scholarly journals From Amorphous Silicones to Si-Containing Highly Ordered Polymers: Some Romanian Contributions in the Field

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1605
Author(s):  
Maria Cazacu ◽  
Carmen Racles ◽  
Mirela-Fernanda Zaltariov ◽  
Mihaela Dascalu ◽  
Adrian Bele ◽  
...  
Keyword(s):  
Self Assembly ◽  
Helical Structure ◽  
Ordered Structures ◽  
Molecular Weights ◽  
Secondary Building Units ◽  
High Flexibility ◽  
High Degree ◽  
Very High ◽  
1D Chains ◽  
Mixture Of Ligands

Polydimethylsiloxane (PDMS), in spite of its well-defined helical structure, is an amorphous fluid even at extremely high molecular weights. The cause of this behavior is the high flexibility of the siloxane backbone and the lack of intermolecular interactions attributed to the presence of methyl groups. These make PDMS incompatible with almost any organic or inorganic component leading to phase separation in siloxane-siloxane copolymers containing blocks with polar organic groups and in siloxane-organic copolymers, where dimethylsiloxane segments co-exist with organic ones. Self-assembly at the micro- or nanometric scale is common in certain mixed structures, including micelles, vesicles, et cetera, manifesting reversibly in response to an external stimulus. Polymers with a very high degree of ordering in the form of high-quality crystals were obtained when siloxane/silane segments co-exist with coordinated metal blocks in the polymer chain. While in the case of coordination of secondary building units (SBUs) with siloxane ligands 1D chains are formed; when coordination is achieved in the presence of a mixture of ligands, siloxane and organic, 2D structures are formed in most cases. The Romanian research group’s results regarding these aspects are reviewed: from the synthesis of classic, amorphous silicone products, to their adaptation for use in emerging fields and to new self-assembled or highly ordered structures with properties that create perspectives for the use of silicones in hitherto unexpected areas.

scholarly journals Self-Assembly of Low-Molecular-Weight Asymmetric Linear Triblock Terpolymers: How Low Can We Go?

Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5527
Author(s):  
Christina Miskaki ◽  
Ioannis Moutsios ◽  
Gkreti-Maria Manesi ◽  
Konstantinos Artopoiadis ◽  
Cheng-Yen Chang ◽  
...  
Keyword(s):  
Self Assembly ◽  
Low Molecular Weight ◽  
Ordered Structures ◽  
Low Dimensions ◽  
X Ray ◽  
Molecular Weights ◽  
Transmission Electron ◽  
First Time ◽  
Triblock Terpolymers ◽  
Structure Properties

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their corresponding molecular and bulk characterizations were performed. Very low dimensions are evident from the characterization in bulk from transmission electron microscopy studies, verified by small-angle X-ray data, since sub-16 nm domains are evident in all three cases. The self-assembly results justify the assumptions that the high Flory–Huggins parameter, χ, even in low molecular weights, leads to significantly well-ordered structures, despite the complexity of the systems studied. Furthermore, it is the first time that a structure/properties relationship was studied for such systems in bulk, potentially leading to prominent applications in nanotechnology and nanopatterning, for as low as sub-10 nm thin-film manipulations.

Electron Microscopy in Molecular Biology

1967 ◽  
Vol 25 ◽  
pp. 2-3
Author(s):  
Cecil E. Hall
Keyword(s):  
Electron Microscopy ◽  
Molecular Biology ◽  
Noise Level ◽  
Molecular Structures ◽  
Material Structure ◽  
The Arts ◽  
Shadow Casting ◽  
Electron Image ◽  
High Degree ◽  
Very High

The visualization of organic macromolecules such as proteins, nucleic acids, viruses and virus components has reached its high degree of effectiveness owing to refinements and reliability of instruments and to the invention of methods for enhancing the structure of these materials within the electron image. The latter techniques have been most important because what can be seen depends upon the molecular and atomic character of the object as modified which is rarely evident in the pristine material. Structure may thus be displayed by the arts of positive and negative staining, shadow casting, replication and other techniques. Enhancement of contrast, which delineates bounds of isolated macromolecules has been effected progressively over the years as illustrated in Figs. 1, 2, 3 and 4 by these methods. We now look to the future wondering what other visions are waiting to be seen. The instrument designers will need to exact from the arts of fabrication the performance that theory has prescribed as well as methods for phase and interference contrast with explorations of the potentialities of very high and very low voltages. Chemistry must play an increasingly important part in future progress by providing specific stain molecules of high visibility, substrates of vanishing “noise” level and means for preservation of molecular structures that usually exist in a solvated condition.

