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Analyzing social wrongs
(2023)
All-in-One "Schizophrenic" self-assembly of orthogonally tuned thermoresponsive diblock copolymers
(2019)
Smart, fully orthogonal switching was realized in a highly biocompatible diblock copolymer system with variable trigger-induced aqueous self-assembly. The polymers are composed of nonionic and zwitterionic blocks featuring lower and upper critical solution temperatures (LCSTs and UCSTs). In the system investigated, diblock copolymers from poly(N-isopropyl methacrylamide) (PNIPMAM) and a poly(sulfobetaine methacrylamide), systematic variation of the molar mass of the latter block allowed for shifting the UCST of the latter above the LCST of the PNIPMAM block in a salt-free condition. Thus, successive thermal switching results in "schizophrenic" micellization, in which the roles of the hydrophobic core block and the hydrophilic shell block are interchanged depending on the temperature. Furthermore, by virtue of the strong electrolyte-sensitivity of the zwitterionic polysulfobetaine block, we succeeded to shift its UCST below the LCST of the PNIPMAM block by adding small amounts of an electrolyte, thus inverting the pathway of switching. This superimposed orthogonal switching by electrolyte addition enabled us to control the switching scenarios between the two types of micelles (i) via an insoluble state, if the LCST-type cloud point is below the UCST-type cloud point, which is the case at low salt concentrations or (ii) via a molecularly dissolved state, if the LCST-type cloud point is above the UCST-type cloud point, which is the case at high salt concentrations. Systematic variation of the block lengths allowed for verifying the anticipated behavior and identifying the molecular architecture needed. The versatile and tunable self-assembly offers manifold opportunities, for example, for smart emulsifiers or for sophisticated carrier systems.
Potentially disabled?
(2022)
Ten years ago, I was diagnosed with a rare illness called Myasthenia Gravis. Myasthenia Gravis is a long-term neuromuscular autoimmune disease where antibodies block or destroy specific receptors at the junction between nerve and muscle; hence, nerve impulses fail to trigger muscle contractions. The disease leads to varying degrees of muscle weakness. Currently, I have only minor symptoms, I am not seriously impaired, and I do not suffer from any social disadvantage because of my illness. Yet, my life and my body since my diagnosis feel different than before. In this paper I aim to make this feeling intelligible and propose that it is a state of what I call ‘latent impairment’. Latent impairment is a state of being ‘in between’, different from being actually impaired and also different from being abled-bodied. The theory takes its cues both from social constructionist theories of disability as well as theories of (chronic) illness and their focus on the importance of subjectivity. Furthermore, I suggest that a phenomenological understanding of latent impairment can show possible ways of becoming an ally to the DRM.
The Cotentin Peninsula (Normandy, France) displays sequences of marine terraces and rasas, the latter being wide Late Cenozoic coastal erosion surfaces, that are typical of Western European coasts in Portugal, Spain, France and southern England. Remote sensing imagery and field mapping enabled reappraisal of the Cotentin coastal sequences. From bottom to top, the N Cotentin sequence includes four previously recognized Pleistocene marine terraces (T1 to T4) at elevations <40 m as well as four higher and older rasas (R1 to R4) reaching 200 +/- 5 m in elevation. Low-standing marine terraces are not observed in the central part of the Peninsula and a limited number of terraces are described to the south. The high-standing rasas are widespread all over the peninsula. Such strandline distributions reveal major changes during the Late Cenozoic. Progressive uplift of an irregular sea-floor led to subaerial exposure of bathymetric highs that were carved into rocky platforms, rasas and marine terraces. Eventually, five main islands coalesced and connected to the mainland to the south to form the Cotentin Peninsula. On the basis of previous dating of the last interglacial maximum terrace (i.e. Marine Isotopic Stage, MIS 5e), sequential morphostratigraphy and modelling, we have reappraised uplift rates and derived: (i) mean Upper Pleistocene (i.e. since MIS 5e similar to 122 +/- 6 ka, i.e. kilo annum) apparent uplift rates of 0.04 +/- 0.01 mm/yr, (ii) mean Middle Pleistocene eustasy-corrected uplift rates of 0.09 +/- 0.03 mm/yr, and (iii) low mean Pleistocene uplift rates of 0.01 mm/yr. Extrapolations of these slow rates combined with geological evidence implies that the formation of the sequences from the Cotentin Peninsula occurred between 3 Ma (Pliocene) and 15 Ma (Miocene), which cannot be narrowed down further without additional research. Along the coasts of Western Europe, sequences of marine terraces and rasas are widespread (169 preserve the MIS Se benchmark). In Spain, Portugal, S England and other parts of western France, the sequences morphostratigraphy is very similar to that of Cotentin. The onset of such Western European sequences occurred during the Miocene (e.g. Spain) or Pliocene (e.g. Portugal). We interpret this Neogene-Quaternary coastal uplift as a symptom of the increasing lithospheric compression that accompanies Cenozoic orogenies. (C) 2017 Elsevier B.V. All rights reserved.
