Identification of Chitin Allomorphs in Poorly Crystalline Samples Based on the Complexation with Ethylenediamine.

Chitin is a key component of hard parts in many organisms, but the biosynthesis of the two distinctive chitin allomorphs, α- and ß-chitin, is not well understood. The accurate determination of chitin allomorphs in natural biomaterials is vital. Many chitin-secreting living organisms, however, produce poorly crystalline chitin. This leads to spectrums with only broad lines and imprecise peak positions under conventional analytical methods such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy, resulting in inconclusive identification of chitin allomorphs. Here, we developed a novel method for discerning chitin allomorphs based on their different complexation capacity and guest selectivity, using ethylenediamine (EDA) as a complexing agent. From the peak shift observed in XRD profiles of the chitin/EDA complex, the chitin allomorphs can be clearly discerned. By testing this method on a series of samples with different chitin allomorphs and crystallinity, we show that the sensitivity is sufficiently high to detect the chitin allomorphs even in near-amorphous, very poorly crystalline samples. This is a powerful tool for determining the chitin allomorphs in phylogenetically important chitin-producing organisms and will pave the way for clarifying the evolution and mechanism of chitin biosynthesis.

Decalcification and survival of benthic foraminifera under the combined impacts of varying pH and salinity.

Coastal areas display natural large environmental variability such as frequent changes in salinity, pH, and carbonate chemistry. Anthropogenic impacts - especially ocean acidification - increase this variability, which may affect the living conditions of coastal species, particularly, calcifiers. We performed culture experiments on living benthic foraminifera to study the combined effects of lowered pH and salinity on the calcification abilities and survival of the coastal, calcitic species Ammonia sp. and Elphidium crispum. We found that in open ocean conditions (salinity ∼35) and lower pH than usual values for these species, the specimens displayed resistance to shell (test) dissolution for a longer time than in brackish conditions (salinity ∼5 to 20). However, the response was species specific as Ammonia sp. specimens survived longer than E. crispum specimens when placed in the same conditions of salinity and pH. Living, decalcified juveniles of Ammonia sp. were observed and we show that desalination is one cause for the decalcification. Finally, we highlight the ability of foraminifera to survive under Ωcalc < 1, and that high salinity and [Ca2+] as building blocks are crucial for the foraminiferal calcification process.

Nonbacterial thrombotic endocarditis involving all four cardiac valves.

This report describes a case of nonbacterial thrombotic endocarditis caused by Waldenström macroglobulinemia, with diffuse endocardial lesions and involvement of all 4 cardiac valves. A 77-year-old man presented with heart failure due to severe regurgitation of all 4 cardiac valves; surgical repair using bioprosthetic valves was indicated. A pathological study revealed fibrin-triggered thrombus formation that confirmed the diagnosis of nonbacterial thrombotic endocarditis. In cases of nonbacterial thrombotic endocarditis, the underlying cause should be investigated.

Proton pumping accompanies calcification in foraminifera.

Ongoing ocean acidification is widely reported to reduce the ability of calcifying marine organisms to produce their shells and skeletons. Whereas increased dissolution due to acidification is a largely inorganic process, strong organismal control over biomineralization influences calcification and hence complicates predicting the response of marine calcifyers. Here we show that calcification is driven by rapid transformation of bicarbonate into carbonate inside the cytoplasm, achieved by active outward proton pumping. Moreover, this proton flux is maintained over a wide range of pCO2 levels. We furthermore show that a V-type H+ ATPase is responsible for the proton flux and thereby calcification. External transformation of bicarbonate into CO2 due to the proton pumping implies that biomineralization does not rely on availability of carbonate ions, but total dissolved CO2 may not reduce calcification, thereby potentially maintaining the current global marine carbonate production.

Granulomatosis with Polyangiitis (Wegener's Granulomatosis) Complicated with Ruptured Posteromedial Papillary Muscle in the Absence of Coronary Angiographic Findings.

