Trace metal speciation in natural waters: Computational vs. analytical     

D. Kirk Nordstrom 《Water, air, and soil pollution》1996,90(1-2):257-267

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.  相似文献   

Antioxidant functions of selected allium thiosulfinates and S-alk(en)yl-L-cysteine sulfoxides   总被引：6，自引：0，他引：6  

Xiao H  Parkin KL 《Journal of agricultural and food chemistry》2002,50(9):2488-2493

Pure thiosulfinates, R-S(O)S-R (2), where R = Me (2a), Pr (2b), or All (2c), at levels up to 4 mM were not capable of scavenging hydrogen peroxide or superoxide anion. Relative to standard antioxidants (ascorbic acid, n-propyl gallate, butylated hydroxytoluene, Trolox, and reduced glutathione), these thiosulfinates were 1-3 orders of magnitude less efficient at reducing 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, 0.5-2 orders of magnitude less efficient at quenching singlet oxygen, and about equally effective at scavenging hydroxyl radical. Generally, AllS(O)SAll (2c) was the most effective and PrS(O)SPr (2b) was the least effective thiosulfinate in these assays, except that MeS(O)SMe (2a) exhibited no quenching effect toward singlet oxygen. These thiosulfinates were also incapable at levels up to 0.1 mM (where they were toxic) of in vitro induction of quinone reductase (QR) in murine hepatoma (hepa 1c1c7) cells. However, S-1-propenyl-L-cysteine sulfoxide (isoalliin, 1a) and cycloalliin (3) induced QR in this system at 2 mM and 1 mM, respectively, although doubling of QR required levels of 10-15 mM.  相似文献   

Novel fatty acid esters of p-coumaryl alcohol in epicuticular wax of apple fruit     

Whitaker BD  Schmidt WF  Kirk MC  Barnes S 《Journal of agricultural and food chemistry》2001,49(8):3787-3792

Hexane extracts of epicuticular wax from cv. Gala apples were noted to have an unusual, broad absorbance maximum at approximately 258 nm, which led us to isolate and identify the primary UV-absorbing compounds. Column and thin-layer chromatography yielded a fraction that gave a series of paired, 260-nm-absorbing peaks on C(18) HPLC. These were shown to be a family of phenolic fatty acid esters, for which retention times increased with increasing fatty acid chain length, and paired peaks were esters of two related phenolics with the same fatty acid moiety. Alkaline hydrolysis of the esters released two water-soluble phenolics separable by C(18) HPLC. Electrospray ionization mass spectrometry gave a molecular mass of 150 for both, and (1)H NMR plus UV absorbance spectra identified them as E and Z isomers of p-coumaryl alcohol. Alkaline cleavage of the fatty acid esters in the presence of methanol or ethanol resulted in partial derivatization of E-p-coumaryl alcohol to the corresponding gamma-O-methyl or O-ethyl ether. Gradient HMQC NMR of the HPLC-purified stearate ester of E-p-coumaryl alcohol indicated that fatty acid esterification occurs at the gamma-OH rather than at the 4-OH on the phenyl ring. This is the first report of fatty acid esters of monolignols as a natural plant product.  相似文献   

Long-term anaesthesia with propofol and alfentanil in the dog and its partial reversal with nalbuphine     

P. A. Flecknell  A. J. B. Kirk  C. E. Fox  J. H. Dark 《Veterinary anaesthesia and analgesia》1990,17(1):11-16

Prolonged surgical anaesthesia in the dog was induced with propofol (6.5 ± 1.3 mg/kg) followed by alfentanil (25.5 ± 5 μg/kg) (mean ± 1 sd) and maintained with a continuous infusion of propofol (0.14 to 0.18 mg/kg/min) and alfentanil (2 to 3 μg/kg/min). Neuromuscular blockade was produced with vecuronium (0.1 mg/kg). After induction of anaesthesia with propofol, administration of alfentanil to dogs which had received no pre-anaesthetic medication produced cardiac arrest and apnoea. Administration of atropine intravenously immediately prior to alfentanil prevented these cardiac depressant effects. The cardiac depressant effect of alfentanil was not as severe in a second group of dogs in which anaesthesia was induced with thiopentone. After commencing the continuous infusion anaesthetic regime and establishment of IPPV, blood pressure and heart rate remained stable during the remaining 4 to 6 h period of anaesthesia. Recovery from anaesthesia was smooth and uneventful. The depressant effects of alfentanil on respiration and on consciousness were reversed rapidly by administration of nalbuphine (10 mg total dose). The smooth recovery and the integration of anaesthesia and post operative analgesia attained by the reversal of alfentanil with nalbuphine make this an attractive anaesthetic regime for major surgery in dogs, provided that facilities for IPPV are available.  相似文献   

