Living cationic polymerization of 1H,1H,2H,2H perfluorooctyl vinyl ether

Summary Cationic polymerization of 1H,1H,2H,2H perfluorooctyl vinyl ether (CH₂=CH-O-C₂H₄-C₆F₁₃), initiated by the HI/ZnI₂ system in 1,1,2 trichloro trifluoro ethane at-30°C, leads to living polyvinyl ethers bearing a fluoroalkyl group. Results indicate that the polymerization is indeed free from chain transfer and termination reactions and that polyethers of controlled molecular weight and a narrow molecular weight distribution can be made available.     

1H,1H,2H,2H-全氟烷基丙烯酸酯的自压催化合成

以丙烯酸钾盐和全氟烷基乙烯基加成物(PFOEI)为原料,在反应体系自身产生的压力下,催化合成1H,1H,2H,2H-全氟烷基丙烯酸酯,考察了在原料配比为,n(PFOEI):n(丙烯酸钾):n(叔戊醇):n(PIC):n(阻聚剂)=1:1.5:20:0.06:0.05、反应时间为9 h下,溶剂、相转移催化剂和反应温度对酯...     

5,6-二氨基-1-甲基-2,4-(1H,3H)嘧啶二酮的合成

甲基脲和氰乙酸乙酯在乙醇钠中缩合环化得到6-氨基尿嘧啶钠盐,钠盐酸化得6-氨基-1-甲基-2,4-(1H,3H)嘧啶二酮,再与亚硝酸盐亲电加成得到5-亚硝基-6-氨基-1-甲基-2,4-(1H,3H)嘧啶二酮,最后经连二亚硫酸钠还原得到5,6-二氨基-1-甲基-2,4-(1H,3H)嘧啶二酮,总收率为91.6%,其结构经1HNMR和IR表征。     

组胺H1受体与拮抗剂的相互作用

利用分子对接手段对H1受体与组胺以及各种拮抗剂的相互作用进行研究发现,组胺和各类拮抗剂与靶点之间的相互作用各有不同。组胺与靶点间的相互作用是以氢键为主的电性相互作用。经典的H1受体拮抗剂与受体间则以p-π、π-π相互作用为主,而无嗜睡作用的H1受体拮抗剂更是氢键、p-π、π-π相互作用皆有体现。     

5-[(4-氨基苯基)二氮烯基]嘧啶-2,4,6(1H,3H,5H)-三酮的合成

以对硝基苯胺和巴比妥酸为原料,通过重氮化及偶合反应合成了5-[(4-硝基苯基)二氮烯基]嘧啶-2,4,6(1H,3H,5H)-三酮(A),化合物A经硫化物还原,得到单偶氮化合物5-[(4-氨基苯基)二氮烯基]嘧啶-2,4,6(1H,3H,5H)-三酮(B),该化合物可作为重氮组分与一些具有活泼氢的偶合组分反应,从而制备出酰胺键多、对称性高及稳定性强的双偶氮化合物。考察了还原剂用量、反应时间及反应温度对化合物B收率的影响,结果表明:投料比n(A)∶n(Na2S)=1∶1.7,105℃下回流48h,化合物B的收率为84.6%。利用1H NMR、FT-IR及元素分析对产物的结构进行了表征。     

Photoinduced H1b and H1c centers in some natural treated diamonds

Three natural, treated-color diamonds present photoinduced H1b/H1c centers after UV exposure. As the H1b/H1c absorptions increase, that of the 595 nm center decreases. Recovery occurs by simple exposure to a standard incandescent 100 W lamp. The centers implied are all related to nitrogen and to the existence of a treatment, the formation of H1b/H1c centers coming from the trapping of the 595 nm center. The photoinduced behavior seems to confirm the close relation between the 595 nm center and the H1b/H1c centers, and might help in gemological identification.     

Poly(di-1H,1H,2H,2H-perfluoroalkylitaconate) films: surface organisation phenomena, surface energy determinations and force of adhesion measurements

The significance of the Liftshitz/van der Waals, Lewis-acid, and Lewis-base contributors to the total surface energy of an homologous series of poly(di-1H,1H,2H,2H-perfluoroalkylitaconate)s is discussed in terms of the molecular design features and surface organisation phenomena characterising these, comb-like, polymers. Comparison of the characteristics specific to films prepared from this class of materials with those of the previously-studied homologous series of poly(perfluoroalkylacrylate)s, poly(perfluoroalkylmethacrylate)s and poly(methylpropenoxyalkyl siloxane)s suggests that, of the molecular design requirements for low-surface-energy polymers, an increase in the packing density of pendent side-chains has little effect on the contributors to surface energy but an adverse effect on the roughness of the film.     

