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/

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

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

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

Light-induced reversible modification of the work function of a new perfluorinated biphenyl azobenzene chemisorbed on Au (111)

This work was financially supported by EC through the Marie-Curie ITN SUPERIOR (PITN-GA-2009-238177) and IEF MULTITUDES (PIEF-GA-2012-326666), the ERC project SUPRAFUNCTION (GA-257305), the Agence Nationale de la Recherche through the LabEx project Chemistry of Complex Systems (ANR-10-LABX-0026_CSC), and the International Center for Frontier Research in Chemistry (icFRC). The work in Mons is further supported by the Interuniversity Attraction Poles Programme (P7/05) initiated by the Belgian Science Policy Office, and by the Belgian National Fund for Scientific Research (FNRS). J.C. is an FNRS research director. The synthesis team in Switzerland acknowledges financial support by the Swiss National Science Foundation (SNF) and the Swiss Nanoscience Institute (SNI)

Graphene via Molecule-Assisted Ultrasound-Induced Liquid-Phase Exfoliation: A Supramolecular Approach

Graphene is a two-dimensional (2D) material holding unique optical, mechanical, thermal and electrical properties. The combination of these exceptional characteristics makes graphene an ideal model system for fundamental physical and chemical studies as well as technologically ground breaking material for a large range of applications. Graphene can be produced either following a bottom-up or top-down method. The former is based on the formation of covalent networks suitably engineered molecular building blocks undergoing chemical reaction. The latter takes place through the exfoliation of bulk graphite into individual graphene sheets. Among them, ultrasound-induced liquid-phase exfoliation (UILPE) is an appealing method, being very versatile and applicable to different environments and on various substrate types. In this chapter, we describe the recently reported methods to produce graphene via molecule-assisted UILPE of graphite, aiming at the generation of high-quality graphene. In particular, we will focus on the supramolecular approach, which consists in the use of suitably designed organic molecules during the UILPE of graphite. These molecules act as graphene dispersion-stabilizing agents during the exfoliation. This method relying on the joint effect of a solvent and ad hoc molecules to foster the exfoliation of graphite into graphene in liquid environment represents a promising and modular method toward the improvement of the process of UILPE in terms of the concentration and quality of the exfoliated material. Furthermore, exfoliations in aqueous and organic solutions are presented and discussed separately

Theory of mechanical unfolding of homopolymer globule: all-or-none transition in force-clamp mode vs phase coexistence in position-clamp mode

Equilibrium mechanical unfolding of a globule formed by long flexible homopolymer chain collapsed in a poor solvent and subjected to an extensional force f (force-clamp mode) or extensional deformation D (position-clamp mode) is studied theoretically. Our analysis, like all previous analysis of this problem, shows that the globule behaves essentially differently in two modes of extension. In the force-clamp mode, mechanical unfolding of the globule with increasing applied force occurs without intramolecular microphase segregation, and at certain threshold value of the pulling force the globule unfolds as a whole ("all-or-none" transition). The value of the threshold force and the corresponding jump in the distance between the chain ends increase with a deterioration of the solvent quality and/or with an increase in the degree of polymerization. In the position-clamp mode, the globule unfolding occurs via intramolecular microphase coexistence of globular and extended microphases followed by an abrupt unraveling transition. Reaction force in the microphase segregation regime demonstrates an "anomalous" decrease with increasing extension. Comparison of deformation curves in force and position-clamp modes demonstrates that at weak and strong extensions the curves for two modes coincide, differences are observed in the intermediate extension range. Another unfolding scenario is typical for short globules: in both modes of extension they unfold continuously, without jumps or intramolecular microphase coexistence, by passing a sequence of uniformly elongated configurations.Comment: 19 pages, 13 figures, 1 tabl

Punctured Two-Dimensional Sheets for Harvesting Blue Energy

The challenges of global climate change and the world’s growing demand for energy have brought the need for new renewable energy sources to the top of the international community’s agenda. We have known for many centuries that energy is released upon mixing seawater and freshwater, yet it was just a few decades ago that it became clear how this energy can be converted into electricity instead of heat. As a result, the blue energy rush has raised and set new strategies in different science and technology sectors, leading to the construction of a new generation of plants and other technological investments. Among many approaches, pressure-retarded osmosis has emerged as a promising method to collect the largest amount of produced blue energy. In this Perspective, we highlight the advances in the development of ultrathin membranes based on two-dimensional materials. We discuss the most relevant synthetic methods devised to generate atomically thin membranes for pressure-retarded osmosis and retarded electrodialysis applications, and we provide some critical views on the greatest challenges in this thrilling research area