不同软段结构聚氨酯-酰亚胺嵌段共聚物的合成及热性能研究

用二步法合成了不同软段 (PPO ,PEG ,PEPA)聚氨酯 酰亚胺 (PUI)嵌段共聚物 ,FTIR光谱表征了所有合成PUI分子主链均含有酰亚胺链段 ,并研究了PUI嵌段共聚物的热性能受软段类型及长度的影响 .DSC研究表明聚酯型PUI的软硬段之间的相容性比聚醚型PUI好 ,随相同软段分子量的增加 ,PUI体系的软硬段兼容性变差 ,并显示了相分离的特征 ;热失重 (TGA)研究得出不同软段的PUI样品的热稳定性大小顺序为 :PEPA PUI >PEG PUI>PPO PUI ;动态力学 (DMTA)研究给出了所合成的PUI样品在 5 0～ 2 0 0℃范围内均出现了较长的模量平台显示出有较好的耐热性 ,且随硬段含量的升高其储能模量不断增强     

Synthesis, characterization, antitumor activity of nickel(Ⅱ) and cobalt (Ⅱ) complexes of 2,2''''-diamino-4,4''''-bithiazole and their interaction with dGMP

New complexes,of bis(2,2'-diamino-4,4'-bithiazole)sulfate nickel(Ⅱ) and bis(2,2'-diami-no-4,4'-bithiazole)sulfate cobalt(Ⅱ),have been prepared.The complexes were characterized by infrared and UV-Vis spectroscopy,1H NMR,elemental analyses and molar conductivity.The effect of these complexes on the DNA synthesis of sarcoma 180 cells has been studied by the technique of isotopic liquid scintillation.The results indicated that complexes show ability to inhibit DNA synthesis of the tumor cells.In order to provide a molecular basis for understanding the biological effects,the probe,[trana-en2Os(η2-H2)](CF3SO3)2 (en,ethylenediamine) as a monitor was first used to explore interaction of the complexes with 2'-deoxyguanosine-5'-monophosphate (dGMP).     

Synthesis of α, ω perfluoropolyether iodides

Perfluoropolyether (PFPE) diacyl halides of formula XCOCF₂O[(CF₂O)_n(CF₂CF₂O)_m]_pCF₂COX, with X = Cl, F and molecular weight (MW) 400-4000 g mol⁻¹ are smoothly converted in high yields to the corresponding α, ω diiodides in the absence of solvent, employing KI or LiI at 210 °C with extrusion of CO. During the reactions, β-elimination of COF₂ from the terminal difluoromethylene oxide units (CF₂O, C₁ unit) occurs to some extent until a tetrafluoroethylene oxide unit (OCF₂CF₂, C₂ unit) is encountered yielding a OCF₂CF₂I terminus. This considerably alters the MW distribution of the final diiodide especially for low MW PFPEs. Operating in supercritical conditions of CO (scCO) or both scCO and CO₂ (scCO₂) on low (<600 g mol⁻¹) MW diacyl halides, lowers β-elimination from 95 to 52 mol% if KI is used or from 43 to 30 mol% if LiI is used. With higher MW (>600 g mol⁻¹) β-elimination is lowered from 15 to <1 mol% in scCO conditions employing KI.     

Synthesis of naturally occurring bioactive butyrolactones: maculalactones A-C and nostoclide I

Starting from citraconic anhydride (13), a simple multistep (9-10 steps) synthesis of naturally occurring butyrolactones maculalactone A (3), maculalactone B (1), maculalactone C (2) and nostoclide I (4) have been described with good overall yields via dibenzylmaleic anhydride (20) and benzylisopropylmaleic anhydride (27). The two anhydrides 20 and 27 were prepared by S_N2′ coupling reactions of appropriate Grignard reagents with dimethyl bromomethylfumarate (14), LiOH-induced hydrolysis of esters to acids, bromination of carbon-carbon double bond, in situ dehydration followed by dehydrobromination and chemoselective allylic substitution of bromoatom in disubstituted anhydrides 19 and 26 with appropriate Grignard reagents. The NaBH₄ reduction of these anhydrides 20 and 27 furnished the desired lactones 21 and 29, respectively. The lactone 21 on Knoevenagel condensation with benzaldehyde, furnished maculalactone B (1), which on isomerization gave maculalactone C (2). Selective catalytic hydrogenation of 1 gave maculalactone A (3). The conversion of lactone 29 to nostoclide I (4) is known.     

Reactive polymeric nanoparticles based on unconventional dextran derivatives

Unconventional dextran derivatives with reactive tosyl- and deoxy-azido moieties were synthesized homogeneously under various reaction conditions. Well soluble tosyl dextran of a high degree of substitution up to 1.66 was prepared applying N,N-dimethylacetamide/LiCl as solvent. Almost 50% of secondary toslyate moieties could be replaced by nucleophilic displacement reaction with azide ions. The structure of the products was efficiently analyzed by NMR spectroscopy also after peracylation of the unconventional dextran derivatives. Applying a simple dialysis technique, nanospheres with a size in the range from 160 to 420 nm (D50%) were obtained that possess reactive functional tosyl- and deoxy-azido groups.     

