2-C-支链-1,6-脱水吡喃葡萄糖的开环反应及吡喃烯糖的合成研究

在糖化学合成中，1,6-脱水吡喃糖不仅是合成具有生物活性低聚糖、糖共体、抗原、抗体以及天然产物等化合物重要原料，而且还是许多具有生物活性的天然产物的结构单元。同时，它还具有[3,2,1]的双环缩醛结构，使其在糖化学合成中具有高的立体选择性和区域选择性，同时减少了C-1 和C-6 位的保护和去保护的优点。此外，环内的缩醛开环后，又可以相应地在C-1 和C-6 位进行官能团转化以及糖苷化反应。 本文报道了一种新的1,6-脱水吡喃糖的合成方法，并设计合成了2-C-支链-1,6-脱水吡喃葡萄糖1-195、1-197、1-198 以及2-C-支链-6-硫代1,6-脱水吡喃葡萄糖1-225。到目前为止，1,6-脱水糖开环并进行糖苷化反应，存在选择性较差、产率低的缺点。我们发现，在乙腈做溶剂的条件下，NiCl5 能高立体选择性高产率地催化化合物1-195、1-197、1-198 开环并与ROH、RSH 发生糖苷化反应。在NiCl5-乙腈条件下，合成了一系列2-C-支链-α-糖苷和2-C-支链-β-硫代糖苷，并对2-C-支链1,6-脱水吡喃葡萄糖的生成机理以及开环机理进行了探讨。 烯糖在糖化学合成中是重要的起始原料，从Fischer 首次合成烯糖至今，一直不断地有新的合成方法出现。但目前文献报道的方法存在所用试剂有毒、价格贵和操作繁琐等缺点。我们对Fischer-Zach 方法进行了改进， 发现Zn-NaH2PO4-H2O 和Zn-PEG600-H2O 体系都能很好地合成烯糖。该方法具有条件温和、绿色环保、操作简单的优点。在Zn-NaH2PO4 溶液或Zn-PEG600 条件下，以溴代糖为原料，高产率地合成一系列的烯糖。 The 1,6-anhydrohexopyranoses are crucial subunits of myriad bioactive nature products, as well as important syntons of carbohydrate chemistry which have been extensively used to prepare the biologically potential oligosaccharides, glycoconjugates, antibiotics, and structurally varied nature products. Their particular [3.2.1] bicyclic skeleton makes them have high regio- and stereo-control in a variety of reactions, and such structure avoids protecting hydroxyl groups at C1 and C6.Additionally, the cleavage of the internal acetal under acidic conditions could be beneficial for further transformations of functional group and glycosylation of the corresponding pyranosyl sugar at the C6 or C1 site. Herein we developed a novel approach to prepare the 1,6-anhydrohexopyranose, and synthesized the 2-C-branched-1,6-anhydrohexopyranose 1-195, 1-197, 1-198 and 2-C-branched-6-thio-1,6-anhydrohexopyranose 1-225. Until now, glycosylation of 1,6-anhydrohexopyranoses has been limited because of the low yields and low stereoselectivity. In this paper, we found that NiCl5-MeCN system could selectively cleave the ring of 1,6-anhydrohexopyranoses with alcohols and thiols at room temperature in high yields. A series of 2-C-branched-α-glycosides and 2-C-branched-β-thioglycosides have been synthesized via NiCl5-catalyzed. Furthermore, we investigated the formation and ring-opening mechanism of 2-C-acetylmethyl-1,6-anhydrohexopyranose. Glycals are significant starting material in carbohydrate chemistry. After the Fischer-Zach method for forming glucal was reported for the first time, the numerous synthetic methods for glycals have been explored. However, there are several drawbacks in the existing methods, such as the usage of very expensive and toxic reagents, intricate operation, and the influence of acid-sensitive and base-sensitive functional group. We improved the Fischer-Zach method and developed a facile, mild and environmentally benign methodology towards the synthesis of the glycals in Zn-NaH2PO4-H2O or Zn-PEG600-H2O system. Our method involves the treatment of glycosyl bromides with Zn in NaH2PO4 aqueous solution or PEG600-H2O at room temperature, affording various glycals in excellent yields.

A new zirconocene complex, [{eta(5)-C5H4-C(CH2)(5)(CH2)(2)CH(CH3)(2)}2ZrCl2]

The title compound, dichlorobis{eta(5)-[1-(3-methylbutyl)-cyclohex-1 -yl]cyclopentadienyl}zirconium(IV), [ZrCl2-(C16H25)(2)], has a pseudo-tetrahedral bent-metallocene structure in which the substituted cyclopentadienyl rings are asymmetrically bonded to the central Zr atom, due primarily to the interaction between the large substituents and the Cl atoms. The molecule has local C-2 symmetry with the substituents positioned in a trans arrangement and directed towards the lateral sectors of the bent-metallocene unit.

