Conellae, enigmatic structures on cephalopod shells—shapes, distribution, and formation

Conellae, enigmatic cone-shaped structures which can be found on the surface of internal moulds of cephalopod shells (predominantly of ammonoids), are regarded herein as the product of remote (biologically induced) biomineralization formed in closed-off cavities during lifetime and might be primarily composed of vaterite, aragonite, or calcite. To date conellae have been interpreted in many different ways: (i) as organisms (gastropods, cirriped crustaceans, or disciniscid brachiopods), (ii) pre-diagenetic syn vivo features, i.e., biologically controlled or induced, the product of remote biomineralization, (iii) and diagenetic, i.e., abiogenic origin and post-mortem. The proposed processes of conellae formation seem insufficient to explain conellae related phenomena. Further, their assumed primary aragonitic or calcitic mineralogy are reviewed and based on new material critically assessed. The stratigraphic range of conellae extends from the Middle Ordovician and probably to modern Nautilus. Predominantly, conellae can be found on internal moulds along the keel, ribs or nodes, umbilical shoulder, at the transition between phragmocone and body chamber, and can be associated with repaired scars. However, conellae are also common on the smooth body chambers of large macroconchs of Jurassic ammonites. Conellae, which are located on ammonite body chambers, are filled with the same material found in the body chamber and can contain small burrows, sand grains, or coprolites. Some of these conellae are partially covered with nacreous shell material. Limonitic conellae were also found on the limonitic internal moulds of orthocone nautiloids. Moreover, disciniscid brachiopods found on inoceramid bivalves were re-identified herein as conellae. A short guide for conellae identification has been provided herein

The soft-tissue attachment scars in Late Jurassic ammonites from Central Russia

Soft-tissue attachment scars of two genera and four species of Late Jurassic craspeditid ammonites from the Russian Platform are described. A previously suggested relationship between lateral attachment scars and ammonoid hyponome is confirmed, however, a new interpretation is proposed for dorsal attachment scars: they could have been areas not only for attachment of the dorsal (nuchal) retractors, but also of the cephalic retractors. The new type of the soft-tissue attachment—anterior lateral sinuses, located between the lateral attachment scars and the aperture of the ammonite body chamber is described. Enclosed elliptical or subtriangular areas in apertural parts of the anterior lateral sinuses were found for the first time. Their presence and location suggest that this structure could have been used for attaching the funnel-locking apparatus, similar to those of coleoids. A transformation of shape and position of lateral attachment scars through the evolution of the Late Jurassic craspeditid lineage starting from platycones (Kachpurites fulgens) to keeled oxycones (Garniericeras catenulatum) is recognized

Structure of the calcitic layer of the aptychus of the ammonite genus Peltoceras

The aptychi of ammonites combined the functions of lower jaws and protective opercula. They consist of two parts: an inner organic layer and an outer calcitic lamella. In different evolutionary lineages of ammonites, the shape of aptychi, the sculpture of their surface and the microstructure of the calcitic layer vary greatly. However, the structure of the aptychi is not known for all evolutionary lineages of ammonites. Although numerous aptychi have been described for the Jurassic family Aspidoceratidae, almost all of them belong to only one evolutionary branch of this family – the Aspidoceratinae (sensu lato). For the second branch – the Peltoceratinae, only one aptychus had been described to date and the structure of its calcitic layer remained unknown. In this article, for the first time, the structure of the aptychus of the Peltoceratinae (upper Callovian Peltoceras) is described. The surface of this aptychus is covered with rough ribs and the calcitic part consists of only one layer of dense calcite. The thickness of the aptychus is much greater than that of the aptychi of supposed ancestors of the Peltoceratinae. The increase in the thickness of the aptychi in both the Aspidoceratinae and the Peltoceratinae, contemporaneously with the appearance of spines on their shells, is most likely related to increasing the protective function of the aptychi of these ammonites in the late Callovian

A new type of shell malformation caused by epizoans in Late Jurassic ammonites from Central Russia

A new type of shell damage on Late Jurassic ammonite Kachpurites fulgens is described. The new type of shell malformation consists of small elongated pits, arranged in groups on the surface of ammonite shell and concentrated near the terminal aperture. The examination of the pits demonstrated no signs of drilling, biting, or healing of punctures. The shell layers in the pits are bent downward without changing in thickness. At the same time the pits, in some cases, significantly distort the shape of the shell walls. Deformed growth lines are associated with some of the pits. All of this supports the hypothesis that the pits had been formed by epifauna located at a flexible uncalcified part of the periostracum in the apertural region of the growing ammonite shell. It is likely that epizoan attachment led to the deformation of the thin periostracum film and to the distortion of the growing shell wall. The nature of epizoans is discussed, but remains unclear due to their rather poor preservation. The relationship between epizoans and ammonites is also an open question: they could have been parasites, but other types of biotic relationships cannot be entirely ruled out

