Tunable,Grating-Gated,Graphene-On-Polyimide Terahertz Modulators

An electrically switchable graphene terahertz (THz) modulator with a tunable-by-design optical bandwidth is presented and it is exploited to compensate the cavity dispersion of a quantum cascade laser (QCL). Electrostatic gating is achieved by a metal grating used as a gate electrode, with an HfO₂/AlO_x gate dielectric on top. This is patterned on a polyimide layer, which acts as a quarter wave resonance cavity, coupled with an Au reflector underneath. The authors achieve 90% modulation depth of the intensity, combined with a 20 kHz electrical bandwidth in the 1.9–2.7 THz range. The modulator is then integrated with a multimode THz QCL. By adjusting the modulator operational bandwidth, the authors demonstrate that the graphene modulator can partially compensate the QCL cavity dispersion, resulting in an integrated laser behaving as a stable frequency comb over 35% of the operational range, with 98 equidistant optical modes and a spectral coverage ~1.2 THz. This paves the way for applications in the terahertz, such as tunable transformation-optics devices, active photonic components, adaptive and quantum optics, and metrological tools for spectroscopy at THz frequencies.     

A comprehensive investigation of dye–chitosan blended films for green chemistry applications

In this paper, the ability of chitosan film to remove dyestuff from wastewater was evaluated for environmental applications, using three commercial direct azo dyes. Two chitosan films were adopted: the standard one prepared following a well‐known procedure to form it, and a novel one, with a weakly acidic character. Moreover, to improve the adsorption process, the hydrophobic character of the films was investigated. The pH of the dye solutions was also changed, showing an excellent ability in dye removal at pH 12. The films were characterized by means of spectroscopic and morphologic methods to better understand the nature of interactions between dyes and chitosan chains. Swelling ratio measurements were also performed. All analyses suggest that all dyes showed a strong affinity to chitosan polymer chains, with the presence of extended hydrogen bonds and Van der Waals forces perturbing the chitosan network. Interestingly, very good results were obtained in recycling experiments related to the dyeing capacities of chitosan blended films in the presence of textiles. An ecofriendly application is thus presented in this paper. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45945.     

Improved in vitro anti-tumoral activity, intracellular uptake and apoptotic induction of gemcitabine-loaded pegylated unilamellar liposomes

Anaplastic thyroid carcinoma is one of the most aggressive and lethal solid carcinomas affecting humans. A major limit of the chemotherapeutic agents is represented by their low therapeutic index. In this work, we investigated the possibility of improving the anti-tumoral activity of gemcitabine by using pegylated unilamellar liposomes. Liposomes were made up of 1,2-dipalmitoyl-sn-glycero-3-phospocholine monohydrate/cholesterol/N-(carbonyl-methoxypolyethylene glycol-2000)-1, 2-distearoyl-sn-glycero-3-phosphoethanolamine (6:3:1 molar ratio) and they were prepared with a pH gradient to improve the gemcitabine loading capacity. The anti-tumoral efficacy of the liposomal formulation was tested in vitro on human anaplastic thyroid carcinoma cells (ARO) in culture, comparing the effects with those of the free drug. Gemcitabine-loaded unilamellar liposomes had a mean size approximately 200 nm with a zeta potential approximately -2 mV. The liposomal carrier noticeably improved the anti-tumoral activity of gemcitabine against ARO cells in terms of both dose-dependent cytotoxic effect and of drug exposition effect. Namely, gemcitabine-loaded liposomes showed a cytotoxic effect (58.2% increase of cell mortality at 1 microM with respect to free drug) after 12 h incubation, while the free drug showed a significant activity only after 72 h incubation. Moreover, a significant effect on the cell mortality appeared at 0.1 microM and 100% mortality was detected at a concentration of 1 microM of gemcitabine-loaded liposomes, while the free drug elicited the same effect at a concentration of 100 microM. The improved anti-tumoral activity of gemcitabine determined by the liposomal carrier was due to a greater intracellular uptake. The intracellular gemcitabine levels as a function of time showed a sinusoidal profile with peaks after 2 h, 6 h and 11 h, related to the cellular cycle of ARO. PARP cleavage and DNA fragmentation analysis provided clear evidence of the apoptosis induction in ARO cells by treatment with liposomally entrapped gemcitabine after 72 h incubation. Thus, gemcitabine-loaded liposomes may have a potential therapeutic relevance for the treatment of anaplastic thyroid carcinoma.     

