The distribution of anthocyanins in grape skin extracts of port wine cultivars as determined by high performance liquid chromatography

The distribution of anthocyanins in methanolic skin extracts of 16 grape cultivars used for port wine production and grown at five sites in the Douro Valley in Northern Portugal has been assessed by high performance liquid chromatography. Results are confined to the seven most readily separated and identified anthocyanins and are expressed as percentages of their total (88–99% of the total integrated area). Anthocyanins based on malvidin (Mv) predominated. Of these, Mv 3-glucoside was the major pigment (33–60%), being exceeded by Mv 3-p-coumarylglucoside (2–51%) in only two cultivars; Mv 3-acetylglucoside (1–15%) was consistently the lowest. Peonidin 3-glucoside (1–27%) was prominent in four cultivars, but delphinidin 3-glucoside (1–11%), petunidin 3-glucoside (2–11%) and cyanidin 3-glucoside (trace-6%) were of low proportions throughout. The ratio Mv 3-acetylglucoside/total Mv glucosides appeared characteristic of cultivar, independent of site, and a useful aid to identification of grape cultivars. The coloured pulp of some cultivars contained peonidin 3-glucoside as a major component, present in greater proportions than in the skin; the percentage of Mv 3-p-coumarylglucoside was lower in pulp than in skin. The identities of six of the seven anthocyanins were confirmed by fast atom bombardment mass spectrometry and the structures of the Mv derivatives were determined by nuclear magnetic resonance. The formation of formyl and acetyl anthocyanin artefacts is described.     

Effect of 0.1 at.% zirconium on the cyclic oxidation resistance ofβ-NiAl

The effect of 0.1 at.% Zr (0.2 wt.% Zr) on the cyclic oxidation of hipped -NiAl was studied. Oxidation testing was performed in static air at 1100–1200 °C, using 1-hr exposure cycles for test times up to 3000 hr. The weight change versus time data were modeled with the COSP computer program to analyze and predict cyclic-oxidation behavior. Zr additions significantly change the nature of the scale-spalling process during cooling so that the oxide spalls near the oxide-air interface at a relatively low depth within the scale. Without Zr, the predominantly -Al₂O₃ scale tends to spall randomly to bare metal at relatively high effective-scale-loss rates, particularly at 1150°C and 1200°C. This leads to higher rates of Al consumption for the Zr-free aluminide and much earlier depletion of Al, leading to eventual breakaway (i.e., failure).     

Microhardness and corrosion behavior in CrN/electroless Ni/mild steel complex coating

The electroless nickel–phosphorous (Ni–P) coating was chosen as an interlayer to improve the properties of the CrN/mild steel (MS) composite. A hypophosphite-reduced acid solution was used to first deposit electroless Ni–P onto MS substrates, and then the CrN overlayer was deposited by reactive r.f. magnetron sputtering onto the electroless Ni–P modified substrate. The electroless Ni–P layer crystallizes with the precipitation of a Ni₃P phase during r.f. sputtering, and thus a coating–substrate composite of CrN/Ni–Ni₃P/MS is formed. The electroless Ni–P coating increases the surface hardness of the steel substrate to more than three times. The surface hardness of the CrN coating modified by an electroless Ni–P interlayer exhibits a hardness higher than 2000 HK_0.015. The usual substrate effect on the microhardness of the coatings is nearly eliminated with the complex coating feature, and a significant enhancement of surface hardness in the coating assembly is achieved. The corrosion tests indicate that the Ni–Ni₃P/MS configuration exhibits a more positive E_corr value (i.e. less electronegative) than CrN/MS and the corresponding potential curve is shifted toward the low-current side, indicating a better anti-corrosion performance. Through comparison of the E_corr values and the polarization curves, it is demonstrated that the CrN/Ni–Ni₃P/MS composite exhibits significantly higher corrosion resistance than the Ni–Ni₃P/MS and CrN/MS coating configurations.     