2,2′-联吡啶的吸附行为与其对细胞色素c电化学反应的促进作用

2,2′-联吡啶在金电极上需长达10 h 左右才能达到吸附平衡和有足够量的分子来促进细胞色素 c 的电化学反应.需用长时间浸泡膜转移法,减小因促进剂分子吸附强度的变化而造成的差别.

Low energy C-13(+) and C-13(2+) ion irradiation of water ice

In this paper we report the results of the first experimental study of the irradiation of low temperature water ice (30 and 90 k) using low energy (4keV) C-13(+) and C-(2+) ions. (CO2)-C-13 and H2o2 were readily formed within the H2O ice with the product ion yield and grwoth rate observed to be highly dependent on both the sample temperature and the ion charge state.

Ethanol (C2H5OH) spray of sub-micron droplets for laser driven negative ion source

Liquid ethanol (C₂H₅OH) was used to generate a spray of sub-micron droplets. Sprays with different nozzle geometries have been tested and characterised using Mie scattering to find scaling properties and to generate droplets with different diameters within the spray. Nozzles having throat diameters of 470 µm and 560 µm showed generation of ethanol spray with droplet diameters of (180 ± 10) nm and (140 ± 10) nm, respectively. These investigations were motivated by the observation of copious negative ions from these target systems, e.g., negative oxygen and carbon ions measured from water and ethanol sprays irradiated with ultra-intense (5 × 1019 W/cm2), ultra short (40 fs) laser pulses. It is shown that the droplet diameter and the average atomic density of the spray have a significant effect on the numbers and energies of accelerated ions, both positive and negative. These targets open new possibilities for the creation of efficient and compact sources of different negative ion species.

Fucoidan is a novel platelet agonist for the C-type lectin-like receptor 2 (CLEC-2)

Fucoidan, a sulfated polysaccharide from Fucus vesiculosus, decreases bleeding time and clotting time in hemophilia, possibly through inhibition of tissue factor pathway inhibitor. However, its effect on platelets and the receptor by which fucoidan induces cellular processes has not been elucidated. In this study, we demonstrate that fucoidan induces platelet activation in a concentration-dependent manner. Fucoidan-induced platelet activation was completely abolished by the pan-Src family kinase (SFK) inhibitor, PP2, or when Syk is inhibited. PP2 abolished phosphorylations of Syk and Phospholipase C-γ2. Fucoidan-induced platelet activation had a lag phase, which is reminiscent of platelet activation by collagen and CLEC-2 receptor agonists. Platelet activation by fucoidan was only slightly inhibited in FcRγ-chain null mice, indicating that fucoidan was not acting primarily through GPVI receptor. On the other hand, fucoidan-induced platelet activation was inhibited in platelet-specific CLEC-2 knock-out murine platelets revealing CLEC-2 as a physiological target of fucoidan. Thus, our data show fucoidan as a novel CLEC-2 receptor agonist that activates platelets through a SFK-dependent signaling pathway. Furthermore, the efficacy of fucoidan in hemophilia raises the possibility that decreased bleeding times could be achieved through activation of platelets.

Study of 3 Lambda H and 4 Lambda H in the reaction of 6 Li + 12 C at 2 A GeV

Die Produktion von Hyperkernen wurde in peripheren Schwerionenreaktionen untersucht, bei denen eine Kohlenstofffolie mit $^6$Li Projektilen mit einer Strahlenergie von $2 A$~GeV bestrahlt wurde. Es konnten klare Signale f{"{u}}r $Lambda$, $^3_{Lambda}$H, $^4_{Lambda}$H in deren jeweiligen invarianten Massenverteilungen aus Mesonenzerfall beobachtet werden.rnrnIn dieser Arbeit wird eine unabh{"{a}}ngige Datenauswertung vorgelegt, die eine Verifizierung fr"{u}herer Ergebnisse der HypHI Kollaboration zum Ziel hatte. Zu diesem Zweck wurde eine neue Track-Rekonstruktion, basierend auf einem Kalman-Filter-Ansatz, und zwei unterschiedliche Algorithmen zur Rekonstruktion sekund"{a}rer Vertices entwickelt.rn%-Rekonstruktionsalgorithmen .rnrnDie invarianten Massen des $Lambda$-Hyperon und der $^3_{Lambda}$H- und $^4_{Lambda}$H-Hyperkerne wurden mit $1109.6 pm 0.4$, $2981.0 pm 0.3$ und $3898.1 pm 0.7$~MeV$/c^2$ und statistischen Signifikanzen von $9.8sigma$, $12.8sigma$ beziehungsweise $7.3sigma$ bestimmt. Die in dieser Arbeit erhaltenen Ergebnisse stimmen mit der fr{"{u}}heren Auswertung {"{u}}berein.rnrnDas Ausbeutenverh{"{a}}ltnis der beiden Hyperkerne wurde als $N(^3_{Lambda}$H)/$N(^4_{Lambda}$H)$ sim 3$ bestimmt. Das deutet darauf hin, dass der Produktionsmechanismus f{"{u}}r Hyperkerne in Schwerionen-induzierten Reaktionen im Projektil-Rapidit{"{a}}tsbereich nicht allein durch einen Koaleszenzmechanismus beschrieben werden kann, sondern dass auch sekund{"{a}}re Pion-/Kaon-induzierte Reaktionen und Fermi-Aufbruch involviert sind.rn

