Polymerizable Self-Organized Membranes: A Novel Class of Organic Compounds

1994 ◽  
Vol 351 ◽  
Author(s):  
Alok Singh ◽  
Michael Markowitz ◽  
Gan Moog Chow
Keyword(s):  
Self Assembly ◽  
Lipid Membranes ◽  
Neutral Lipids ◽  
Acyl Chain ◽  
Metal Particles ◽  
Glycerol Backbone ◽  
Ordered Structures ◽  
Practical Applications ◽  
Self Organized ◽  
Hydrophilic Region

ABSTRACTMolecular Self-assembly of amphiphilic phospholipid molecules (containing a hydrophobic acyl chain and a hydrophilic phosphate group attached to glycerol backbone) and other amphiphiles offers a versatile approach to form ordered structures. Stabilization of lipid microstructures by polymerization renders them useful for practical applications in the areas ranging from controlled release technology to template mediated synthesis of metals. Our efforts are focussed on the development and use of polymerizable diacetylenic phospholipids and their microstructures as template for chemical synthesis. The surface of vesicles and lipid microcylinders (0.5 μm dia.) is made reactive by chemically modifying the hydrophilic region of phospholipids. Lipids with chemically reactive sites were incorporated into lipid membranes predominantly formed from charge neutral lipids and used for binding metal ions and growing fine metal particles.

Tuning cooperative vesicle templating and liquid crystal templating simply by varying silica source

2010 ◽  
Vol 25 (4) ◽  
pp. 648-657 ◽  
Author(s):  
Jun Zhang ◽  
Meihua Yu ◽  
Pei Yuan ◽  
Hongning Wang ◽  
Kun Qian ◽  
...  
Keyword(s):  
Self Assembly ◽  
Composite Structures ◽  
Attenuated Total Reflection ◽  
Practical Applications ◽  
Self Organized ◽  
Mesostructured Materials ◽  
Silica Source ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Poly Propylene

The cooperative self-assembly of organic–inorganic siliceous composite structures has been studied from the aspect of inorganic precursors. We reveal that the vesicular or mesostructured materials can be obtained selectively by just changing the silica sources in one templating system. For poly(ethylene oxide)-type block copolymers with either poly(propylene oxide) or poly(butylene oxide) as the hydrophobic moieties, when the other synthesis parameters are exactly the same, the use of tetramethyl orthosilicate (TMOS) as a silica source gives rise to highly ordered mesostructures, while the use of tetraethyl orthosilicate (TEOS) leads to vesicles or foams. The attenuated total reflection Fourier transform infrared (ATR-FTIR) technique is used to monitor the silicate species derived from the hydrolysis and condensation of TMOS and TEOS as a function of the reaction time. On the basis of the ATR-FTIR results, we propose a “differentiating effect” at relatively high pH (4.7) to interpret the influence of different silica sources on the self-organized composite structures. For comparison, a “leveling effect” at relatively low pH (strong acidic conditions) is revealed to explain that both TMOS and TEOS lead to the same mesostructures. Our contribution provides a feasible and designable method to synthesize from conventional ordered mesostructures to novel vesicular structures, which are significant for their future practical applications.

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 Electrochemical Properties of Lipid Membranes Self-Assembled from Bicelles

Membranes ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 11
Author(s):  
Damian Dziubak ◽  
Kamil Strzelak ◽  
Slawomir Sek
Keyword(s):  
Electrochemical Properties ◽  
Self Assembly ◽  
Lipid Membranes ◽  
Lipid Membrane ◽  
Membrane Resistance ◽  
Electrochemical Characteristics ◽  
Freeze Thaw ◽  
Lipid Films ◽  
Supported Lipid Membranes

Supported lipid membranes are widely used platforms which serve as simplified models of cell membranes. Among numerous methods used for preparation of planar lipid films, self-assembly of bicelles appears to be promising strategy. Therefore, in this paper we have examined the mechanism of formation and the electrochemical properties of lipid films deposited onto thioglucose-modified gold electrodes from bicellar mixtures. It was found that adsorption of the bicelles occurs by replacement of interfacial water and it leads to formation of a double bilayer structure on the electrode surface. The resulting lipid assembly contains numerous defects and pinholes which affect the permeability of the membrane for ions and water. Significant improvement in morphology and electrochemical characteristics is achieved upon freeze–thaw treatment of the deposited membrane. The lipid assembly is rearranged to single bilayer configuration with locally occurring patches of the second bilayer, and the number of pinholes is substantially decreased. Electrochemical characterization of the lipid membrane after freeze–thaw treatment demonstrated that its permeability for ions and water is significantly reduced, which was manifested by the relatively high value of the membrane resistance.

scholarly journals Tripeptide Self-Assembly into Bioactive Hydrogels: Effects of Terminus Modification on Biocatalysis

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 173
Author(s):  
Marina Kurbasic ◽  
Ana M. Garcia ◽  
Simone Viada ◽  
Silvia Marchesan
Keyword(s):  
Self Assembly ◽  
The Self ◽  
Chemical Modifications ◽  
Ability To Work ◽  
Active Compounds ◽  
Future Design ◽  
Self Organized ◽  
The Future ◽  
Bio Material ◽  
Supramolecular Catalysts

