Analysis and Design of a 1.8-GHz CMOS LC Quadrature VCO

This paper presents a quadrature voltage-controlled oscillator (QVCO) based on the coupling of two LC-tank VCOs. A simplified theoretical analysis for the oscillation frequency and phase noise displayed by the QVCO in the 1/f/sup 3/ region is developed, and good agreement is found between theory and simulation results. A prototype for the QVCO was implemented in a 0.35-/spl mu/m CMOS process with three standard metal layers. The QVCO could be tuned between 1.64 and 1.97 GHz, and showed a phase noise of -140 dBc/Hz or less across the tuning range at a 3-MHz offset frequency from the carrier, for a current consumption of 25 mA from a 2-V power supply. The equivalent phase error between I and Q signals was at most 0.25/spl deg/

Novel Strategies for Recycling Poly(butylene adipate-co-terephthalate)-Starch-Based Plastics: Selective Solubilization and Depolymerization-Repolymerization Processes

Starch-based plastics (SBPs) containing poly(butylene adipate-co-terephthalate) (PBAT) are among the most produced bioplastics on the market and are currently managed at their end of life (EoL) through composting. In view of developing novel EoL approaches, SBPs were characterized here in terms of their main components (PBAT, starch, and plasticizer), and three strategies for their recycling were investigated: (I) the selective solubilization of PBAT with ethyl acetate; (II) a two-step depolymerization-repolymerization process that consists of the catalytic selective alcoholysis of PBAT into its oligomers, followed by their repolymerization to PBAT with no need of adding a new catalyst; and (III) the complete selective depolymerization of PBAT, followed by the recovery and purification of butanediol (1,4-BD), dimethyl terephthalate (DMT), and dimethyl adipate (DMA). Up to 99, 95, and 93% recovery of the SBP components was obtained, respectively, following these three methods. Extensive characterization of the recovered PBAT was performed through molecular weight and thermal and thermomechanical analyses, demonstrating the efficiency of the processes. The environmental sustainability of the proposed approaches was also preliminarily evaluated through the calculation of their environmental factor (E-factor)

Conductivity in organic semiconductors hybridized with the vacuum field

Organic semiconductors have generated considerable interest for their potential for creating inexpensive and flexible devices easily processed on a large scale [1-11]. However technological applications are currently limited by the low mobility of the charge carriers associated with the disorder in these materials [5-8]. Much effort over the past decades has therefore been focused on optimizing the organisation of the material or the devices to improve carrier mobility. Here we take a radically different path to solving this problem, namely by injecting carriers into states that are hybridized to the vacuum electromagnetic field. These are coherent states that can extend over as many as 10^5 molecules and should thereby favour conductivity in such materials. To test this idea, organic semiconductors were strongly coupled to the vacuum electromagnetic field on plasmonic structures to form polaritonic states with large Rabi splittings ca. 0.7 eV. Conductivity experiments show that indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility as revealed when the structure is gated in a transistor configuration. A theoretical quantum model is presented that confirms the delocalization of the wave-functions of the hybridized states and the consequences on the conductivity. While this is a proof-of-principle study, in practice conductivity mediated by light-matter hybridized states is easy to implement and we therefore expect that it will be used to improve organic devices. More broadly our findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.Comment: 16 pages, 13 figure

Chemical Recycling of Polyhydroxybutyrate (PHB) into Bio-Based Solvents and Their Use in a Circular PHB Extraction

Two novel protocols for the chemical valorization of polyhydroxybutyrate (PHB) were developed, aiming at the production of two bio-based molecules: methyl 3-hydroxybutyrate (MHB) and methyl 3-methoxybutyrate (MMB). Optimized reaction conditions were applied to pure PHB and PHB inclusions inside bacterial cells as starting materials. MHB was synthesized through a single-step catalytic methanolysis, while MMB was synthesized through a three-step process: thermolytic distillation to give crotonic acid (CA), esterification to give methyl crotonate (MC), and oxa-Michael addition of MeOH. The obtained MHB and MMB were tested as solvents for the recovery of PHB itself both from freeze-dried single strain cultures (SSC) and mixed microbial cultures (MMC) with low to medium contents of PHB (22-57 wt %). High PHB recovery was achieved: up to 96 ± 1% through MHB and up to 98 ± 1% through MMB. Extraction from MMC slurry (with a PHB content of 39% on dry weight) was also performed, recovering 77 ± 2% using MHB and 92 ± 2% using MMB. High purities and excellent molecular weights and polydispersity indexes of extracted PHB were obtained with both MHB and MMB. Solubility in water, octanol/water partition coefficients (log Kow), and aerobic ready biodegradability of both solvents were also evaluated

Life cycle assessment and energy balance of a novel polyhydroxyalkanoates production process with mixed microbial cultures fed on pyrolytic products of wastewater treatment sludge