Breakdown of the adiabatic Born-Oppenheimer approximation in graphene

The adiabatic Born-Oppenheimer approximation (ABO) has been the standard ansatz to describe the interaction between electrons and nuclei since the early days of quantum mechanics. ABO assumes that the lighter electrons adjust adiabatically to the motion of the heavier nuclei, remaining at any time in their instantaneous ground state. ABO is well justified when the energy gap between ground and excited electronic states is larger than the energy scale of the nuclear motion. In metals, the gap is zero and phenomena beyond ABO (such as phonon-mediated superconductivity or phonon-induced renormalization of the electronic properties) occur. The use of ABO to describe lattice motion in metals is, therefore, questionable. In spite of this, ABO has proved effective for the accurate determination of chemical reactions, molecular dynamics and phonon frequencies in a wide range of metallic systems. Here, we show that ABO fails in graphene. Graphene, recently discovered in the free state, is a zero-bandgap semiconductor that becomes a metal if the Fermi energy is tuned applying a gate voltage, Vg. This induces a stiffening of the Raman G peak that cannot be described within ABO.     

Topologically controlled growth of magnetic-metal-functionalized semiconductor oxide nanorods

Colloidal semiconductor-magnetic hybrid nanocrystals with topologically controlled composition are fabricated by heterogeneous nucleation of spherical epsilon-Co domains onto anatase TiO2 nanorods. The latter can be selectively decorated at either their tips or at multiple locations along their longitudinal sidewalls, forming lattice-matched heterointerfaces regardless of the metal deposition sites. The possibility of switching between either heterostructure growth modes arises from the facet-dependent chemical reactivity of the oxide seeds, which is governed mainly by selective adhesion of the surfactants rather than by small differences in misfit-induced interfacial strain at the relevant junction points.     

In situ observations of catalyst dynamics during surface-bound carbon nanotube nucleation

We present atomic-scale, video-rate environmental transmission electron microscopy and in situ time-resolved X-ray photoelectron spectroscopy of surface-bound catalytic chemical vapor deposition of single-walled carbon nanotubes and nanofibers. We observe that transition metal catalyst nanoparticles on SiOx support show crystalline lattice fringe contrast and high deformability before and during nanotube formation. A single-walled carbon nanotube nucleates by lift-off of a carbon cap. Cap stabilization and nanotube growth involve the dynamic reshaping of the catalyst nanocrystal itself. For a carbon nanofiber, the graphene layer stacking is determined by the successive elongation and contraction of the catalyst nanoparticle at its tip.     

In-House Validation and Comparison of Two Wheat (<Emphasis Type="Italic">Triticum aestivum</Emphasis>) Taxon-Specific Real-Time PCR Methods for GMO Quantification Supported by Droplet Digital PCR

Common wheat is one of the most important staple food crops worldwide. However, unlike other important staple crops such as maize or soybean, genetically modified (GM) wheat is not yet present in the global food market. Nonetheless, in the recent past, the adventitious presence of GM glyphosate-tolerant volunteers was reported in open wheat fields in the USA. The European Union Reference Laboratory for GM Food and Feed (EURL-GMFF) was therefore called to develop a strategy to detect such unauthorised GM wheat in wheat samples by using both taxon-specific and screening tests. Two candidate common wheat taxon-specific real-time PCR methods were suggested, one targeting ssII-D gene coding for starch synthase and the other targeting waxy-D1 gene, coding for granule-bound starch synthase. In the present study, the two above-mentioned real-time PCR taxon-specific methods were in-house verified and compared, proposing droplet digital PCR (ddPCR) as a new tool for supporting the application of the European Network of GMO Laboratories (ENGL) established method performance criteria. Preliminary performance data of waxy-D1 and ssII-D methods in ddPCR format are shown too to give a contribution to the bridging process from the consolidated to the emerging quantitative PCR methodology.     

