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91.
The supermolecular structure of dissolving pulps produced from hardwood by the organosolv processes Acetosolv, Formacell, and Milox was characterized by physical methods (TEM, WAXS, SAXS, NMR) and compared with conventional Sulfite and standard commercial dissolving pulps. The suitability of the pulps for the NMMO technology was tested by spinning fibres and blowing films, whose structural and mechanical properties have also been determined. With TEM it was shown that the TCF-bleached organosolv pulps have only the primary (Formacell), the primary and S1 (Milox), or mainly the S1 (Acetosolv) layers exposed to the surface, whereas Sulfite pulping exposes the S2 cell wall layer. Especially for Milox and Acetosolv Eucalyptus wood pulps, a reduced degree of crystallinity was found, both with WAXS and NMR. The SAXS results indicate a lower pore intersection length for the new pulps as compared to conventional pulps. Unbleached organosolv pulps show a lower crystallinity, very low pore intersection lengths, and an average crystallite shape different from their bleached counterparts. The dissolution behaviour in NMMO and the processability of the bleached organosolv pulps was satisfactory so far. Fibres and films could be produced with structural and mechanical properties comparable with conventional Sulfite and standard commercial dissolving pulp products. However, unbleached organosolv pulps did not meet the requirements of the NMMO process.  相似文献   
92.
93.
The diastereoisomeric 2-substituted 2-azabicyclo[2.2.1]hept-5-enes 2 – 4 were prepared by aza-Diels-Alder reaction of cyclopentadiene with the corresponding methaniminium ions. Their relative configurations were deduced using 1H, 1H-ROESY experiments, and their absolute configurations were assigned from the crystal structure of the aziridinium derivative (?)- 5 . The absolute configuration of (+)- 1 , i.e. (1R), was assigned by CD spectroscopy.  相似文献   
94.
ABSTRACT

The synthesis of 7-O-α-L-daunosaminyl-4-O-methyl-β-rhodomycinone (3) and the determination of its cytotoxic potency compared to that of the natural 7-O-α-L-dau-nosaminyl-β-rhodomycinone (4) are described. Starting with natural β-rhodomycinone (7), trimethylsilyl protecting groups were attached to the hydroxy groups at position 7 and 10, and the 4-OH group was subsequently methylated (MeI/Cs2CO3), thus providing the 4-O-methyl-7, 10-bis-O-trimethylsilyl-β-rhodomycinone (10). The two TMS groups were then deblocked to give 4-O-methyl-β-rhodomycinone (12). In a 3-stage synthesis 12 was converted into 4-O-methyl-10-O-trifiuoroacetyl-ß-rhodomycinone (15) to which l, 4-bis-O-p-nitrobenzoyl-3-N-trifluoroacetyl-L-daunosamine 16 was selectively linked to afford the 7-O-α-glycoside 17. The acyl protective groups are removed by treatment with 1N NaOH to give 3.  相似文献   
95.
A series of viscose fibres from the tyre cord type varying in mechanical parameters and titre were compounded with polypropylene to produce fibre reinforced composites. Single fibre strength is analysed in detail and conclusions are drawn with respect to effective strength values in composite applications. Composites were analysed in terms of tensile and impact properties. Correlations between single fibre and composite properties are studied. High fibre elongation leads to favourable composite impact properties via high composite elongations at break. Using water as a plastisizing agent increasing fibre elongation, notched Charpy impact strength can be improved by more than 50%. Using a modified rule of mixtures and a shear lag model for the composite modulus it was shown how a titre reduction improves the composite stiffness by an increased interfacial area. A direct fibre-composite strength correlation was not found.  相似文献   
96.
Using angle-resolved X-ray photoelectron spectroscopy (ARXPS), we investigate the topmost nanometers of various binary ionic liquid (IL) mixtures at different temperatures in the liquid state. The mixtures consist of ILs with the same [PF6] anion but two different cations, namely 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF6], and 1-butyl-3-methylimidazolium hexafluorophosphate, [C4C1Im][PF6], with 10, 25, 50 and 75 mol % content of [PFBMIm][PF6]. We observe a preferential enrichment of the fluorinated chain in the topmost layer, relative to the bulk composition, which is most pronounced for the lowest content of [PFBMIm][PF6]. Upon cooling the mixtures stepwise from 95 °C until surface charging effects in XPS indicate solidification, we observe a pronounced increase in surface enrichment of the fluorinated chain with decreasing temperature in the liquid state. In contrast to the mixtures with lower [PFBMIm][PF6] contents, cooling the 75 mol % mixture additionally shows an abrupt decrease of the fluorinated chain signal before complete solidification occurs, which is assigned to partial precipitation effects.  相似文献   
97.
Reaction of the tricyclic psychotropic drug opipramol ( 1 ) with an excess of HNO2 affords a product mixture mutagenic for Salmonella typhimurium. The main product is a tetracyclic furoxan 2 (yield ca. 80%), resulting from nitrosation at C(10) and C(11) of 1 . Compound 2 is not mutagenic. The essential mutagen is a nitroarene 3 formed via contraction of the central ring of 1 , and nitrosation at C(2). Its yield is extremely low (<0.1%). Nitroarenes have previously not been encountered as mutagenic products of the interaction of drugs with nitrite.  相似文献   
98.
We studied the formation and surface behavior of Pt(II) and Pd(II) complexes with ligand systems derived from two nitrile-functionalized ionic liquids (ILs) in solution using angle-resolved X-ray photoelectron spectroscopy (ARXPS). These ligand systems enabled a high solubility of the metal complexes in IL solution. The complexes were prepared by simple ligand substitution under vacuum conditions in defined excess of the coordinating ILs, [C3CNC1Im][Tf2N] and [C1CNC1Pip][Tf2N], to immediately yield solutions of the final products. The ILs differ in the cationic head group and the chain length of the functionalized substituent. Our XPS measurements on the neat ILs gave insights in the electronic properties of the coordinating substituents revealing differences in donation capability and stability of the complexes. Investigations on the composition of the outermost surface layers using ARXPS revealed no surface affinity of the nitrile-functionalized chains in the neat ILs. Solutions of the formed complexes in the nitrile ILs showed homogeneous distribution of the solute at the surface with the heterocyclic moieties preferentially orientated towards the vacuum, while the metal centers are rather located further away from the IL/vacuum interface.  相似文献   
99.
100.
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