One-dimensional zig-zag type coordination polymers of Ni(II) and Cu(II) containing 1,3-benzenedicarboxylate and 1,3-diaminopropane: Structural, spectral and thermal studies

Two coordination polymers [Ni(ipt)(dap)₂]_n (1) and [Cu(ipt)(dap)H₂O]_n · nH₂O (2) with an overall one-dimensional arrangement and having isophthalate (ipt) as bridging moieties and chelating 1,3-diaminopropane (dap) as structure modulating units have been prepared and characterized by crystallographic, spectroscopic and thermo-analytical studies. Both have an overall one-dimensional zig-zag nature but with a distorted octahedral NiN₄O₂ chromophore for 1 and a distorted square pyramidal CuN₂O₃ chromophore for 2. Even though the ipt units are acting as bridging units through mono-dentatively coordinating carboxylate functions in both polymers, compound 1 has the carboxylate oxygen linkages at the trans positions, while in 2 the oxygen linkages occur at the cis positions leading to a different type of zig-zag arrangement. Relevant spectral and bonding parameters also could be evaluated for the compounds using UV-Vis and EPR spectra. Thermal stability and possible structural modifications on thermal treatment of the compounds were also investigated and the relevant thermodynamic and kinetic parameters evaluated from the thermal data.     

Digestive performance in five Mediterranean lizard species: effects of temperature and insularity

Temperature sensitivity of digestive processes has important ramifications for digestive performance in ectothermic vertebrates. We conducted a comparative analysis of temperature effects on digestive processes [gut passage times (GPTs) and apparent digestive efficiencies (ADEs)] in five lacertid lizards occurring in insular (Podarcis erhardii, P. gaigeae), and mainland (P. muralis, P. peloponnesiaca, Lacerta graeca) Mediterranean environments. GPTs were negatively correlated to temperature with mainland taxa having 10–20% longer GPTs than island taxa. In contrast to previous studies that estimate ADEs using bomb calorimetry, we compare ADEs by analyzing discrete efficiencies for lipids, sugars and proteins at three temperature regimes (20, 25, and 30°C); each of these categories produces different results. ADEs for lipids and sugars showed a monotonic increase with temperature whereas ADEs for proteins decreased with temperature. Island taxa had consistently higher ADEs than their mainland counterparts for lipids and for proteins but not for sugars. They are characterized by superior energy acquisition abilities despite significantly shorter GPTs. Their increased digestive performance relative to the mainland species appears to allow them to maximize energy acquisition in unproductive island environments where food availability is spatially and seasonally clustered.     

Rectal,telemetry pill and tympanic membrane thermometry during exercise heat stress

We compared the accuracy of an ingestible telemetry pill method of core temperature (T_c) measurement and an infrared tympanic membrane thermometer to values from a rectal thermistor during exercise-induced heat stress. Ten well-trained subjects completed four exercise trials consisting of 40 min constant-load exercise at 63% of maximum work rate followed by a 16.1 km time trial at 30 °C and 70% relative humidity. Temperature at rest was not different between the three methods of T_c measurement (T_re: 37.2±0.3 °C; T_p: 37.2±0.2 °C; T_ty: 37.1±0.3 °C; P=0.40$P=0.40$). Temperature rose continuously during the exercise period (ΔT_re: 2.2±0.5 °C; ΔT_p: 2.2±0.5 °C; ΔT_ty: 1.9±0.5 ±°C and there were no differences between T_re and T_p measurements at any time throughout exercise (P=0.32$P=0.32$). While there were no differences between T_re and T_ty after 10 min (P=0.11$P=0.11$) and 20 min (P=0.06$P=0.06$) of exercise, T_ty was lower than T_re after 30 min of exercise (P<0.01$P<0.01$) and remained significantly lower throughout the remainder of the exercise period. These results demonstrate that the telemetry pill system provides a valid measurement of trunk temperature during rest and exercise-induced thermal strain. T_ty was significantly lower than T_re when temperature exceeded 37.5 °C. However, whether these differences are due to selective brain cooling or imperfections in the tympanic membrane thermometer methodology remains to be determined.     