Part 3. Copolymers of 1H,1H,2H,2H‐perfluorodecyl acrylate and 2,2,2‐trifluoroethyl methacrylate with butyl methacrylate

Copolymers of 2,2,2‐trifluoroethyl methacrylate, or 1H,1H,2H,2H‐perfluorodecyl acrylate (XFDA) and butyl methacrylate (BMA) have been irradiated in air under artificial solar light and their photo‐oxidative stability has been investigated. Molecular and chemical changes occurring during the treatments have been monitored by weight loss and gel content determination, size exclusion chromatography and FTIR spectroscopy. It has been determined that the overall behaviour of both copolymers is controlled by the BMA units, independently of the total fluorine content. The photo‐ageing takes place mainly via the mechanism of oxidation of methacrylic polymers containing long side ester groups, whose flexibility favours macroradical coupling reactions. The tendency to crosslink is balanced only in the case of the initial stages of degradation of XFDA/BMA by the scission reactions derived from the direct attack of oxygen on the fluorinated acrylic units. © 2001 Society of Chemical Industry     

High structural retention during pulsed plasma polymerization of 1H,1H,2H-perfluorododecene: an NMR and TOF-SIMS study

A combined NMR and TOF-SIMS study has been carried out on 1H,1H,2H-perfluorododecene plasma polymers. Pulsed plasma polymerization is found to give rise to a high level of structural retention for the perfluoroalkyl groups, whereas continuous wave conditions lead to monomer fragmentation and cross linking. This investigation provides unequivocal proof that pulsed plasma deposition is a simple and highly effective method for functionalising solid surfaces.     

Synthesis of Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate copolymers and their application on cotton fabrics

Bis(1H, 1H, 2H, 2H‐perfluoro‐octyl)methylenesuccinate (FOM)/ethyl acrylate (EA)/methyl methacrylate (MMA) copolymer (FOME) latexes, FOM/butyl acrylate (BA)/MMA copolymer (FOMB) latexes, and FOM/octyl acrylate (OA)/MMA copolymer (FOMO) latexes were synthesized by continuous emulsion polymerization. Solution polymerization was also carried out to prepare FOMB. The influences of fluorine content and curing conditions on the surface properties of polymer films were discussed. The water and oil repellency of cotton fabrics treated with the FOM copolymers was better than that of conventional poly(fluoroalkyl acrylate)s containing the same fluorinated chain. The polymer films or the treated fabrics were characterized by Fourier transform infrared, scanning electron microscope, atomic force microscopy, thermogravimetric analysis, x‐ray photoelectron spectrometry, and wide angle x‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

甲型H1N1流感疫苗免疫安全性观察

目的观察国产甲型H1N1流感疫苗的免疫安全性。方法对3～65岁的人群接种国产甲型H1N1流感疫苗和接种季节性流感疫苗进行接种副反应观察。结果 78972人接种甲型H1N1流感疫苗者,有91人次局部轻微红肿,另有6人出现发热,1人出现过敏,接种反应率为0.124%。季节性流感疫苗接种24899人次,局部轻微红肿26人次,发热2人次,接种反应率为0.112%,结论国产甲型H1N1流感疫苗副反应少,免疫安全性可靠,群众可放心接种。     

Dispersion polymerization of MMA in supercritical CO2 in the presence of poly(poly(ethylene glycol) methacrylate-co-1H,1H,2H,2H-perfluorooctylmethacrylate)

Various random copolymers of poly(poly(ethylene glycol) methacrylate-co-1H,1H,2H,2H-perfluorooctylmethacrylate) (p(PEGMA-co-FOMA)) with different poly(ethylene glycol) (PEG) chain length (M_n = 300, 475, and 1100) and different FOMA content have been synthesized in supercritical carbon dioxide (scCO₂) via free-radical polymerization. The copolymers containing above 50 wt% FOMA could be used as a stabilizer for the polymerization of methyl methacrylate (MMA) in scCO₂. For PEGMA (300) and PEGMA (475) copolymers, the copolymeric stabilizer with 67–69 wt% FOMA content was shown to be optimal to produce micrometer-size spherical PMMA powder. The size of pendant PEG group and the composition of copolymer as well as the concentration of MMA affected on the size of PMMA particles and the stability of PMMA latexes in CO₂.     