A Low-Noise, High-Gain Quasi-Millimeter-Wave Receiver MMIC with a Very High Degree of Integration Using 3D-MMIC Technology

2011 ◽  
Vol E94-C (10) ◽  
pp. 1548-1556 ◽  
Author(s):  
Takana KAHO ◽  
Yo YAMAGUCHI ◽  
Kazuhiro UEHARA ◽  
Kiyomichi ARAKI
Keyword(s):  
Millimeter Wave ◽  
High Gain ◽  
Low Noise ◽  
High Degree ◽  
Very High ◽  
Millimeter Wave Receiver

Investigation of Au SAMs Photoclick Derivatization by PM-IRRAS

2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge
Keyword(s):  
Cell Adhesion ◽  
Self Assembly ◽  
Materials Science ◽  
Fibroblast Cell ◽  
Fine Tuning ◽  
Chemical System ◽  
Infrared Reflection ◽  
Assembled Monolayers ◽  
One Step ◽  
High Degree

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>

scholarly journals Nano- and Micropatterning on Optical Fibers by Bottom-Up Approach: The Importance of Being Ordered

2021 ◽  
Vol 11 (7) ◽  
pp. 3254
Author(s):  
Marco Pisco ◽  
Francesco Galeotti
Keyword(s):  
Optical Fiber ◽  
Optical Fibers ◽  
Self Assembly ◽  
Ordered Structures ◽  
Bottom Up ◽  
Photonic Structures ◽  
Fiber Technology ◽  
Optical Fiber Probes ◽  
Fiber Probes ◽  
Self Assembled

The realization of advanced optical fiber probes demands the integration of materials and structures on optical fibers with micro- and nanoscale definition. Although researchers often choose complex nanofabrication tools to implement their designs, the migration from proof-of-principle devices to mass production lab-on-fiber devices requires the development of sustainable and reliable technology for cost-effective production. To make it possible, continuous efforts are devoted to applying bottom-up nanofabrication based on self-assembly to decorate the optical fiber with highly ordered photonic structures. The main challenges still pertain to “order” attainment and the limited number of implementable geometries. In this review, we try to shed light on the importance of self-assembled ordered patterns for lab-on-fiber technology. After a brief presentation of the light manipulation possibilities concerned with ordered structures, and of the new prospects offered by aperiodically ordered structures, we briefly recall how the bottom-up approach can be applied to create ordered patterns on the optical fiber. Then, we present un-attempted methodologies, which can enlarge the set of achievable structures, and can potentially improve the yielding rate in finely ordered self-assembled optical fiber probes by eliminating undesired defects and increasing the order by post-processing treatments. Finally, we discuss the available tools to quantify the degree of order in the obtained photonic structures, by suggesting the use of key performance figures of merit in order to systematically evaluate to what extent the pattern is really “ordered”. We hope such a collection of articles and discussion herein could inspire new directions and hint at best practices to fully exploit the benefits inherent to self-organization phenomena leading to ordered systems.

scholarly journals Multi-Locus Selection and the Structure of Variation at the white Gene of Drosophila melanogaster

Genetics ◽  
1996 ◽  
Vol 144 (2) ◽  
pp. 635-645 ◽  
Author(s):  
David A Kirby ◽  
Wolfgang Stephan
Keyword(s):  
Drosophila Melanogaster ◽  
White Gene ◽  
Transcriptional Unit ◽  
North American Population ◽  
Evolutionary Mechanisms ◽  
Locus Selection ◽  
Neutral Equilibrium ◽  
History Of ◽  
High Degree ◽  
Very High

Abstract We surveyed sequence variation and divergence for the entire 5972-bp transcriptional unit of the white gene in 15 lines of Drosophila melanogaster and one line of D. simulans. We found a very high degree of haplotypic structuring for the polymorphisms in the 3′ half of the gene, as opposed to the polymorphisms in the 5′ half. To determine the evolutionary mechanisms responsible for this pattern, we sequenced a 1612-bp segment of the white gene from an additional 33 lines of D. melanogaster from a European and a North American population. This 1612-bp segment encompasses an 834bp region of the white gene in which the polymorphisms form high frequency haplotypes that cannot be explained by a neutral equilibrium model of molecular evolution. The small number of recombinants in the 834bp region suggests epistatic selection as the cause of the haplotypic structuring, while an investigation of nucleotide diversity supports a directional selection hypothesis. A multi-locus selection model that combines features from both-hypotheses and takes the recent history of D. melanogaster into account may be the best explanation for these data.