The Paleocene–Eocene Thermal Maximum as recorded by Tethyan planktonic foraminifera in the Forada section (northern Italy)

The Forada section in the Venetian Pre-Alps of northern Italy represents an expanded record of the Paleocene–Eocene Thermal Maximum (PETM) at a depositional paleodepth of about 1 km ± 0.5 km. High-resolution planktonic foraminiferal analysis of this section, in a time interval of approximately 1.3 Myr across the Paleocene/Eocene boundary, reveals striking faunal changes that allow the identification of eight phases (a–h). The late Paleocene was represented by stable, warm and oligotrophic surface water conditions (phase a). Unstable environmental conditions start well before the onset of PETM (ca. 150 kyr, phase b) and involved a change towards eutrophy, as marked by the increase of Subbotina and the concomitant decrease of Morozovella. This step is also characterized by enhanced fragmentation and dissolution.The interval corresponding to the main body of the carbon isotope excursion (CIE) is characterized by a marked increase of Acarinina, though with some differences in the species composition and relative abundance, both in high-and low-latitudes, particularly in the Tethyan area. Forada is no exception to this pattern. However, at Forada, two prominent peaks in abundance of acarininids are recorded ca. 30 kyr prior to the onset of the CIE, thus suggesting an increase in temperature heralding the onset of the PETM (phase c). Interestingly, the lower peak in abundance of Acarinina just precedes the 1‰ carbon isotope negative shift occurring below the onset of the main CIE. The basalmost Eocene, corresponding to the lower part of CIE curve, is represented by intense planktonic foraminiferal dissolution, implying an extraordinary rise of the CCD. This interval has an estimated duration of about 16 kyr (phase d).The dominance of acarininids in the lower part of the CIE (phase e, f; ca. 14 and 22.5 kyr) is interpreted as a consequence of the extreme warmth coupled with eutrophic conditions characterizing the Forada depositional environment at that time. These acarininids include at Forada also the temporally constrained Acarinina sibaiyaensis and A. africana. The morphological similarity between these peculiar species with the radially elongated chambered forms characterizing the Cretaceous anoxic events, suggests the hypothesis that depletion of oxygen in the upper water column might have been one of the factors causing their conspicuous occurrence at the PETM.The recovery in abundance of the specialized morozovellids and of other planktonic foraminiferal groups (e.g., biserials, globanomalinids, igorinids, planorotalids and pseudohastigerinids), occurring in the middle part of the CIE (ca. 30 kyr after the onset of the PETM), indicates an initial environmental recovery (phase g). A new stable state is definitely reached in the upper part of the Forada section where the relative proportions of the main component of planktonic foraminiferal assemblages move towards values similar to those of the late Paleocene conditions (phase h). However, the perturbation during the PETM produced significant changes in the ocean geochemistry that endured after the PETM event, as testified by the prominent high carbonate dissolution characterizing the marly levels, and the large variability in relative abundance among different components of the planktonic foraminiferal assemblages. These striking oscillations were not present in the latest Paleocene.     

All-year reproduction and possible thermal melanism in <Emphasis Type="Italic">Amblystogenium pacificum</Emphasis> (Coleoptera: Carabidae) on the sub-Antarctic Ile de la Possession (Iles Crozet)

