74 research outputs found
New RM734-like fluid ferroelectrics enabled through a simplified protecting group free synthesis
We report a novel and simplified synthetic procedure for making analogues of the widely studied ferroelectric nematogen RM734. Our new procedure focuses on building materials starting from the nitro-terminus and eschewing protecting groups, in contrast to previously reported syntheses. This new synthetic approach confers two principal advantages: firstly, the synthesis of the variants described herein is expedient, being a single step as opposed to three or more via the classical route. Secondly, by forgoing the use of benzyl groups as utilised in the original synthesis we can include functionality that is incompatible with hydrogenolysis conditions (e.g. olefins, late halogens, unsaturated heterocycles). Several of the RM734-like materials we report exhibit ferroelectric nematic phases, and we rationalise the behaviour of these materials with aid of electronic structure calculations, potential energy surface scans and atomistic molecular dynamics simulations
Rapid conformational analysis of semi-flexible liquid crystals.
We present an approach for rapid conformational analysis of semi-flexible liquid crystals. We use a simple graphical user interface (GUI) tool that leverages rules-based methods for efficient generation of bend-angle distributions, offering a significant improvement over traditional single-conformer analysis. Our methods demonstrated proficiency in approximating molecular shapes comparable to those obtained from molecular dynamics (MD) simulations, albeit with notable deviations in the under sampling of hairpin conformations and oversampling of extended configurations. Re-evaluation of existing data revealed an apparent weak correlation between NTB transition temperatures and bend angles, underscoring the complexity of molecular shapes beyond mere geometry. Furthermore, we integrated this conformational analysis into a pipeline of algorithmic molecular design, utilising a fragment-based genetic algorithm to generate novel cyanobiphenyl-containing materials. This integration opens new avenues for the exploration of liquid crystalline materials, particularly in systems where systematic conformer searches are impractical, such as large oligomeric systems. Our findings highlight the potential and growing importance of computational approaches in accelerating the design and synthesis of next-generation liquid crystalline materials
A convenient one-pot synthesis, and characterisation of the ω-bromo-1-(4-cyanobiphenyl-4’-yl) alkanes (CBnBr)
A convenient synthetic route based on a sodium-mediated aromatic cross-coupling reaction is described for the multi-gram preparation of the ω-bromo-1-(4-cyanobiphenyl-4’−yl) alkanes (CBnBr, n = 2–10). These materials are not only key intermediates in the synthesis of oligomers and polymers but also exhibit fascinating liquid crystal behaviour in their own right. Nematic behaviour is observed for n⩾5, and the nematic-isotropic transition temperature, TNI, increases in essentially a linear manner on n. The properties of the ω-bromo-1-(4-cyanobiphenyl-4’−yloxy) alkanes (CBOnBr, n = 2–9) are also reported, and nematic behaviour is seen for n⩾3. The values of TNI show a weak odd-even effect on n in which the odd members show the higher values. The sense of this alternation is opposite to that seen for the 4-alkyloxy-4’-cyanobiphenyls, and this is attributed to the steric bulk of the bromine atom. The absence of smectic behaviour for both the CBnBr and CBOnBr series is attributed largely to electrostatic interactions that would arise from the concentration of the bromine atoms at the layer interfaces in an interdigitated smectic phase. A comparison of a range of cyanobiphenyl-based materials containing a chain with a terminal polar or polarisable group suggests that their phase behaviour is governed largely by their average molecular shapes
Spontaneous Symmetry Breaking in Polar Fluids
Spontaneous symmetry breaking and emergent polar order are each of fundamental importance to a range of scientific disciplines, as well as generating rich phase behaviour in liquid crystals (LCs). Here, we show the union of these phenomena to lead to two previously undiscovered polar liquid states of matter. Both phases have a lamellar structure with an inherent polar ordering of their constituent molecules. The first of these phases is characterised by polar order and a local tilted structure; the tilt direction processes about a helix orthogonal to the layer normal, the period of which is such that we observe selective reflection of light. The second new phase type is anti-ferroelectric, with the constituent molecules aligning orthogonally to the layer normal. This has led us to term the phases the SmCHP and SmAAF phases, respectively. Further to this, we obtain room temperature ferroelectric
nematic (NF) and SmCHP phases via binary mixture formulation of the novel materials described here with a standard NF compound (DIO), with the resultant materials having melting points (and/or glass transitions) which are significantly below ambient temperature. The new soft matter phase types discovered herein can be considered as electrical analogues of topological structures of magnetic spins in hard matter
(Sub)mm Interferometry Applications in Star Formation Research
This contribution gives an overview about various applications of (sub)mm
interferometry in star formation research. The topics covered are molecular
outflows, accretion disks, fragmentation and chemical properties of low- and
high-mass star-forming regions. A short outlook on the capabilities of ALMA is
given as well.Comment: 20 pages, 7 figures, in proceedings to "2nd European School on Jets
from Young Star: High Angular Resolution Observations". A high-resolution
version of the paper can be found at
http://www.mpia.de/homes/beuther/papers.htm
Observational diagnostics of gas in protoplanetary disks
Protoplanetary disks are composed primarily of gas (99% of the mass).
