Structure and function in native and pathological erythrocytes: A quantitative view from the nanoscale

The red blood cells (RBCs) are among the most simple and less expensive cells to purify; for this reason and for their physiological relevance, they have been extensively studied with a variety of techniques. The picture that results is that these cells have several peculiarities including extreme mechanical performances, relatively simple architecture, biological relevance and predictable behavior that make them a perfect laboratory of testing for novel techniques, methodologies and ideas. These include the re-evaluation of old concepts, such as the relationship between structure and function (which is one of the guideline of this report) but considered at the cellular level. The studies reported on this paper, indeed, exploit the full potential of an high resolution quantitative microscopy such as the atomic force microscopy (AFM) to investigate different aspect of the erythrocytes' life, death and interaction with the environment. Indeed, the erythrocytes have a special relationship with the environment that is able to deeply influence their morphology as consequence of alteration of their biochemical or biophysical status. In this context the conditions under which the erythrocytes can be considered as biochemically programmable systems have been investigated by analyzing different environmentally induced alteration of the cell's morphology and comparing the results with naturally occurring pathological morphologies. This class of studies takes great advantage by the additional consideration of the nanomechanical properties of the cells. These latter are particularly important for the cell functionality and are shown to be of practical usefulness to discriminate and partition environmental effects charging different cellular structure (e.g. membrane or membrane-skeleton). Moreover, the development of novel morphological parameter can be important to push the level of investigation on the RBCs' status towards the molecular level. In particular, we describe the introduction and use of the plasma membrane roughness as a morphometric parameter of simple derivation from the AFM images and that results sensitive to the structural integrity of the cells' membrane-skeleton. This offer a remarkable opportunity to investigate the relationship between structure and function in normal and pathological cells by using a morphometric parameter that probes the cell surface at the nanoscale level. At last, a complex but physio-pathologically important phenomenon such as the erythrocytes aging was considered. To properly analyze the many variation that the cells experience during the whole aging path we used all the parameters that the AFM can provides: quantitative imaging, analysis of the membrane roughness and local measure of the nanomechanical properties analyzed together with biochemical parameter such as the ATP content. The picture that emerged is that the aging path is triggered by the ATP intracellular concentration that influence the membrane-skeleton structure and the support exerted on the plasma membrane. The consequences of the membrane-skeleton involvement can be monitored by AFM and showed the occurrence of peculiar morphologies and morphological defects that appear in the very place where the membrane-skeleton contact with the membrane became loose. As a whole, the collected data enable to describe the entire phenomenon as a sequence of morphological intermediates following one another along the aging path.     

Formamide and the origin of life

The complexity of life boils down to the definition: “self-sustained chemical system capable of undergoing Darwinian evolution” (Joyce, 1994) [1]. The term “self-sustained” implies a set of chemical reactions capable of harnessing energy from the environment, using it to carry out programmed anabolic and catabolic functions. We briefly present our opinion on the general validity of this definition.Running anabolic and catabolic functions entails complex chemical information whose stability, reproducibility and evolution constitute the core of what is dubbed genetics.Life as-we-know-it is made of the intimate interaction of metabolism and genetics, both built around the chemistry of the most common elements of the Universe (hydrogen, oxygen, nitrogen, carbon). Other elements like phosphorus and sulphur play important but ancillary and potentially replaceable roles.The reproducible interaction of metabolic and genetic cycles results in the hypercycles of organization and de-organization of chemical information that we consider living entities. In order to approach the problem of the origin of life it is therefore reasonable to start from the assumption that both metabolism and genetics had a common origin, shared a common chemical frame, were embedded in physical–chemical conditions favourable for the onset of both.The most abundant three-atoms organic compound in interstellar environment is hydrogen cyanide HCN, the most abundant three-atoms inorganic compound is water H₂O. The combination of the two results in the formation of formamide H₂NCOH. We have explored the chemistry of formamide in conditions compatible with the synthesis and the stability of compounds of potential pre-genetic and pre-metabolic interest. We discuss evidence showing (i) that all the compounds necessary for the build-up of nucleic acids are easily obtained abiotically, (ii) that essentially all the steps leading to the spontaneous generation of RNA are abiotically possible, (iii) that the key compounds of extant metabolic cycles are obtained in the same chemical frame, often in the same test tube.How close are these observations to a plausible scenario for the origin of life?     

ESCA surface study of polystyrene photodegradation accelerated by 2-(2-methoxy-5-methylphenyl)-2H-benzotriazole

The accelerated ageing of polystyrene by means of 2-(2-methoxy-5-methylphenyl)-2H-benzotriazole, under conditions reproducing the outdoor environment, was studied. The results show that this benzotriazole derivative appreciably accelerates the rate of photodegradation at the surface of polystyrene.     

Theoretical investigation and computational evaluation of overtone and combination features in resonance Raman spectra of polyenes and carotenoids

We review the theory for overtones and combinations in resonant Raman spectroscopy introduced by Nafie, Stein and Peticolas in 1971 on the basis of time‐ordered diagrams, and we apply it to β‐carotene with the support of density functional theory calculations. Comparison with experimental results obtained by Tasumi's group in 1994 is provided. The theory here presented allows a prompt evaluation of resonant Raman intensities with presently available quantum chemistry tools. Copyright © 2014 John Wiley & Sons, Ltd.     

Functionalization of a polyaspartamide with glycidyl methacrylate: A useful method to prepare hydrogels through gamma irradiation

α,β-Poly(N-2-hydroxyethyl)-DL-aspartamide (PHEA) was derivatized with glycidyl methacrylate (GMA). Aqueous solutions of the obtained copolymer PHEA-GMA (PHG) were irradiated by gamma rays with a dose rate of 0.5 KGy/h and at zero°C in the presence or in the absence of N, N'-methylenebisacrylamide (BIS). New hydrogel systems were obtained and characterized by FT-IR analyses and swelling measurements in aqueous medium at different pH values.     

Poly(organophosphazenes) containing azo dyes

In this paper we describe a method for the functionalization of catenapoly[bis(4-hydroxyphenoxy)-λ⁵-phosphazene] with diazonium salts to form new, deeply-coloured, phosphazene copolymers containing variable amounts of azo dyes attached to the polyphosphazene skeleton. The degree of functionalization in these substrates is regulated in order not to exceed 20% of the sites available in the pristine polyphosphazene and to maintain a high percentage of unreacted, free, hydroxy groups, in the final, coloured copolymers. These species are still very reactive and able to undergo further functionalization reactions.     

PANI-CSA: An Easy Method to Avoid ITO Photolithography in PLED Manufacturing

In order to optimize polymer light emitting diode (PLED) performances, devices with holes injected through an Indium Tin Oxide (ITO) / Polyaniline (PANI) electrode into the polymer are much more efficient than devices fabricated with the anode made only by ITO. We demonstrated that by using doped PANI as hole injection layer in a polymer light emitting diode the manufacturing process can become simpler. Indeed, the pattern of conductive layer can be produced without ITO photolithography by UV exposition. As hole transporter layer, Poly(N-vinylcarbazole) (PVK) was spin coated over the doped PANI layer and a layer of tris (8-hydroxy) quinoline aluminum (Alq₃) was then thermally evaporated so as to form the electron transport layer. To complete the device structure, Aluminum contacts were deposited onto the organic layers by vacuum evaporation at low pressure. The layers were characterized by X-ray small-angle diffraction, IR Raman and UV-Vis spectroscopies. Devices without PANI and with PANI as HIL were studied.