The understanding of bidimensional materials dynamics and its electrolyte interface equilibrium, such as graphene oxide (GO), is critical for the development of a capacitive biosensing platform. The interfacial capacitance (C-i) of graphene-based materials may be tuned by experimental conditions such as pH optimization and cation size playing key roles at the enhancement of their capacitive properties allowing their application as novel capacitive biosensors. Here we reported a systematic study of C-i of multilayer GO films in different aqueous electrolytes employing electrochemical impedance spectroscopy for the application in a capacitive detection system. We demonstrated that the presence of ionizable oxygen-containing functional groups within multilayer GO film favors the interactions and the accumulation of cations in the structure of the electrodes enhancing the GO C-i in aqueous solutions, where at pH 7.0 (the best condition) the C-i was 340 mu F mg(-1) at -0.01 V vs Ag/AgCl. We also established that the hydrated cation radius affects the mobility and interaction with GO functional groups and it plays a critical role in the Ci, as demonstrated in the presence of different cations Na+=640 mu F mg(-1), Li+=575 mu F mg(-1) and TMA(+)=477 mu F mg(-1). As a proof-of-concept, the capacitive behaviour of GO was explored as biosensing platform for standard streptavidin-biotin systems. For this system, the C-i varied linearly with the log of the concentration of the targeting analyte in the range from 10 pg mL(-1) to 100 ng mL(-1), showing the promising applicability of capacitive GO based sensors for label-free biosensing.
Polymeric electrophosphorescent LEDs with internal quantum efficiencies approaching unity have been fabricated. Such performance levels are previously unknown for OLEDs. The key to this success is redox chemically doped oxetane- crosslinkable hole-transporting layers with multilayer capability (see figure). They improve hole injection and act as electron-blocking layers, without the need to include exciton-or hole-blocking layers
This contribution reports the combined influences of odd-even effects and the specific positioning of alkoxy side chains OR1 = (OCn+H-10(2(n+10)+1)) and OR2 = (OCnH2n+1) (with n = 6, 7, 8, 9) on the phenylene-ethynylene and phenylene- vinylene segments, respectively, on the optical properties of hybrid polymers P(n+10)/n of general repeating unit: -Ph-C equivalent to C-Ph-C equivalent to C-Ph-CH=CH-Ph-CH=CH-. For the polymeric materials, visual color impression varies alternatively between orange red (P16/6 and P18/8) and yellow (P17/7 and P19/9) according to the odd and even features of the alkoxy side chains, where odd or even relates to the total number of sp(3)-hybridized atoms within the side chains. This side chain related effect is ascribed to both absorptive and emissive behaviors of the polymers on the basis of photophysical investigations in the bulk. Almost identical thin film absorption spectra were obtained for all four materials; however, the photoluminescence of the odd polymers, P16/6 (lambda(f) = 556 nm) and P18/ 8 (lambda(f) = 614 nm), was red-shifted relative to that of their even counterparts (lambda(f) = 535 nm). Further, the P18/8 maximum at 614 nm can be readily assigned to excimer emission, as evidenced by the largest Stokes shift (5600 cm(- 1)), largest fwhmf-value (3700 cm(-1))(,) and the lowest Phi(f)-value of 24%. The strong pi-pi interchain interaction in P18/8, due to loose alkoxy side chains packing, does not only favor fluorescence quenching but also enable an effective inter- as well as intra-molecular recombination of the generated positive and negative polarons in electrolurninescence, which explains the good EL properties of this polymer irrespective of the solvent used. A voltage-dependent blue shift of the EL spectra of up to 100 nm was observed for P18/8 devices prepared from aromatic solvents. This red to green EL shift as observed with increasing voltage is assigned to conformational changes of the polymer chains with increasing temperature