In the fell-field habitat at 140–270 m altitude on the sub-Antarctic Ile de la Possession, Iles Crozet, the dimorphic beetle Amblystogenium pacificum Putzeys (Coleoptera: Carabidae) was studied monthly throughout the southern year 1993–1994 by timed hand collections involving turning stones on the rocky fell-field. There were many mating couples and females containing well-developed eggs in every month and the species reproduced throughout the year, with no evidence of a winter cessation of egg production. However, the frequency of mating couples was about twice as great in the summer half-year (October–March) as in the winter half (April–September). Relatively small differences in monthly mean temperatures between the summer and winter at Iles Crozet render all-year reproduction not unexpected when comparisons are made with the temperatures and phenology of Carabidae in cool habitats in other parts of the world. Mating pairs were collected at unusually high frequencies for carabids. The frequency of such pairs, taken per unit effort by hand collecting, was highest in October–December, lower from January to May and intermediate from June to September. Comparison of beetles taken as solitary, non-mating individuals with those taken as mating couples showed that in summer, females of the black morph of this dimorphic species were more frequently involved in mating than expected, but no differences were detected in winter. Female beetles were divided into younger individuals (putative age 1–2 years) and older females (putative age 3–5 years or more) by the amount of claw-wear on individuals of this species. This division indicated that about 40% of the older females showed no egg development when captured, but only about 20% of the younger females were non-breeding. However, of the reproducing beetles, young and old females matured similar numbers of eggs. An altitude transect showed that the proportion of the black morph increased significantly with altitude. Studies at 140–270 m showed that a significantly smaller proportion of the older females of the brown morph were breeding than in the younger brown individuals, and this effect was particularly evident in the colder winter period. No such age differences existed amongst the black morph.     

Effects of increasing temperatures on population dynamics of the zebra mussel <Emphasis Type="Italic">Dreissena polymorpha</Emphasis>: implications from an individual-based model

Zebra mussels (Dreissena polymorpha, Pallas, 1771) have had unprecedented success in colonizing European and North American waters under strongly differing temperature regimes. Thus, the mussel is an excellent model of a species which is able to cope with increasing water temperatures expected under global change. We study three principle scenarios for successful survival of the mussel under rising temperatures: (1) no adaptation to future thermal conditions is needed, existing performance is great enough; (2) a shift (adaptation) towards higher temperatures is required; or (3) a broadening of the range of tolerated temperatures (adaptation) is needed. We developed a stochastic individual-based model which describes the demographic growth of D. polymorpha to determine which of the alternative scenarios might enable future survival. It is a day-degree model which is determined by ambient water temperature. Daily temperatures are generated based on long-term data of the River Rhine. Predictions under temperature conditions as recently observed for this river that are made for the phenology of reproduction, the age distribution and the shell length distribution conform with field observations. Our simulations show that temporal patterns in the life cycle of the mussel will be altered under rising temperatures. In all scenarios spawning started earlier in the year and the total reproductive output of a population was dominated by the events later in the spawning period. For maximum temperatures between 20 and 26°C no thermal adaptation of the mussel is required. No extinctions and stable age distributions over generations were observed in scenario 2 for all maximum temperatures studied. In contrast, no population with a fixed range of tolerated temperatures survived in scenario 3 with high maximum temperatures (28, 30, 32°C). Age distributions showed an excess of 0+ individuals which resulted in an extinction of the population for several thermal ranges investigated. Priority programme of the German Research Foundation—contribution 14.     

Dual mode of binding of anti cancer drug epirubicin to G-quadruplex [d-(TTAGGGT)]4 containing human telomeric DNA sequence induces thermal stabilization

Epirubicin exerts its anti cancer action by blocking DNA/RNA synthesis and inhibition of topoisomerase-II enzyme. Recent reports on its influence on telomere maintenance, suggest interaction with G-quadruplex DNA leading to multiple strategies of action. The binding of epirubicin with parallel stranded inter molecular G-quadruplex DNA [d-(TTAGGGT)]₄ comprising human telomeric DNA sequence TTAGGG was investigated by absorption, fluorescence, circular dichroism and nuclear magnetic resonance spectroscopy. The epirubicin binds as monomer to G-quadruplex DNA with affinity, K_b1 = 3.8 × 10⁶ M⁻¹ and K_b2 = 2.7 × 10⁶ M⁻¹, at two independent sites externally. The specific interactions induce thermal stabilization of DNA by 13.2–26.3 °C, which is likely to come in the way of telomere association with telomerase enzyme and contribute to epirubicin-induced apoptosis in cancer cell lines. The findings pave the way for drug designing in view of the possibility of altering substituent groups on anthracyclines to enhance efficacy using alternate mechanism of its interaction with G4 DNA, causing interference in telomere maintenance pathway by inducing telomere dysfunction.     

