Molecular mechanisms driving the microgels behaviour: a Raman spectroscopy and Dynamic Light Scattering study

Responsive microgels based on poly(N-isopropylacrylamide) (PNIPAM) exhibit peculiar behaviours due to the competition between the hydrophilic and hydrophobic interactions of the constituent networks. The interpenetration of poly-acrilic acid (PAAc), a pH-sensitive polymer, within the PNIPAM network, to form Interpenetrated Polymer Network (IPN) microgels, affects this delicate balance and the typical Volume-Phase Transition (VPT) leading to complex behaviours whose molecular nature is still completely unexplored. Here we investigate the molecular mechanism driving the VPT and its influence on particle aggregation for PNIPAM/PAAc IPN microgels by the joint use of Dynamic Light Scattering and Raman Spectroscopy. Our results highlight that PNIPAM hydrophobicity is enhanced by the interpenetration of PAAc promoting interparticle interactions, a crossover concentration is found above which aggregation phenomena become relevant. Moreover we find that, at variance with PNIPAM, for IPN microgels a double-step molecular mechanisms occurs upon crossing the VPT, the first involving the coil-to-globule transition typical of PNIPAM and the latter associated to PAAc steric hindrance.Comment: preprint versio

Folate-based single cell screening using surface enhanced Raman microimaging

Recent progress in nanotechnology and its application to biomedical settings have generated great advantages in dealing with early cancer diagnosis. The identification of the specific properties of cancer cells, such as the expression of particular plasma membrane molecular receptors, has become crucial in revealing the presence and in assessing the stage of development of the disease. Here we report a single cell screening approach based on Surface Enhanced Raman Scattering (SERS) microimaging. We fabricated a SERS-labelled nanovector based on the biofunctionalization of gold nanoparticles with folic acid. After treating the cells with the nanovector, we were able to distinguish three different cell populations from different cell lines (cancer HeLa and PC-3, and normal HaCaT lines), suitably chosen for their different expressions of folate binding proteins. The nanovector, indeed, binds much more efficiently on cancer cell lines than on normal ones, resulting in a higher SERS signal measured on cancer cells. These results pave the way for applications in single cell diagnostics and, potentially, in theranostic

“For Asia market only”: a green tattoo ink between safety and regulations

Due to the increasing tattoo practicing in Eastern countries and general concern on tattoo ink composition and safety, the green tattoo inks Green Concentrate by Eternal, for European and “for Asia Market Only” were analyzed, under the premise that only the former falls under a composition regulation. A separation of the additives from the pigment was carried out by successive extraction in solvents of different polarities, i.e., water, acetone and dichloromethane. The solid residues were analyzed by IR and Raman spectroscopies, the liquid fractions by GC/mass spectrometry. The relative pigment load and element traces were also estimated. We found that the European and the Asian inks are based on the same pigment, PG7, restricted in Europe, though at different loads. They have a similar content of harmful impurities, such as Ni, As, Cd and Sb and both contain siloxanes, including harmful D4. Furthermore, they have different physical-chemical properties, the European ink being more hydrophilic, the Asian more hydrophobic. Additionally, the Asian ink contains harmful additives for the solubilization of hydrophobic matrices and by-products of the phthalocyanine synthesis. Teratogenic phthalates are present as well as chlorinated teratogenic and carcinogenic compounds usually associated to the laser treatment for removal purposes, to a larger extent in the European ink. The composition of the inks does not seem to reflect regulatory restrictions, where issued

Dyes of a Shadow Theatre: Investigating Tholu Bommalu Indian Puppets through a Highly Sensitive Multi-Spectroscopic Approach

Tholu Bommalu are typical leather puppets of the traditional Indian shadow theatre. Two of these objects are part of a collection in the International Puppets Museum “Antonio Pasqualino” (Palermo, Sicily, Italy), which can count on one hundred-seventy-three of artifacts. These Indian puppets were investigated to obtain information related to the use of dyes for their manufacturing through a multi-technical approach exploiting the combination of highly sensitive spectroscopic techniques. Wet cotton stubbons were used to entrap small particles of dyes on the fibers from the art objects for the consequent analyses. Visible Light Micro-Reflectance spectroscopy was employed for the preliminary identification of the molecular class of dyes directly on the swabs, while Surface Enhanced Raman Scattering allowed the identification of the specific dye. Several synthetic dyes belonging to different typologies of coloring compounds were identified. The study resulted in an interesting overview of dyes used in recent Tholu Bommalata manufacturing through the combination of micro-invasive techniques directly on the sampling substrate

The Puzzling Problem of Cardiolipin Membrane-Cytochrome c Interactions: A Combined Infrared and Fluorescence Study

The interaction of cytochrome c (cyt c) with natural and synthetic membranes is known to be a complex phenomenon, involving both protein and lipid conformational changes. In this paper, we combined infrared and fluorescence spectroscopy to study the structural transformation occurring to the lipid network of cardiolipin-containing large unilamellar vesicles (LUVs). The data, collected at increasing protein/lipid ratio, demonstrate the existence of a multi-phase process, which is characterized by: (i) the interaction of cyt c with the lipid polar heads; (ii) the lipid anchorage of the protein on the membrane surface; and (iii) a long-distance order/disorder transition of the cardiolipin acyl chains. Such effects have been quantitatively interpreted introducing specific order parameters and discussed in the frame of the models on cyt c activity reported in literature

Wearable and Portable Devices for Acquisition of Cardiac Signals while Practicing Sport: A Scoping Review