The use of random skin flaps in equine reconstructive surgery     

Llewellyn C. Peyton  Martha L. Campbell  Gregory A. Wolf  William W. Kirk 《Journal of Equine Veterinary Science》1983,3(3):80-87

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Indirect inguinal hernia in two rhesus monkeys     

C A Rawlings  J H Kirk  J F Harwell  W F Capps 《Journal of the American Veterinary Medical Association》1971,159(5):621-622

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Neurophysiologic maps of cutaneous innervation of the hind limb of sheep     

E J Kirk  R L Kitchell  R D Johnson 《American journal of veterinary research》1987,48(10):1485-1491

The area of skin supplied by afferent fibers in a peripheral nerve is called the cutaneous area (CA) of that nerve. The CA of hind limb nerves that were responsive to movement of wool/hairs were mapped neurophysiologically in 25 barbiturate-anesthetized sheep. The CA of the dorsal cutaneous branches of the caudal lumbar spinal nerves and of the sacral spinal nerves extended over the lateral aspect of the thigh. The CA of the lateral cutaneous femoral nerve was restricted to the stifle region, that of the saphenous nerve did not reach the digits, that of the deep peroneal nerve lay between the 3rd and 4th digits, and that of the lateral plantar nerve was confined to the lateral aspect of the 4th digit. The CA of the superficial peroneal nerve enveloped the dorsal, medial, and lateral aspects of the distal portions of the hind limb. In some sheep, the boundaries of the CA of the superficial peroneal nerve were juxtaposed caudally in such way that the medial plantar nerve did not have an autonomous zone. Differences in sizes of the CA resulted in corresponding differences in the overlap between adjacent CA and concomitant differences in the sizes of autonomous zones.  相似文献   

Endometriosis in four irradiated rhesus monkeys   总被引：3，自引：0，他引：3  

G A Splitter  J H Kirk  W F Mac Kenzie  C A Rawlings 《Veterinary pathology》1972,9(4):249-262

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Equine amniotic membrane transplantation for corneal ulceration and keratomalacia in three horses   总被引：1，自引：1，他引：0  

Lassaline ME  Brooks DE  Ollivier FJ  Komaromy AM  Kallberg ME  Gelatt KN 《Veterinary ophthalmology》2005,8(5):311-317

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Locomotive disorders associated with sow mortality in Danish pig herds     

Kirk RK  Svensmark B  Ellegaard LP  Jensen HE 《Journal of veterinary medicine. A, Physiology, pathology, clinical medicine》2005,52(8):423-428

Given the increase in sow mortality in Danish pig herds over the last 10 years, we have investigated the causes of spontaneous death and killing of sows, especially those due to locomotive disorders. A total of 265 culled sows (93 spontaneously dead sows and 172 killed sows) from 10 different herds were sent for complete necropsy, and grouped according to primary diagnoses. From 35 of these sows, tissue for histological evaluation and samples for bacteriological cultivation were also collected, and secondary diagnoses and body condition were recorded. The main causes for killing were related to the locomotive system (72%), arthritis (24%) and fractures (16%) being the most frequent lesions. The main causes of spontaneous death were related to the gastrointestinal system and spleen (45%) and the reproductive system (24%). Arthrosis was a secondary diagnosis in 88% of the killed sows and in 92.5% of the spontaneously dead sows. Arcanobacterium pyogenes was the main cause of arthritis. The killed sows had significantly lower body condition compared with spontaneously dead sows. The first two parities and the time around farrowing were associated with the highest mortality in both groups. Hopefully, these observations can guide breeding units attempting to monitor, control and reduce sow mortality.  相似文献