scholarly journals Nucleation of Ga droplets self-assembly on GaAs(111)A substrates

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Artur Tuktamyshev ◽  
Alexey Fedorov ◽  
Sergio Bietti ◽  
Stefano Vichi ◽  
Riccardo Tambone ◽  
...  
Keyword(s):  
Quantum Dots ◽  
Size Distribution ◽  
Self Assembly ◽  
Cluster Size ◽  
Droplet Size Distribution ◽  
Local Environment ◽  
The Self ◽  
Critical Cluster ◽  
Droplet Nucleation ◽  
High Degree

AbstractWe investigated the nucleation of Ga droplets on singular GaAs(111)A substrates in the view of their use as the seeds for the self-assembled droplet epitaxial quantum dots. A small critical cluster size of 1–2 atoms characterizes the droplet nucleation. Low values of the Hopkins-Skellam index (as low as 0.35) demonstrate a high degree of a spatial order of the droplet ensemble. Around $$350\,^{\circ }\hbox {C}$$ 350 ∘ C the droplet size distribution becomes bimodal. We attribute this observation to the interplay between the local environment and the limitation to the adatom surface diffusion introduced by the Ehrlich–Schwöbel barrier at the terrace edges.

scholarly journals Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1412
Author(s):  
Eunkyung Ji ◽  
Cian Cummins ◽  
Guillaume Fleury
Keyword(s):  
Thin Film ◽  
Block Copolymers ◽  
Self Assembly ◽  
Ring Opening ◽  
Periodic Structures ◽  
One Pot ◽  
Ordered Structures ◽  
Carbonyl Chloride ◽  
Thin Film Patterning ◽  
Nanoporous Templates

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.

A comparison of the compressibilities of some gases with that of nitrogen at pressures below one atmosphere

1950 ◽  
Vol 200 (1061) ◽  
pp. 201-218 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Differential Method ◽  
Linear Extrapolation ◽  
Volume Changes ◽  
Pure Nitrogen ◽  
Molecular Weights ◽  
Nitrous Oxide Oxygen ◽  
The Individual ◽  
Straight Lines ◽  
High Degree

A differential method for comparing the compressibilities of gases at pressures below 1 atm. has been developed in which many of the errors inherent in methods employed previously have been to a large extent eliminated, especially those due to meniscus volume changes and capillary depression. Using pure nitrogen as a standard the low-pressure isothermals of carbon monoxide, carbon dioxide, nitrous oxide, oxygen, ethylene and propane have been determined at a temperature of 22-05° C. The deviations of the individual points from straight lines do not in most cases exceed 2 parts in 100,000. In no case, even with propane, was any curvature in the isotherms detectable. The contention of Moles and other recent workers that the molecular weights of liquefiable gases can be determined to a high degree of accuracy by linear extrapolation is rendered highly probable by this fresh evidence.

Chiral Molecular Cavities of Calix[4]Crown on Au(111)

2008 ◽  
Vol 8 (11) ◽  
pp. 5702-5707 ◽  
Author(s):  
Ge-Bo Pan ◽  
Jun Luo ◽  
Qi-Yu Zheng ◽  
Li-Jun Wan
Keyword(s):  
Self Assembly ◽  
Chiral Recognition ◽  
Scanning Tunneling ◽  
Racemic Mixture ◽  
Tunneling Microscopy ◽  
Geometrical Structures ◽  
Simple Method ◽  
Ordered Structures ◽  
Ordered Arrays ◽  
Stm Images

Well-ordered arrays of chiral molecular cavities have been constructed by self-assembly of inherently chiral calix[4]crown on Au(111) in 0.1 M HClO4 solution and investigated by scanning tunneling microscopy (STM). The chiral features are clearly observed in high resolution STM images. It is found that the adsorption of the two enantiomers results in the same ordered structures with upright orientation on Au(111). Moreover, only phase separation has been observed for the racemic mixture of the two enantiomers in the experiment. This is mainly due to the weak molecule-substrate interaction as well as asymmetric geometrical structures of the two enantiomers. The present study provides a simple method for construction of ordered arrays of chiral molecular cavities, which are of potential in chemical sensors, chiral recognition, and nonlinear optics.

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