Nevertheless, relatively few observational constraints exist for the gas in
disks. In this review, I discuss several observational diagnostics in the UV,
optical, near-IR, mid-IR, and (sub)-mm wavelengths that have been employed to
study the gas in the disks of young stellar objects. I concentrate in
diagnostics that probe the inner 20 AU of the disk, the region where planets
are expected to form. I discuss the potential and limitations of each gas
tracer and present prospects for future research.Comment: Review written for the proceedings of the conference "Origin and
Evolution of Planets 2008", Ascona, Switzerland, June 29 - July 4, 2008. Date
manuscript: October 2008. 17 Pages, 6 graphics, 134 reference
Massive Star Formation
This chapter reviews progress in the field of massive star formation. It
focuses on evidence for accretion and current models that invoke high accretion
rates. In particular it is noted that high accretion rates will cause the
massive young stellar object to have a radius much larger than its eventual
main sequence radius throughout much of the accretion phase. This results in
low effective temperatures which may provide the explanation as to why luminous
young stellar objects do not ionized their surroundings to form ultra-compact H
II regions. The transition to the ultra-compact H II region phase would then be
associated with the termination of the high accretion rate phase. Objects
thought to be in a transition phase are discussed and diagnostic diagrams to
distinguish between massive young stellar objects and ultra-compact H II
regions in terms of line widths and radio luminosity are presented.Comment: 21 pages, 6 figures, chapter in Diffuse Matter from Star Forming
Regions to Active Galaxies - A Volume Honouring John Dyson, Edited by T.W.
Hartquist, J. M. Pittard, and S. A. E. G. Falle. Series: Astrophysics and
Space Science Proceedings. Springer Dordrecht, 2007, p.6
Características produtivas de cordeiros terminados em confinamento com dietas contendo diferentes teores de borra de soja
The Origin, Early Evolution and Predictability of Solar Eruptions
Coronal mass ejections (CMEs) were discovered in the early 1970s when space-borne coronagraphs revealed that eruptions of plasma are ejected from the Sun. Today, it is known that the Sun produces eruptive flares, filament eruptions, coronal mass ejections and failed eruptions; all thought to be due to a release of energy stored in the coronal magnetic field during its drastic reconfiguration. This review discusses the observations and physical mechanisms behind this eruptive activity, with a view to making an assessment of the current capability of forecasting these events for space weather risk and impact mitigation. Whilst a wealth of observations exist, and detailed models have been developed, there still exists a need to draw these approaches together. In particular more realistic models are encouraged in order to asses the full range of complexity of the solar atmosphere and the criteria for which an eruption is formed. From the observational side, a more detailed understanding of the role of photospheric flows and reconnection is needed in order to identify the evolutionary path that ultimately means a magnetic structure will erupt
Comprehensive Molecular Characterization of Muscle-Invasive Bladder Cancer
We report a comprehensive analysis of 412 muscle-invasive bladder cancers characterized by multiple TCGA analytical platforms. Fifty-eight genes were significantly mutated, and the overall mutational load was associated with APOBEC-signature mutagenesis. Clustering by mutation signature identified a high-mutation subset with 75% 5-year survival. mRNA expression clustering refined prior clustering analyses and identified a poor-survival “neuronal” subtype in which the majority of tumors lacked small cell or neuroendocrine histology. Clustering by mRNA, long non-coding RNA (lncRNA), and miRNA expression converged to identify subsets with differential epithelial-mesenchymal transition status, carcinoma in situ scores, histologic features, and survival. Our analyses identified 5 expression subtypes that may stratify response to different treatments. A multiplatform analysis of 412 muscle-invasive bladder cancer patients provides insights into mutational profiles with prognostic value and establishes a framework associating distinct tumor subtypes with clinical options
- …