Granulomatosis with polyangiitis (GPA) is a systemic necrotizing vasculitis, associated with antineutrophil cytoplasmic autoantibody-associated systemic vasculitis, and it can affect many organ systems via the inflammation of small-to-medium-sized vessels. Cardiac involvements in GPA are relatively rare. We report a 75-year-old woman who was diagnosed with GPA and rapid progressive glomerulonephritis that resulted in a partial posteromedial papillary muscle rupture, but with no coronary angiographic findings. The surgical and pathological findings with regard to the ruptured papillary muscle revealed necrotic muscle and acute ischemic change. The mechanism of papillary muscle rupture in GPA is coronary vasculitis leading to myocardial infarction. The ischemic change is not always detected on coronary angiography, so assessment using an echocardiogram is important.

Experimental demonstration, using polarized Raman and infrared spectroscopy, that both conventional and de Vries smectic-A phases may exist in smectic liquid crystals with a first-order A-C* transition.

Two models exist for the orientational distribution of the long molecular axes in smectic-A liquid crystals: the conventional unimodal distribution and the "cone-shaped" de Vries distribution. The de Vries hypothesis provides a plausible picture of how, at a molecular level, a first-order Sm-A to Sm-C* transition may occur, especially if there is little or no concomitant shrinkage of the layer spacing. This work investigates two materials with such transitions: C7 and TSiKN65. The azimuthal distribution of in-layer directors is probed using IR and polarized Raman spectroscopy, which allows us to obtain orientational order parameters. In C7, we observe a discontinuous change in the order parameter, the magnitude of which is small compared with the corresponding change in the in-layer director tilt angle Theta . Assuming that the smectic-A liquid crystal is of the de Vries type, we calculate the Theta required to reproduce the apparent order parameter app, obtained from IR, by using the true order parameter , obtained from polarized Raman scattering. The results indicate that, for C7, the tilt angle so calculated is much smaller than that in the Sm-C* angle and hence de Vries behavior may not be the appropriate explanation in this case. Conversely, we find that TSiKN65 shows a different behavior to C7, which can be explained in terms of the de Vries concept. Thus, we conclude that either type of distribution may exist in Sm-A phases which undergo a first-order transition to the Sm-C* phase. We also discuss the changes in the smectic layer spacing and the orientational order parameters across the Sm-A-Sm-C* phase transition, together with changes in birefringence with applied electric field.

Evidence for de Vries structure in a smectic-A liquid crystal observed by polarized Raman scattering.

The second- and fourth-order apparent orientational order parameters of the core part of the molecule P2 (app) and P4 (app) , have been measured by polarized vibrational Raman spectroscopy for a homogeneously aligned ferroelectric smectic liquid crystal with three dimethyl siloxane groups in the achiral terminal chain, which shows de Vries-type phenomena, i.e., very large electroclinic effect in the smectic- A (Sm-A) phase and a negligible layer contraction at the phase transition between the Sm-A and Sm- C(*) phases. The apparent orientational order parameters of the rigid core part of the molecule are extremely small both with and without the external electric field in Sm-A . These results provide evidence for the existence of the de Vries Sm-A phase, where the local molecular director is tilted at a large angle.

Intrinsic aspect of V-shaped switching in ferroelectric liquid crystals: biaxial anchoring arising from peculiar short axis biasing in the molecular rotation around the long axis.

To clarify the intrinsic aspect of practically usable thresholdless V-shaped switching in ferroelectric liquid crystals, we have observed textures and measured polarized Raman scattering as well as optical transmittance in a thin homogeneous cell of a single compound by applying an electric field. The results indicate that the so-called surface stabilized ferroelectric states are destabilized, and that there exist rather stable two domains with broad and narrow molecular orientational distributions, both of which show the almost ideal V-shaped switching with considerably low transmittance at the tip of the V. We have concluded that the main cause of the V-shaped switching is the biaxial anchoring on the substrates coated with polyimide, which makes the most polarizable short axis normal to the substrates. It is in competition with the ordinary anchoring that favors the director parallel to the substrates, when the material has such a bulk intrinsic property that this short axis is parallel to the tilt plane. The competition makes the total anchoring energy almost independent of the azimuthal angle and gives rise to the V-shaped switching.