Synthesis of TiO2-Au composites by titania-nanorod-assisted generation of gold nanoparticles at aqueous/nonpolar interfaces

Hydrophobically coated anatase TiO(2) nanorods can assist the reduction of AuCl(4) (-)ions at aqueous/nonpolar solvent interfaces, which results in the generation of organic-soluble Au nanoparticles with tunable size in the absence of any metal ligands and/or phase-transfer agents. The titania-nanorod-driven modulation of interfacial energy and catalysis of gold nucleation provide straightforward access to nanocomposite solutions of TiO(2)-stabilized Au nanoparticles. Among colloidal approaches, this method represents a unique tool for the surfactantless, large-scale preparation of nanostructured semiconductor-metal hybrid systems with relevant technological potential in catalysis, photocatalysis, and charge-storage processes.     

Nanoparticles from polylactide and polyether block copolymers: formation, properties, encapsulation, and release of pyrene--fluorescent model of hydrophobic drug

Polylactide-b-polyglycidol-b-poly(ethylene oxide) terpolymers and their derivatives with carboxyl and 4-(phenylazo)phenyl labels in polyglycidol blocks were used for formation of nanoparticles. Nanoparticles were produced by self assembly of terpolymer macromolecules in water above the critical aggregation concentration and by dialysis of terpolymer solutions in 1,4-dioxane against water. For terpolymers with 4-(phenylazo)phenyl labels critical aggregation concentrations increased after irradiation with UV light (300 < lambda < 400 nm) inducing conformational change of the label from trans- to cis-conformation. Diameters of nanoparticles obtained by self-assembly of macromolecules ranged from 20 to 44 nm. Dialysis yielded nanoparticles with bimodal diameter distribution. One fraction had diameters below 35 nm and diameters of the second fraction were in a range from 350 to 2300 nm, depending on terpolymer structure. Mixtures of terpolymers with poly(L,L-lactide) and poly(D,D-lactide) blocks yielded nanoparticles with diameters from 350 to 440 nm. Pyrene was incorporated into nanoparticles by partition between solution and nanoparticles or directly during particle formation by dialysis. Monitoring of pyrene release from nanoparticles suggests that a fraction of this compound was entrapped into the polylactide core whereas the remaining one was located in the polyether rich shell. The release from shells is faster for nanoparticles made from copolymers with carboxyl labels in polyglycidol blocks.     

Columnar Fe2O3 arrays via plasma-enhanced growth: Interplay of fluorine substitution and photoelectrochemical properties

A single-step plasma enhanced-chemical vapor deposition (PE-CVD) route for the synthesis of F-doped iron(III) oxide nanomaterials is presented. Growth experiments, performed from a fluorinated Fe(II) β-diketonate precursor on Indium Tin Oxide (ITO) between 200 and 400 °C, yielded columnar β-Fe₂O₃ arrays with a preferential (100) growth direction. The fluorine content in the deposits could be adjusted by the sole variation of the deposition temperature controlling, in turn, the optical absorption and energy bandgap. Photocurrent measurements and Mott–Schottky analyses, carried out in Na₂SO₄ solution under one sun illumination, evidenced a conductivity switch from n- to p-type upon increasing fluorine amount in the obtained nanomaterials. The sample photocurrent density, donor content and flatband potential support the hypothesis that a progressive substitution of oxygen by fluorine in the iron(III) oxide lattice can alter electronic structure and extend charge carrier lifetimes, making anion-doped β-Fe₂O₃ an efficient water oxidation catalyst.