Validation of the Chinese version of the Problem Areas in Diabetes (PAID-C) scale

OBJECTIVE To examine the psychometric properties of a Chinese version of the Problem Areas In Diabetes (PAID-C) scale. RESEARCH DESIGN AND METHODS The reliability and validity of the PAID-C were evaluated in a convenience sample of 205 outpatients with type 2 diabetes. Confirmatory factor analysis, Bland-Altman analysis, and Spearman's correlations facilitated the psychometric evaluation. RESULTS Confirmatory factor analysis confirmed a one-factor structure of the PAID-C (χ2/df ratio = 1.894, goodness-of-fit index = 0.901, comparative fit index = 0.905, root mean square error of approximation = 0.066). The PAID-C was associated with A1C (rs = 0.15; P < 0.05) and diabetes self-care behaviors in general diet (rs = −0.17; P < 0.05) and exercise (rs = −0.17; P < 0.05). The 4-week test-retest reliability demonstrated satisfactory stability (rs = 0.83; P < 0.01). CONCLUSIONS The PAID-C is a reliable and valid measure to determine diabetes-related emotional distress in Chinese people with type 2 diabetes.

Investigation of the 1758G>C and 2880A>G variants within the NCOA3 gene in a breast cancer affected Australian population

NCOA3 is a known low to moderate-risk breast cancer susceptibility gene, amplified in 5–10% and over expressed in about 60% of breast tumours. Additionally, this over expression is associated with Tamoxifen resistance and poor prognosis. Previously, two variants of NCOA3, 1758G > C and 2880A > G have been associated with breast cancer in two independent populations. Here we assessed the influence of the two NCOA3 variants on breast cancer risk by genotyping an Australian case–control study population. 172 cases and 178 controls were successfully genotyped for the 1758G > C variant and 186 cases and 182 controls were successfully genotyped for the 2880A > G variant using high-resolution melt analysis (HRM). The genotypes of the 1758G > C variant were validated by sequencing. χ2 tests were performed to determine if significant differences exist in the genotype and allele frequencies between the cases and controls. χ2 analysis returned no statistically significant difference (p > 0.05) for genotype frequencies between cases and controls for 1758G > C (χ2 = 0.97, p = 0.6158) or 2880A > G (χ2 = 2.09, p = 0.3516). Similarly, no statistical difference was observed for allele frequencies for 1758G > C (χ2 = 0.07, p = 0.7867) or 2880A > G (χ2 = 0.04, p = 0.8365). Haplotype analysis of the two SNPs also showed no difference between the cases and the controls (p = 0.9585). Our findings in an Australian Caucasian population composed of breast cancer sufferers and an age matched control population did not support the findings of previous studies demonstrating that these markers play a significant role in breast cancer susceptibility. Here, no significant difference was detected between breast cancer patients and healthy matched controls by either the genotype or allele frequencies for the investigated variants (all p ≥ 0.05). While an association of the two variants and breast cancer was not detected in our case–control study population, exploring these variants in a larger population of the same kind may obtain results in concordance with previous studies. Given the importance of NCOA3 and its involvement in biological processes involved in breast cancer and the possible implications variants of the gene could have on the response to Tamoxifen therapy, NCOA3 remains a candidate for further investigations.

Structure of 5'-O-acetyl-2',3'-O-isopropylideneuridine, C14H18N2O7

M r = 326.3, monoclinic, P21, a --= 6.510 (2), b=8.432 (2), c= 15.114 (2),a, /~= 101.42 (3) ° , Z = 2, V= 813.15 A 3, D x = 1-33 Mg m -3, F(000) = 172, 2(Cu Ka) = 1.5418/~,, g(Cu Ka) = 0.906 mm -~, final R = 6.4% for 1924 observed counter reflections. The conformation about the glycosidic bond is syn [torsion angle C(6)-N(1)-C(1')-O(4')=-103.9(3)°]. The sugar pucker is C(2')-exo,C(3')-endo (3Tz). The conformation about the C(4')-C(5') bond is gauche-trans. An uncommon intermolecular hydrogen bond involving the ribose-ring oxygen O(1') and the base-nitrogen N(3) stabilizes the crystal structure.

