Kinetic and stoichiometric assessment of the antioxidant activity of flavonoids by electron spin resonance spectroscopy

There is current interest in the use of naturally occurring flavonoids as antioxidants for the preservation of foods and the prevention of diseases such as atherosclerosis and cancers. To establish the molecular characteristics required for maximum antioxidant activity, electron spin resonance (ESR) spectroscopy has been used to determine the stoichiometry and kinetics of the hydrogen-donating ability of 15 flavonoids and d-alpha-tocopherol to galvinoxyl, a resonance-stabilized, sterically protected aryloxyl radical. The second-order reaction rates, which will be governed by O-H bond dissociation energies, were myricetin > morin > quercetin > fisetin approximately catechin > kaempferol approximately luteolin > rutin > d-alpha-tocopherol > taxifolin > tamarixetin > myricetin 3',4',5'-trimethyl ether > datiscetin > galangin > hesperitin approximately apigenin. Reactivity is highly dependant on the configuration of OH groups on the flavonoid B and C rings, there being little contribution from the A ring to antioxidant effectiveness. Highest reaction rates and stoichiometries were observed with flavonols capable of being oxidized to orthoquinones or extended paraquinones. However, rates and stoichiometries did not always correlate and the data suggest that kinetic factors may be of greater importance within a biological context.     

Evaluation of a regimen using a progesterone releasing intravaginal device (CIDR) and PMSG as a treatment for post partum anoestrus in dairy cattle

Anoestrous dairy cows in seasonally calving herds in the Macalister Irrigation District of Gippsland, Victoria were treated at the start of the mating period with a progesterone releasing intravaginal device (CIDR). The CIDR was inserted for 7 days and 400 IU of PMSG was injected intramuscularly at removal. There was no clinically useful difference among cows receiving the CIDR, a placebo and untreated cows in the interval from treatment to either first oestrus or conception, the conception rate to first service or percent pregnant by the end of mating. Analyses of data from 2-year-old cows, older cattle, cows calved at least 45 days or cows calved at least 55 days and cows treated 3 weeks after the start of mating did not show improved reproductive performance following treatment with the CIDR.     

Bilateral ovarian adenocarcinoma in a mare causing haemoperitoneum and colic

Abstract

CASE HISTORY: A 13-year-old Thoroughbred mare was presented with a history of mild colic over 3 days. This colic had acutely exacerbated and was unresponsive to analgesic treatment, and was referred to Massey University Veterinary Teaching Hospital.

CLINICAL FINDINGS: On examination the heart rate was 100 beats per minute, and mucous membranes were pale and tacky. A large mass was detected on transrectal palpation in the caudal abdomen to the left of midline. Explorative laparotomy revealed severe haemoperitoneum and several masses that were associated with the reproductive tract. The mare was then subject to euthanasia. On post-mortem examination, adjacent and attached to each ovary were soft, lobulated dark red masses up to 200 mm in diameter. Similar masses were present in the omentum and on the peritoneal surface of the diaphragm and the serosa of the spleen and liver. Histopathology revealed that the neoplastic component of the masses comprised proliferating cuboidal to columnar cells forming disorganised acini and cords separated by dense collagenous stroma. Immunohistochemistry showed the neoplastic cells were positive for cytokeratin AE1/AE3 and vimentin, but negative for cytokeratin 7 and inhibin α.

DIAGNOSIS: Bilateral ovarian adenocarcinoma with transcoelomic metastasis and terminal decompensation due to rupture of a neoplastic mass and consequent haemoperitoneum.

CLINICAL RELEVANCE: To the authors' knowledge, bilateral ovarian adenocarcinoma has not been previously reported in a horse. Ovarian adenocarcinoma should be considered when horses present with haemoperitoneum and colic. Further research is required on the immunohistochemical differentiation of adenocarcinoma of ovarian and intestinal origin in the horse.     

A 100,000-year periodicity in the accretion rate of interplanetary dust

Numerical modeling of the orbital evolution of interplanetary dust particles revealed that, over the past 1.2 million years, the rate of accretion of dust by Earth has varied by a factor of 2 to 3. These variations display a 100,000-year periodicity and are anticorrelated with Earth's changing orbital eccentricity. Extraterrestrial helium-3 concentrations in a deep-sea sediment core display a similar periodicity but are 50,000 years out of phase with the predicted variations. Also, because collisions between large bodies in the asteroid belt are inevitable, it is expected that large-amplitude stochastic variations on 10(7)- to 10(8)-year time scales would be superimposed on the 10(5)-year periodic variations.     

Unitary control in quantum ensembles: maximizing signal intensity in coherent spectroscopy

Experiments in coherent magnetic resonance, microwave, and optical spectroscopy control quantum-mechanical ensembles by guiding them from initial states toward target states by unitary transformation. Often, the coherences detected as signals are represented by a non-Hermitian operator. Hence, spectroscopic experiments, such as those used in nuclear magnetic resonance, correspond to unitary transformations between operators that in general are not Hermitian. A gradient-based systematic procedure for optimizing these transformations is described that finds the largest projection of a transformed initial operator onto the target operator and, thus, the maximum spectroscopic signal. This method can also be used in applied mathematics and control theory.     

Local orbital forcing of antarctic climate change during the last interglacial

During the last interglacial, Antarctic climate changed before that of the Northern Hemisphere. Large local changes in precession forcing could have produced this pattern if there were a rectified response in sea ice cover. Results from a coupled sea ice-ocean general circulation model supported this hypothesis when it was tested for three intervals around the last interglacial. Such a mechanism may play an important role in contributing to phase offsets between Northern and Southern Hemisphere climate change for other time intervals.