4,4’-一氧二（苯胺灵）的合成和晶体结构

通过4,4’-一氧二（异氰酸苯酯）与异丙醇加成反应，合成标题化合物 4,4’-一氧二（苯胺灵）(Ⅰ) (C20H24N2O5, Mr=372.41)，并用X射线衍射、红外光谱、13C核磁共振、电子轰击质谱和元素分析对标题化合物进行表征. 晶体属于三斜晶系，空间群为P1晶体学参数为: a=0.85107(17), b=0.91164(18), c=1.45701(3) nm, α=80.44(3)°, β=85.25(3)°, γ=62.88(3)°, V=0.9922(3) nm3, Z=2, Dc=1.247 g•cm－3, μ(Mo Kα)=0.90 cm－1, F(000)=396.两个苯环平面之间的夹角为62.06° (0.06°). 晶体结构经全矩阵最小二乘法修正，最终偏离因子R=0.0520, wR=0.1434(对可观察点).此化合物应具有广谱的生物活性.     

Platination of [3-X-7,8-Ph2-7,8-nido-C2B9H8] (X=Et, F): Synthesis and characterisation of slipped and 1,2→1,7 isomerised products

The reaction of the labelled carborane ligand [3-Et-7,8-Ph₂-7,8-nido-C₂B₉H₈]²⁻ with a source of {Pt(PMe₂Ph)₂}²⁺ affords non-isomerised 1,2-Ph₂-3,3-(PMe₂Ph)₂-6-Et-3,1,2-closo-PtC₂B₉H₈ (1). The analogous reaction between [3-F-7,8-Ph₂-7,8-nido-C₂B₉H₈]²⁻ and {Pt(PMe₂Ph)₂}²⁺ yields 1,8-Ph₂-2,2-(PMe₂Ph)₂-4-F-2,1,8-closo-PtC₂B₉H₈ (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph₂-2,2-(PMe₂Ph)₂-4-Et-2,1,8-closo-PtC₂B₉H₈ (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB₂ face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques.     

Synthesis and nonlinear optical properties of new symmetrically substituted stilbenes

Three new chromophores and trans-4-(N-(ethyl 4″-nitrobenzoate)-N-ethyl amino)-4′-(dimethyl amino) stilbene (DMANHAS) have been synthesized and whose chemical structures have been characterized by ¹H NMR, IR, and elemental analyses. Linear absorption, single-photon-induced fluorescence and two-photon-induced fluorescence are experimentally studied. Trans-4-(N-2-hydroxyethyl-N-ethyl amino)-4′-(dimethyl amino)stilbene (DMAHAS) and trans-4-(N-2-hydroxyethyl-N-ethyl amino)-4′-(diethyl amino)stilbene (DEAHAS) have effective two-photon absorption cross-sections of σ₂=0.91×10⁻⁴⁶ cm⁴ s/photon and σ₂=1.19×10⁻⁴⁶ cm⁴ s/photon at 532 nm by using an open aperture Z-scan technique, respectively. When pumped with 800 nm laser irradiation, DMAHAS and DEAHAS indicate strong two-photon-induced blue fluorescence of 436 and 440 nm, respectively, while trans-4-(N-(ethyl 4″-nitrobenzoate)-N-ethyl amino)-4′-(diethyl amino) stilbene (DEANHAS) and DMANHAS exhibit no fluorescence.     

Synthesis of substituted 4H-thieno[2,3-b][1]benzothiopyran-4-ones as possible schistosomicidal agents

Summary A new series of thiophenic isosters of thioxanthones, namely: 2-substituted-4H-thieno[2,3-b][1]benzothiopyran-4-ones and 5-substituted-2-nitro-8-methyl-4H-thieno[2,3-b][1]benzothiopyran-4-ones were synthesized as potential schistosomicidal agents. The synthesized compounds were characterized by their¹H-NMR data.

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Synthese von substituierten 4H-Thieno[2,3-b][1]benzothiopyran-4-onen als mögliche schistosomicide Wirkstoffe

Zusammenfassung Es wurde eine neue Serie von thiophenischen Isosteren des Thioxanthons, nämlich 2-substituierte 4H-Thieno[2,3-b][1]benzothiopyran-4-one und 5-substituierte 2-Nitro-8-methyl-4H-thieno[2,3-b][1]benzothiopyran-4-one als potentielle schistosomicide Wirkstoffe synthetisiert. Die synthetisierten Verbindungen wurden mittels ihrer¹H-NMR Daten charakterisiert.

     

Indium(III) chloride catalyzed one step synthesis of some new dibenzo(d,f)(1,3)dioxepines and 12H-dibenzo(d,g)(1,3)dioxocin derivatives

In the presence of catalytic amount of indium(III) chloride (10 mol %), 2,2′-dihydroxybiphenyl and bis(2-hydroxyphenyl)methane react quickly, without using any solvent, with ketones or β-keto esters possessing at least one hydrogen atom in α to the ketone-carbonyl group, to afford some new dibenzo(d,f)(1,3)dioxepines and some 12H-dibenzo(d,g)(1,3)dioxocin derivatives, respectively.