Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Nestmate discrimination in the social wasp Ropalidia marginata: chemical cues and chemosensory mechanism

Nestmate discrimination plays an important role in preserving the integrity of social insect colonies. It is known to occur in the primitively eusocial wasp Ropalidia marginata in which non-nestmate conspecifics are not allowed to come near a nest. However, newly eclosed females are accepted in foreign colonies, suggesting that such individuals may not express the cues that permit differentiation between nestmates and non-nestmates. As cuticular hydrocarbons (CHCs) have been implicated as chemosensory cues used in nestmate recognition in other species, we investigated, using bioassays and chemical analyses, whether CHCs can play a role in nestmate recognition in R. marginata. We found that individuals can be differentiated according to colony membership using their CHC profiles, suggesting a role of CHCs in nestmate discrimination. Non-nestmate CHCs of adult females received more aggression than nestmate CHCs, thereby showing that CHCs are used as cues for nestmate recognition. Contrarily, and as expected, CHCs of newly eclosed females were not discriminated against when presented to a foreign colony. Behavioural sequence analysis revealed the behavioural mechanism involved in sensing nestmate recognition cues. We also found that newly eclosed females had a different CHC profile from that of adult females, thereby providing an explanation for why young females are accepted in foreign colonies. (C) 2013 The Association for the Study of Animal Behaviour. Published by Elsevier Ltd. All rights reserved.

On the Benefits of Including Age-structure in Harvest Control Rules

This paper explores the benefits of including age-structure in the control rule (HCR) when decision makers regard their (age-structured) models as approximations. We find that introducing age structure into the HCR reduces both the volatility of the spawning biomass and the yield. Although at a fairly imprecise level the benefits are lower, there are still major advantages for actual assessment precision of the case study. Moreover, we find that when age-structure is included in the HCR the relative ranking of different policies in terms of variance in biomass and yield does not differ. These results are shown both theoretically and numerically by applying the model to the Southern Hake fishery.

Age determination in tropical fish

This essay presents evidence that check marks on the hard parts of tropical fishes can be used for aging these, in spite of the small seasonal temperature and other environmental oscillations prevailing in the tropics. The ideas presented in this article were over 50 years ahead of their time.

Review of size- and age-dependence in batch spawning: implications for stock assessment of fish species exhibiting indeterminate fecundity

Most assessments of fish stocks use some measure of the reproductive potential of a population, such as spawning biomass. However, the correlation between spawning biomass and reproductive potential is not always strong, and it likely is weakest in the tropics and subtropics, where species tend to exhibit indeterminate fecundity and release eggs in batches over a protracted spawning season. In such cases, computing annual reproductive output requires estimates of batch fecundity and the annual number of batches—the latter subject to spawning frequency and duration of spawning season. Batch fecundity is commonly measured by age (or size), but these other variables are not. Without the relevant data, the annual number of batches is assumed to be invariant across age. We reviewed the literature and found that this default assumption lacks empirical support because both spawning duration and spawning frequency generally increase with age or size. We demonstrate effects of this assumption on measures of reproductive value and spawning potential ratio, a metric commonly used to gauge stock status. Model applications showed substantial sensitivity to age dependence in the annual number of batches. If the annual number of batches increases with age but is incorrectly assumed to be constant, stock assessment models would tend to overestimate the biological reference points used for setting harvest rates. This study underscores the need to better understand the age- or size-dependent contrast in the annual number of batches, and we conclude that, for species without evidence to support invariance, the default assumption should be replaced with one that accounts for age- or size-dependence.

Use of eye lens diameter and weight as an age indicator in the carangid fish, Decapterus russelli (Pisces: Carangidae) from Gulf of Oman: preliminary observation

Specimens of Decapterus russelli have been collected from Lema, north of the Gulf of Oman. The ocular lens diameter and weight were tested as an additional age indicator to those already in use. The results showed that this technique could be adopted for determining the age of the species Decapterus russelli when the specimens are in the second year of age in case of eye lens diameter. On the other hand, eye lens weight failed to separate between the four age groups observed. The method is especially useful for age determination when otolith or scale ring are not visible or when false rings give erroneous reading.

A review of spectral properties of plants and their potential use for crop/weed discrimination in row-crops

R. Zwiggelaar, 'A review of spectral properties of plants and their potential use for crop/weed discrimination in row-crops', Crop Protection 17 (3), 189-206 (1998)

Age Effects in Cultural Life Scripts.

Life scripts are culturally shared expectations about the timing of life events in an idealized life course. Because they are cultural semantic knowledge, they should be known by all adult age groups including those who have not lived through all events in the life script, but this has not been tested previously. Young, middle-aged and older adults from the Netherlands were therefore asked in this online study to imagine an ordinary Dutch infant and to name the seven most important events that were likely to take place in the life of this prototypical child. Participants subsequently answered questions about at what ages these events were expected to occur and about their prevalence, importance and valence. We found that the cultural life script was similar for young, middle-aged and older adults and for adults with different educational attainment.