A novel sequence-based antigenic distance measure for H1N1, with application to vaccine effectiveness and the selection of vaccine strains

H1N1 influenza causes substantial seasonal illness and was the subtype of the 2009 influenza pandemic. Precise measures of antigenic distance between the vaccine and circulating virus strains help researchers design influenza vaccines with high vaccine effectiveness. We here introduce a sequence-based method to predict vaccine effectiveness in humans. Historical epidemiological data show that this sequence-based method is as predictive of vaccine effectiveness as hemagglutination inhibition assay data from ferret animal model studies. Interestingly, the expected vaccine effectiveness is greater against H1N1 than H3N2, suggesting a stronger immune response against H1N1 than H3N2. The evolution rate of hemagglutinin in H1N1 is also shown to be greater than that in H3N2, presumably due to greater immune selection pressure.     

Antiviral Gene Expression in Young and Aged Murine Lung during H1N1 and H3N2

Influenza is a respiratory virus that alone or in combination with secondary bacterial pathogens can contribute to the development of acute pneumonia in persons >65 years of age. Host innate immune antiviral signaling early in response to influenza is essential to inhibit early viral replication and guide the initiation of adaptive immune responses. Using young adult (3 months) and aged adult mice infected with mouse adapted H1N1 or H3N2, the results of our study illustrate dysregulated and/or diminished activation of key signaling pathways in aged lung contribute to increased lung inflammation and morbidity. Specifically, within the first seven days of infection, there were significant changes in genes associated with TLR and RIG-I signaling detected in aged murine lung in response to H1N1 or H3N2. Taken together, the results of our study expand our current understanding of age-associated changes in antiviral signaling in the lung.     

Synthesis of 1,9-bis[glycidyloxypropyl]penta(1′H,1′H,2′H,2′H-perfluoroalkylmethylsiloxane)s and copolymerization with piperazine

A series of 1,9-bis[glycidyloxypropyl]pentasiloxanes (IV-VI) were prepared by the platinum catalyzed hydrosilylation of 1,9-dihydridodecamethylpentasiloxane (I), 1,9-dihydrido-3,5,7-tris(3′,3′,3′-trifluoropropyl)heptamethylpentasiloxane (II), and 1,9-dihydrido-3,5,7-tris(1′H,1′H,2′H,2′H-perfluorooctyl)heptamethylpentasiloxane (III) with allyl glycidyl ether. Subsequently, IV-VI were copolymerized with piperazine to form high molecular weight copoly(carbosiloxane)s (VII-IX). The structures of the 1,9-bis[glycidyloxypropyl]penta-siloxanes (IV-VI) and copoly(carbosiloxane)s (VII-IX) were determined by ¹H, ¹³C, ²⁹Si, and ¹⁹F NMR as well as IR spectroscopy. The molecular weight distributions (M_w/M_n) of VII-IX have been characterized by gel permeation chromatography and their thermal properties measured by differential scanning calorimetry and thermal gravimetric analysis.     

以重配技术制备H1N1流感病毒Vero细胞适应株

目的以重配技术制备H1N1流感病毒Vero细胞适应株,为以Vero细胞为基质生产流感疫苗奠定基础。方法以流感病毒Vero细胞适应株A/Yunnan/1/2005Va(H3N2)为母本株,与WHO推荐的2007～2008年度北半球流感疫苗生产用毒株A/Caledonia/20/99(H1N1)共同感染SPF鸡胚和Vero细胞,用抗A/Yunnan/1/2005Va(H3N2)抗体筛选重配病毒,在Vero细胞连续传12代,采用血凝抑制试验和RT-PCR鉴定病毒型别。将重配病毒经Vero细胞大量培养,重配前的病毒经鸡胚大量培养,分别经甲醛灭活,制备灭活疫苗,免疫ICR小鼠,检测其免疫原性。结果获得了1株Vero细胞适应的高产H1N1流感病毒株,连续传9代后,病毒血凝滴度维持在512,免疫原性与重配前的毒株相比,差异无统计学意义。结论通过流感病毒Vero细胞适应株与流行株的重配和抗体筛选,可以获得H1N1流感病毒Vero细胞适应株。     

Umsetzungen substituierter 1-Thiochromone und 4(1H)-Chinolone mit Nucleophilen

Reactions of Substituted 1-Thiochromones and 4(1H)-Quinolones with Nucleophiles 1-Thiochromone 1a and 4(1H)-quinolone 1b react with nucleophiles to substitute the methylthio group. Compounds of type 1 are suitable C₃-fragments for the synthesis of novel heterocycles. Hydroxylamine leads to 2-amino-1-thiochromone-3-carboxamide 7 , whereas 1c gives 2-methylthio-1-thiochromone-oxime 8 .     