A "cradle-to-grave" life cycle assessment is performed to identify the environmental issues of polyhydroxyalkanoates (PHAs) produced through a hybrid thermochemical-biological process using anaerobically digested sewage sludge (ADSS) as feedstock. The assessment includes a measure of the energy performance of the process. The system boundary includes: (i) Sludge pyrolysis followed by volatile fatty acids (VFAs) production; (ii) PHAs-enriched biomass production using a mixed microbial culture (MMC); (iii) PHAs extraction with dimethyl carbonate; and iv) PHAs end-of-life. Three scenarios differing in the use of the syngas produced by both pyrolysis and biochar gasification, and two more scenarios differing only in the external energy sources were evaluated. Results show a trade-off between environmental impacts at global scale, such as climate change and resources depletion, and those having an effect at the local/regional scale, such as acidification, eutrophication, and toxicity. Process configurations based only on the sludge-to-PHAs route require an external energy supply, which determines the highest impacts with respect to climate change, resources depletion, and water depletion. On the contrary, process configurations also integrating the sludge-to-energy route for self-sustainment imply more onsite sludge processing and combustion; this results in the highest values of eutrophication, ecotoxicity, and human toxicity. There is not a categorical winner among the investigated configurations; however, the use of a selected mix of external renewable sources while using sludge to produce PHAs only seems the best compromise. The results are comparable to those of both other PHAs production processes found in the literature and various fossil-based and bio-based polymers, in terms of both non-biogenic GHG emissions and energy demand. Further process advancements and technology improvement in high impact stages are required to make this PHAs production process a competitive candidate for the production of biopolymers on a wide scale

Production of polyhydroxybutyrate by the cyanobacterium cf. Anabaena sp

Polyhydroxybutyrate (PHB) production by the cyanobacterium cf. Anabaena sp. was here studied by varying the medium composition and the carbon source used to induce mixotrophic growth conditions. The highest PHB productivity (0.06 gPHB gbiomass−1 d−1) was observed when cultivating cf. Anabaena sp. in phosphorus-free medium and in the presence of sodium acetate (5.0 g L−1 concentration), after an incubation period of 7 days. A content of 40% of PHB on biomass, a dry weight of 0.1 g L−1, and a photosynthetic efficiency equal to the control were obtained. The cyanobacterium was then grown on a larger scale (10 L) to evaluate the characteristics of the produced PHB in relation to the main composition of the biomass (the content of proteins, polysaccharides, and lipids): after an incubation period of 7 days, a content of 6% of lipids (52% of which as unsaturated fatty acids with 18 carbon atoms), 12% of polysaccharides, 28% of proteins, and 46% of PHB was reached. The extracted PHB had a molecular weight of 3 MDa and a PDI of 1.7. These promising results demonstrated that cf. Anabaena sp. can be included among the Cyanobacteria species able to produce polyhydroxyalkanoates (PHAs) either in photoautotrophic or mixotrophic conditions, especially when it is grown under phosphorus-free conditions

Natural Astaxanthin Is a Green Antioxidant Able to Counteract Lipid Peroxidation and Ferroptotic Cell Death

Astaxanthin is a red orange xanthophyll carotenoid produced mainly by microalgae but which can also be chemically synthesized. As demonstrated by several studies, this lipophilic molecule is endowed with potent antioxidant properties and is able to modulate biological functions. Unlike synthetic astaxanthin, natural astaxanthin (NAst) is considered safe for human nutrition, and its production is considered eco-friendly. The antioxidant activity of astaxanthin depends on its bioavailability, which, in turn, is related to its hydrophobicity. In this study, we analyzed the water-solubility of NAst and assessed its protective effect against oxidative stress by means of different approaches using a neuroblastoma cell model. Moreover, due to its highly lipophilic nature, astaxanthin is particularly protective against lipid peroxidation; therefore, the role of NAst in counteracting ferroptosis was investigated. This recently discovered process of programmed cell death is indeed characterized by iron-dependent lipid peroxidation and seems to be linked to the onset and development of oxidative-stress-related diseases. The promising results of this study, together with the “green sources” from which astaxanthin could derive, suggest a potential role for NAst in the prevention and co-treatment of chronic degenerative diseases by means of a sustainable approach

Lipase catalysed oxidations in a sugar-derived natural deep eutectic solvent

Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation

Evidence of Orientation-Dependent Early States of Prion Protein Misfolded Structures from Single Molecule Force Spectroscopy

Prion diseases are neurodegenerative disorders characterized by the presence of oligomers and amyloid fibrils. These are the result of protein aggregation processes of the cellular prion protein (PrPC) into amyloidal forms denoted as prions or PrPSc. We employed atomic force microscopy (AFM) for single molecule pulling (single molecule force spectroscopy, SMFS) experiments on the recombinant truncated murine prion protein (PrP) domain to characterize its conformations and potential initial oligomerization processes. Our AFM-SMFS results point to a complex scenario of structural heterogeneity of PrP at the monomeric and dimer level, like other amyloid proteins involved in similar pathologies. By applying this technique, we revealed that the PrP C-terminal domain unfolds in a two-state process. We used two dimeric constructs with different PrP reciprocal orientations: one construct with two sequential PrP in the N- to C-terminal orientation (N-C dimer) and a second one in the C- to C-terminal orientation (C-C dimer). The analysis revealed that the different behavior in terms of unfolding force, whereby the dimer placed C-C dimer unfolds at a higher force compared to the N-C orientation. We propose that the C-C dimer orientation may represent a building block of amyloid fibril formation