Discovery of plywood structure in Sphenothallus from Gurovo Formation (Mississippian), Central Russia

Sphenothallus specimens are reported for the first time from the Mississippian of Central Russia. All Sphenothallus specimens have a phosphatic composition and a characteristic laminar structure, which is best observable in the thickened lateral parts of a tube. Most of the lamellae in the tube wall are straight, but some have a wavy morphology and a few are so wrinkled that they form hollow “ribs”. The wrinkled lamellae presumably had an originally higher organic content than the straight lamellae. There are borings on the surfaces of some lamel-lae that are similar in morphology to the bioerosional traces in various hard, biomineral substrates. Lamellae in the inner parts of the tube wall are composed of fibres. The fibres are parallel to the surface of the tube wall and in successive laminae they differ in orientation by irregularly varying angles. It is possible that the plywood micro-structure in Sphenothallus was originally organic and was later phosphatized during fossilization. An alternative, but less likely explanation is that the plywood structure was originally mineralized and therefore is comparable to the phosphatic lamello-fibrillar structures of vertebrates

FRET Pumping of Rhodamine-Based Probe in Light-Harvesting Nanoparticles for Highly Sensitive Detection of Cu2+

In this work we presented novel strategy for increasing the performance of popular fluorescent probes on the basis of rhodamine-lactam platform. This strategy is based on the incorporation of probe molecules into the light-harvesting nanoparticles to pump modulated optical signal by Förster resonant energy transfer. Using the commercially available Cu2+ probe as a reference chemical, we have developed an efficient approach to significantly improve its sensing performance. Within obtained nanoparticles coumarin-30 nanoantenna absorbs excitation light and pumps incorporated sensing molecules providing bright fluorescence to a small number of emitters, while changing the probe-analyte equilibrium from liquid-liquid to solid-liquid significantly increased the apparent association constant, which together provided a ~100-fold decrease in the detection limit. The developed nanoprobe allows highly sensitive detection of Cu2+ ions in aqueous media without organic co-solvents usually required for dissolution of the probe, and demonstrate compatibility with inexpensive fluorometers and the ability to detect low concentrations with the naked eye

Light Harvesting Nanoprobe for Trace Detection of Hg2+ in Water

The continuously increasing flow of toxic heavy metals to the environment due to intensive industrial activity and tightening requirements with regard to the content of metal ions in drinking and discharged waters urges the development of affordable and sensitive devices to the field control of pollutants. Here, we report a new thiated Rhodamine-lactam probe for Hg2+ detection and demonstrate how its sensitivity can be increased via the incorporation of the probe molecules into the optically transparent siloxane-acrylate coatings on polymethyl methacrylate and, alternatively, into the water-dispersible light-harvesting FRET nanoparticles (NPs), in which dye cations are separated by fluorinated tetraphenylborate anions. We have shown that the optimization of the FRET NPs composition had allowed it to reach the antenna effect of ~300 and fabricate “off/on” sensor for Hg2+ ion determination in aqueous solutions with the detection limit of ~100 pM, which is far below the maximum permissible concentration (MPC) of mercury in drinking water recommended by the World Health Organization. Although this work is more proof-of-concept than a ready-to-use analytical procedure, the suggested approaches to fabrication of the FRET NPs based on the popular rhodamine-lactam platform can be used as a background for the development of low-cost portable sensing devices for the extra-laboratory determination of hazardous metal ions

Light Harvesting Nanoprobe for Trace Detection of Hg²⁺ in Water

The continuously increasing flow of toxic heavy metals to the environment due to intensive industrial activity and tightening requirements with regard to the content of metal ions in drinking and discharged waters urges the development of affordable and sensitive devices to the field control of pollutants. Here, we report a new thiated Rhodamine-lactam probe for Hg2+ detection and demonstrate how its sensitivity can be increased via the incorporation of the probe molecules into the optically transparent siloxane-acrylate coatings on polymethyl methacrylate and, alternatively, into the water-dispersible light-harvesting FRET nanoparticles (NPs), in which dye cations are separated by fluorinated tetraphenylborate anions. We have shown that the optimization of the FRET NPs composition had allowed it to reach the antenna effect of ~300 and fabricate “off/on” sensor for Hg2+ ion determination in aqueous solutions with the detection limit of ~100 pM, which is far below the maximum permissible concentration (MPC) of mercury in drinking water recommended by the World Health Organization. Although this work is more proof-of-concept than a ready-to-use analytical procedure, the suggested approaches to fabrication of the FRET NPs based on the popular rhodamine-lactam platform can be used as a background for the development of low-cost portable sensing devices for the extra-laboratory determination of hazardous metal ions