甲型H1N1流感病毒实时荧光PCR诊断试剂盒的制备

目的制备甲型H1N1流感病毒实时荧光PCR诊断试剂盒,并进行验证。方法采用磁珠法从甲型H1N1流感疑似患者咽拭子样品中提取病毒RNA,逆转录合成cDNA。根据NCBI最新公布的大流行甲型H1N1流感病毒(2009)基因序列,设计针对编码基质蛋白M基因的引物和探针,检测甲型流感病毒;设计针对血凝素(HA)基因和神经氨酸酶(NA)基因特异性的引物和探针,检测甲型H1N1流感病毒;同时针对人的RNaseP基因设计用于内部控制的引物和探针。所有探针均为Taqman探针,5'端标记FAM,3'端标记BHQ1。对最佳荧光PCR反应条件进行优化,在此基础上组装成甲型H1N1流感病毒实时荧光PCR诊断试剂盒,对其特异性、灵敏度、精密性和稳定性进行验证。与市售试剂盒的检测结果进行对比,并对63份临床甲型H1N1流感疑似患者咽拭子样品进行检测。结果设计的PCR引物及探针能对甲型H1N1流感病毒进行准确检测,与流感病毒的其他型和亚型无交叉反应;试剂盒的灵敏度为0.004个血凝素单位;试验内变异系数小于2.5%,批间变异系数小于5%;试剂盒放置-20℃保存,稳定性良好;检测20份甲型H1N1流感疑似患者咽拭子样品的结果与市售试剂盒一致;检测63份流感疑似患者咽拭子样品,其中大流行甲型H1N1流感病毒阳性36份,普通甲型流感病毒阳性5份。结论所制备的甲型H1N1流感病毒实时荧光PCR诊断试剂盒具有较高的灵敏度、特异性、精密性和稳定性,可用于目前流行的甲型H1N1流感病毒的快速检测。     

The Structure of 23, 24-Dihydrocucurbitacin-F: Full assignments of the 1H and 13C NMR spectra

23, 24-Dihydrocucurbitacin-F has been isolated from hemsleya amabilis. Its structure was studied in detail by ¹H- and ¹³C-, ¹H, ¹H COSY, ¹H, ¹³C HETCOR, ¹H, ¹³C LOCOR, and 1D NOE NMR spectroscopy. All ¹H- and ¹³C-spectral data for this compound have been assigned, and some assignments of ¹H and ¹³C signals have been revised based on the 2D NMR spectra. In particular, previously unassigned methyl and hydroxy signals have been completely assigned via NOE and ¹H, ¹³C-LOCOR experiments.     

Synthesis and antimicrobial evaluation of some pyrazolo-thiazolyl alkoxy-1H-isoindole-1, 3(2H)-dione derivatives

1,3-Thiazolidine-2,4-dione 2 has been synthesized by the cyclisation reaction of thiourea and chloroacetic acid in the presence of ethanol. The reaction of compound 2 with substituted aromatic aldehyde afforded the corresponding derivatives of substituted 5-benzylidene-1,3-thiazolidinone-2,4-dione 3a–d, which upon reflux with ω-bromoalkoxyphthalimide gave 2-{[-5-(substituted benzylidine)-2,4-dioxo-1,3-thiazolidine-3-yl]alkoxy} -1H-isoindole-1,3(2H)-dione 4a–i. Further, compounds 4a–i were treated with phenyl hydrazine and 2,4 dinitro phenyl hydrazine in the DMF to yield the title compound 2-[5-oxo-2,3-substituted diphenyl-2H-pyrazolo[3,4-d][1,3]thiazol-6(5H)-yl)alkoxy]-1H-isoindole-1,3(2H)-dione 5a–r. Structures of newly synthesized compounds were established based on elemental analysis, IR, ¹H NMR and mass spectral data. Synthesized compounds have been assayed for their antibacterial activities against B. subtilis, K. pneumoniae, P. aeruginosa and S. aureus and antifungal activities against A. fumigatus and C. albicans.