Structure of a thionucleoside: 5'-deoxy-5',6-epithio-5,6-dihydro-2',3'-O-isopropylidene-3-methyluridine

C13HlsN205 S, M r = 314.35, orthorhombic, P212121 with a = 39.526 (4), b = 6.607 (2), c = 5.661 (2) A, Z = 4, V = 1478.36 A 3, D c = 1.412 Mg m -3, Cu Ka radiation. Final R = 0.073 for 1154 observed counter reflections. The sulphur atom is in a pseudo-equatorial position with respect to the dihydrouracil ring. The sugar pucker is predominantly O(l')-exo unlike the C(3')-exo,C(4')-endo observed for 2',3'-O-isopropylideneuridine (ISPU). The fivemembered dioxolane ring has C(7) displaced by 0.497 (7)A from the best plane through atoms 0(2'), C(2'), C(3'), 0(3'), in contrast to ISPU where 0(3') shows the maximum deviation.

Structure of 2-(2,6-dimethoxyphenyl)-2,5- dimethylbicyclo[3.2.1]octane-6,8-dione

C18H2204, orthorhombic, P212~21, a = 7.343 (4), b = 11.251 (4), c = 19.357 (4)A, Z = 4, Dr, ' = 1.20, D e = 1.254 g cm -3, F(000) = 648, p(MoKa) = 0.94 cm -~. X-ray intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.052 (R w = 0.045) for 1053 observed reflections. The stereochemical configuration at C(2) has been shown to be 2-exo-methyl-2-endo-(2,6-dimethoxyphenyl), i.e. (3) in contrast to the structure (2) assigned earlier based on its ~H NMR data.

Structure Of A Thionucleoside - 5'-Deoxy-5',6-Epithio-5,6-Dihydro-2',3'-Ortho-Isopropylidene-3-Methyluridine

C13HlsN205 S, M r = 314.35, orthorhombic, P212121 with a = 39.526 (4), b = 6.607 (2), c = 5.661 (2) A, Z = 4, V = 1478.36 A 3, D c = 1.412 Mg m -3, Cu Ka radiation. Final R = 0.073 for 1154 observed counter reflections. The sulphur atom is in a pseudo-equatorial position with respect to the dihydrouracil ring. The sugar pucker is predominantly O(l')-exo unlike the C(3')-exo,C(4')-endo observed for 2',3' O-isopropylideneuridine (ISPU). The fivemembered dioxolane ring has C(7) displaced by 0.497 (7)A from the best plane through atoms 0(2'), C(2'), C(3'), 0(3'), in contrast to ISPU where 0(3') shows the maximum deviation.

The Structure Of 2',3'-O-Isopropylideneuridine

C12HI6N206 is orthorhombic, P2x2121, with a = 19.890 (5), b = 12.789 (2), c = 5.236 (1) A, Z = 4, U = 1331.9/~ 3, F(000) = 600. Mo Ka (/~ = 0.123 mm -1) intensities for 940 unique reflections up to sin 0/2 = 0.538/k -1 were collected on a CAD-4 diffractometer. Final R = 0.034. The glycosidic torsion angle 2~CN is 3"4 °, significantly smaller than that (56.5 °) in 2',3'- -methoxymethyleneuridine (MMU). The ribose moiety has a C(3')-exo-C(4')-endo twist conformation, in contrast to the C(2')-endo conformation in MMU. However, the maximum amplitudes of pucker for the ribose and dioxolane rings are very nearly the same for the two structures. The conformation about C(4')-C(5') is gauche-gauche (~0oo = -68-4, Ooc = 51.3°).

Structure of 2-(2,6-Dimethoxyphenyl)-2,5-dimethylbicyclo[3.2. l]octane-6,8-dione

C18H2204, orthorhombic, P212~21, a = 7.343 (4), b = 11.251 (4), c = 19.357 (4)A, Z = 4, Dr, ' = 1.20, D e = 1.254 g cm -3, F(000) = 648, p(Mo Ka) = 0.94 cm -~. X-ray intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.052 (R w = 0.045) for 1053 observed reflections. The stereochemical configuration at C(2) has been shown to be 2-exo-methyl-2-endo- (2,6-dimethoxyphenyl), i.e. (3) in contrast to the structure (2) assigned earlier based on its ~H NMR data.