它中间亚稳相。本文还讨论了静高压熔态淬火方法的适用性。     

高压下Al0.77Mn0.19Yb0.04合金准晶T相的形成及结构

利用静高压(4.2GPa)熔态(1300℃)淬火(10~2℃/S)方法,对含稀土的铝锰合金Al_(0.77)Mn_(0.10)Yb_(0.04)进行了研究。首次发现了准晶T相的形成。利用选区透射电子衍射技术,对合金中准晶态的结构对称性进行了观察和分析。根据X射线和电子衍射对其衍射峰进行了指标化。使用扫描电镜和能谱技术进行了成份分析。     

不同压制压力下NiFe2O4纳米固体的ESR研究

 以反滴共沉定法制备了NiFe₂O₄纳米微粉，并在不同压力下将其压制成纳成米固体，然后用XRD谱和ESR谱研究了NiFe₂O₄纳米固体结构和界百状态随压制压力的变化。实验结果表明，NiFe₂O₄纳米固体的结构在高压下没有明显的变化，但其ESR谱的共振线宽和g因子值随着压力升高均表示出先逐渐增大至最大值，然手缓慢下降的规律。这种变化可以归因于纳米固体内部界面离子间的磁相互作用在压力的下所发生和变化。这引起实验结果境示，对于NiFe₂O₄纳米固体而言，最佳的成型压力是4.5 GPa，在此压力下，NiFe₂O₄纳米粒子既可以被压制成致密的纳米固体，又能够保留下它们的纳米结构和纳米性质。