基于虚拟仪器的水电机组在线状态监测系统的研究*

随着水电机组状态检修的不断开展, 需要实现对机组的状态监测, 及时了解机组的运行情况并能及时处理。考虑到水电机组状态监测的多样性和复杂性, 结合实际, 提出水电机组在线状态监测的项目和基于PXI 总线仪器和LabVIEW 的具体实施方案。状态监测系统通过对水电机组状态量的采集、处理和分析, 来实现水电机组运行状态在线实时监测, 极大地提高了机组利用率。该系统在水电机组的状态检修中得到了实际应用。     

Diluent effects on carbonate mobility in bisphenol-A polycarbonate in the solid state

The effect of miscible low molecular weight additives on the mobility of the carbonate group in bisphenol-A polycarbonate (BPAPC) has been studied using n.m.r. and dielectric relaxation experiments in the solid state. Proton-enhanced dipolar-decoupled carbon-13 n.m.r. spectra of BPAPC, isotopically enriched at the carbonate position, are obtained without magic-angle sample spinning. The resolved chemical shift anisotropy allows study of nuclear spin relaxation for the carbonate groups in the polymer that have different orientations relative to the static magnetic field in the laboratory frame. The spin-lattice relaxation time in the rotating frame (T_1?) is measured at a motional-probe frequency of 50 kHz for the undiluted polymer and for BPAPC-diluent blends containing either dibutylphthalate or dinitrobiphenyl. The T_1? exhibits some dependence on orientation in all systems studied. In the blend containing dibutylphthalate (DBP), T_1? is decreased by a factor of two for all orientations of the carbonate group. This implies that DBP substantially increases the spectral density of 50 kHz motions in the carbonate region of the polymer at ambient temperature. In contrast, dinitrobiphenyl does not significantly alter the Fourier component of thermal fluctuations at 50 kHz. Dielectric relaxation measurements at 10 kHz reveal that the primary (T_g) and secondary (β) motional processes in BPAPC are affected by low molecular weight additives. An intermediate relaxation process appears in the temperature interval between the glass transition temperature (T_g) and the sub-T_g β-relaxation (T_β) in the polymer-diluent blends. The n.m.r. spin-lattice relaxation rate in the rotating frame, T^?1_1?, correlates well with the relative magnitude of the dielectric dissipation factor (tan δ_ε) between T_g and T_β.     

High resolution solid state 13C n.m.r. of butadiene grafted polypropylene

¹H dipolar decoupled ¹³C n.m.r. experiments with the aid of the magic angle spinning technique have been used to determine the graft content and the isomer content of the polybutadiene grafts in a graft copolymer with isotactic polypropylene.     

Structures and allelopathic effects ofNuphar alkaloids: Nupharolutine and 6,6′-dihydroxythiobinupharidine

Two of the majorNuphar alkaloids, nupharolutine and 6,6-dihydroxythiobinupharidine, were isolated from the aquatic perennial herbNuphar lutea (L.) Sibth. & Sm., yellow water lily. In a lettuce seedling bioassay of the two pure compounds, the former was inactive and the latter was highly inhibitory of radicle elongation at concentrations greater than 2 ppm. Structures and stereochemistry of the two compounds were confirmed by DEPT,¹H-¹H COSY,¹H-¹³C COSY, and¹H-¹H NOESY experiments.     

Structural analysis of Aleksinac oil shale kerogen by high-resolution solid-state C n.m.r. spectroscopy

A sample of kerogen from Aleksinac oil shale was examined by high-resolution solid-state ¹³C n.m.r. spectroscopy. The presence and relative proportions of kerogen structural units were estimated using a combination of NQS and T_1C methods with a peak-synthesis technique applied to the ¹³C CP—MAS spectrum. Relaxation parameters from these experiments were used to estimate differences in relative ‘mobility’ of various structural units. The kerogen was found to be highly aliphatic and to contain 79% long-chain aliphatic plus alicyclic structures, as well as 9% aromatic structures. These findings are in good agreement with the characterization of the same kerogen from its oxidation products.     

Structural significance of the alkyl substituent at the C-4 of (+)-trans-verbenyl acetate in sex pheromonal activity of the American cockroach

The significance of the alkyl group at the C-4 of (+)-trans-verbenyl acetate, which is the sex pheromone mimic of the American cockroach, was investigated. Seven alcohols possessing an ethyl, propyl, or dimethyl group at this position of the 6,6-dimethylbicyclo[3.1.1]heptane skeleton were synthesized and evaluated by behavioral assay. All of the alcohols were inactive, while three of four acetates of the 2-alcohols induced sexual behavior in male cockroaches at the 0.02 or 0.5 mg dosage level, either of which is many orders of magnitude higher than the threshold level of the natural sex pheromones (10^–8 mg). Among the acetates, the compounds with a methyl group or an -oriented ethyl group at C-4 showed the highest activity. The results are discussed in terms of spatial requirements of the molecules for interactions with the receptor.Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part VIII. For Part VII, seeComp. Biochem. Physiol.,70A: 229–234 (1981).