Wearable and portable devices capable of acquiring cardiac signals are at the frontier of the sport industry. They are becoming increasingly popular for monitoring physiological parameters while practicing sport, given the advances in miniaturized technologies, powerful data, and signal processing applications. Data and signals acquired by these devices are increasingly used to monitor athletes' performances and thus to define risk indices for sport-related cardiac diseases, such as sudden cardiac death. This scoping review investigated commercial wearable and portable devices employed for cardiac signal monitoring during sport activity. A systematic search of the literature was conducted on PubMed, Scopus, and Web of Science. After study selection, a total of 35 studies were included in the review. The studies were categorized based on the application of wearable or portable devices in (1) validation studies, (2) clinical studies, and (3) development studies. The analysis revealed that standardized protocols for validating these technologies are necessary. Indeed, results obtained from the validation studies turned out to be heterogeneous and scarcely comparable, since the metrological characteristics reported were different. Moreover, the validation of several devices was carried out during different sport activities. Finally, results from clinical studies highlighted that wearable devices are crucial to improve athletes' performance and to prevent adverse cardiovascular events

Surface-Enhanced Raman Scattering of DNA-Nanoparticle assemblies

During the last years, soft matter colloids have gained important achievements and a large amount of results have been accomplished to the realisation of innovative and smart nanomaterials. In particular, the understanding in the mastering of DNA-nanoparticle systems, which combine the plasmonic properties of metallic nanoparticles (NPs) with the programmability and self-assembly of DNA strands – opens up a great number of applications in different branches of science, especially in nanoscience. Consequently, the importance of Surface Enhanced Raman Scattering (SERS), which associates a high sensitivity and a specific spectral signature of DNA, is significantly increasing in the detection of specific targets, thus, in the implementation of high-quality biosensors. The DNA base-pairing specificity (A-T, C-G) allows the breakthrough in “programmable bonds” between nanoparticles, serving as the basic building blocks for the creation of mesoscopic plasmonic aggregates. In our labs we provided to the realisation of DNA-NP structures by properly functionalizing metallic gold NPs with complementary and purposely programmed single-stranded DNA. To this aim, we have chosen two specific single-stranded DNA sequences, consisting of 12 base oligomers, with a thiolgroup at the end of each one which allows to covalent bond onto the metallic NP surfaces; the aforementioned sequence assures not only a harder and more reproducible bond but also a more controllable adherence. Therefore, it has been possible an ensuing study of the spectroscopic features of these binary systems through the use of SERS. We have thus characterised the SERS spectrum for both DNA sequences-which were attached on gold NPs and obtained a coherent and reproducible signal. The spectra were obtained by using a direct and label-free protocol, thus, avoiding the loss of information about the intrinsic chemical and structural properties of DNA oligonucleotides that fluorescence methods cause. In addition, we provided the realisation of DNA-nanoparticle aggregates, starting from gold nanoparticles functionalized with the two different 12-base DNA sequences and let them hybridise through the addition of a DNA ‘bridge’ which is a 24 base oligomers complementary to the two chains

First- and second-order Raman scattering from MoTe2 single crystal

We report on Raman experiments performed on a MoTe 2 single crystal. The system belongs to the wide family of transition metal dichalcogenides which includes several of the most interesting two- dimensional materials for both basic and applied physics. Measurements were performed in the standard basal plane configuration, by placing the ab plane of the crystal perpendicular to the wave vector k i of the incident beam to explore the in-plane vibrational modes, and in the edge plane configuration with k i perpendicular to the crystal c axis, thus mainly exciting out-of-plane modes. For both configurations we performed a polarization-dependent study of the first-order Raman components and detailed computation of the corresponding selection rules. We were thus able to provide a complete assignment of the observed first-order Raman peaks, in agreement with previous literature results. A thorough analysis of the second- order Raman bands, as observed in both basal and edge plane configurations, provides new information and allows a precise assignment of these spectral structures. In particular, we have observed and assigned Raman active modes of the M point of the Brillouin zone previously predicted by ab initio calculations but never previously measured

Exploiting SERS sensitivity to monitor DNA aggregation properties

In the last decades. DNA has been considered far more than the system carrying the essential genetic instructions. Indeed, because of the remarkable properties of the base-pairing specificity and thermoreversibility of the interactions, DNA plays a central role in the design of innovative architectures at the nanoscale. Here, combining complementary DNA strands with a custom-made solution of silver nanoparticles, we realize plasmonic aggregates to exploit the sensitivity of Surface Enhanced Raman Spectroscopy (SERS) for the identification/detection of the distinctive features of DNA hybridization, both in solution and on dried samples. Moreover. SERS allows monitoring the DNA aggregation process by following the temperature variation of a specific spectroscopic marker associated with the Watson-Crick hydrogen bond formation. This temperature-dependent behavior enables us to precisely reconstruct the melting profile of the selected DNA sequences by spectroscopic measurements only. (C) 2020 Elsevier B.V. All rights reserved

Channelling and induced defects at ion-bombarded aligned multiwall carbon nanotubes

A detailed investigation of ion channelling and defect production for a highly-ordered array of multi-wall carbon nanotubes is presented. The effects of argon ion bombardment (0.25–5 keV) carried out either parallel (top) or perpendicular (side) to their axis, have been studied by Raman, X-Ray Photoelectron Spectroscopy and Scanning Electron Microscopy. Raman spectra provided evidence of channelling of the Ar+ions observed for top bombardment along the whole 180 μm carbon nanotube length, while the penetration length is limited to the first 10 μm when the ions impinge from the side. The nature of defects, determined through the spectral fingerprints of the C 1s core level as a function of energy and flux, unveils a distorted sp3-like bonding increase and the π-excitation decrease till quenching. Dangling bond states due to displaced carbon atoms become significant only at beam energies higher than 0.25 keV and high flux. These results on anisotropic channelling and selective defects creation open new perspectives in the application of highly-ordered arrays of multi-wall carbon nanotubes as anisotropic detectors