Proteome-wide Analysis of Protein Thermal Stability in the Model Higher Plant Arabidopsis thaliana

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Highlights

• •Over 1700 Arabidopsis proteins with thermal models in multiple replicates.
• •Melting temperature correlates with 1°, 2°, and 3° protein characteristics.
• •Ligand-induced thermal shifts are evident in complex protein extracts.

     

Suitability of frequency modulated thermal wave imaging for skin cancer detection—A theoretical prediction

A theoretical study on the quantification of surface thermal response of cancerous human skin using the frequency modulated thermal wave imaging (FMTWI) technique has been presented in this article. For the first time, the use of the FMTWI technique for the detection and the differentiation of skin cancer has been demonstrated in this article. A three dimensional multilayered skin has been considered with the counter-current blood vessels in individual skin layers along with different stages of cancerous lesions based on geometrical, thermal and physical parameters available in the literature. Transient surface thermal responses of melanoma during FMTWI of skin cancer have been obtained by integrating the heat transfer model for biological tissue along with the flow model for blood vessels. It has been observed from the numerical results that, flow of blood in the subsurface region leads to a substantial alteration on the surface thermal response of the human skin. The alteration due to blood flow further causes a reduction in the performance of the thermal imaging technique during the thermal evaluation of earliest melanoma stages (small volume) compared to relatively large volume. Based on theoretical study, it has been predicted that the method is suitable for detection and differentiation of melanoma with comparatively large volume than the earliest development stages (small volume). The study has also performed phase based image analysis of the raw thermograms to resolve the different stages of melanoma volume. The phase images have been found to be clearly individuate the different development stages of melanoma compared to raw thermograms.     

Microcosm evaluation of bioaugmentation after field-scale thermal treatment of a TCE-contaminated aquifer

This paper investigates effects of combining thermal and biological remediation, based on laboratory studies of trichloroethene (TCE) degradation. Aquifer material was collected 6 months after terminating a full-scale Electrical Resistance Heating (ERH), when the site had cooled from approximately 100°C to 40°C. The aquifer material was used to construct bioaugmented microcosms amended with the mixed anaerobic dechlorinating culture, KB-1^TM, and an electron donor (5 mM lactate). Microcosms were bioaugmented during cooling at 40, 30, 20, and 10°C, as temperatures continually decreased during laboratory incubation. Redox conditions were generally methanogenic, and electron donors were present to support dechlorination. For microcosms bioaugmented at 10°C and 20°C, dechlorination stalled at cis-dichloroethene (cDCE) and vinyl chloride (VC) 150 days after bioaugmentation. However, within 300 days of incubation ethene was produced in the majority of these microcosms. In contrast, dechlorination was rapid and complete in microcosms bioaugmented at 30°C. Microcosms bioaugmented at 40°C also showed rapid dechlorination, but stalled at cDCE with partial VC and ethene production, even after 150 days of incubation when the temperature had decreased to 10°C. These results suggest that sequential bioremediation of TCE is possible in field-scale thermal treatments after donor addition and bioaugmentation and that the optimal bioaugmentation temperature is approximately 30°C. When biological and thermal remediations are to be applied at the same location, three bioremediation approaches could be considered: (a) treating TCE in perimeter areas outside the source zone at temperatures of approximately 30°C; (b) polishing TCE concentrations in the original source zone during cooling from approximately 30°C to ambient groundwater temperatures; and (c) using bioremediation in downgradient areas taking advantages of the higher temperature and potential release of organic matter.