Bioactive hydrogels based on the self-assembly of tripeptides have attracted great interest in recent years. In particular, the search is active for sequences that are able to mimic enzymes when they are self-organized in a nanostructured hydrogel, so as to provide a smart catalytic (bio)material whose activity can be switched on/off with assembly/disassembly. Within the diverse enzymes that have been targeted for mimicry, hydrolases find wide application in biomaterials, ranging from their use to convert prodrugs into active compounds to their ability to work in reverse and catalyze a plethora of reactions. We recently reported the minimalistic l-His–d-Phe–d-Phe for its ability to self-organize into thermoreversible and biocatalytic hydrogels for esterase mimicry. In this work, we analyze the effects of terminus modifications that mimic the inclusion of the tripeptide in a longer sequence. Therefore, three analogues, i.e., N-acetylated, C-amidated, or both, were synthesized, purified, characterized by several techniques, and probed for self-assembly, hydrogelation, and esterase-like biocatalysis. This work provides useful insights into how chemical modifications at the termini affect self-assembly into biocatalytic hydrogels, and these data may become useful for the future design of supramolecular catalysts for enhanced performance.

scholarly journals Self-replication of a quantum artificial organism driven by single-photon pulses

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Daniel Valente
Keyword(s):  
Self Assembly ◽  
Artificial Life ◽  
Single Photon ◽  
Self Organization ◽  
Physical Systems ◽  
Self Organized ◽  
Living Organisms ◽  
A Chain ◽  
Thermodynamic Mechanism ◽  
Self Replication

AbstractImitating the transition from inanimate to living matter is a longstanding challenge. Artificial life has achieved computer programs that self-replicate, mutate, compete and evolve, but lacks self-organized hardwares akin to the self-assembly of the first living cells. Nonequilibrium thermodynamics has achieved lifelike self-organization in diverse physical systems, but has not yet met the open-ended evolution of living organisms. Here, I look for the emergence of an artificial-life code in a nonequilibrium physical system undergoing self-organization. I devise a toy model where the onset of self-replication of a quantum artificial organism (a chain of lambda systems) is owing to single-photon pulses added to a zero-temperature environment. I find that spontaneous mutations during self-replication are unavoidable in this model, due to rare but finite absorption of off-resonant photons. I also show that the replication probability is proportional to the absorbed work from the photon, thereby fulfilling a dissipative adaptation (a thermodynamic mechanism underlying lifelike self-organization). These results hint at self-replication as the scenario where dissipative adaptation (pointing towards convergence) coexists with open-ended evolution (pointing towards divergence).

scholarly journals Long chain sphingomyelin depletes cholesterol from the cytoplasmic leaflet in asymmetric lipid membranes

RSC Advances ◽  
2021 ◽  
Vol 11 (37) ◽  
pp. 22677-22682
Author(s):  
Maria Lyngby Karlsen ◽  
Dennis S. Bruhn ◽  
Weria Pezeshkian ◽  
Himanshu Khandelia
Keyword(s):  
Outer Membrane ◽  
Lipid Membranes ◽  
Acyl Chain ◽  
Outer Membrane Leaflet ◽  
Long Chain

Long acyl chain sphingomyelin and saturated phospholipid tails in the outer membrane leaflet deplete cholesterol from the inner leaflet in mammalian membranes.

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.

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.

scholarly journals Self-assembly of hierarchically ordered structures in DNA nanotube systems

2016 ◽  
Vol 18 (5) ◽  
pp. 055001 ◽  
Author(s):  
Martin Glaser ◽  
Jörg Schnauß ◽  
Teresa Tschirner ◽  
B U Sebastian Schmidt ◽  
Maximilian Moebius-Winkler ◽  
...  
Keyword(s):  
Self Assembly ◽  
Ordered Structures ◽  
Dna Nanotube

scholarly journals Bilayer graphene oxide membranes for a wearable hemodialyzer

2020 ◽  
Author(s):  
Richard P. Rode ◽  
Henry H. Chung ◽  
Hayley N. Miller ◽  
Thomas R. Gaborski ◽  
Saeed Moghaddam
Keyword(s):  
Graphene Oxide ◽  
Cytochrome C ◽  
Self Assembly ◽  
Bilayer Membrane ◽  
Blood Proteins ◽  
High Mechanical Strength ◽  
Practical Applications ◽  
New Process ◽  
Improved Performance ◽  
Oxide Membranes

2D nanomaterials have long been considered for development of ultra-high throughput membranes, due to their atomically thin nature and high mechanical strength. However, current processes have yet to yield a viable membrane for practical applications due to the lack of scalability and substantially improved performance over existing membranes. Herein, a graphene oxide (GO) bilayer membrane with a permeability of 1562 mL/hr.mmHg.m2, two orders of magnitude higher than existing nanofiltration membranes, and a tight molecular weight cut-off (MWCO) is presented. To build such a membrane, we have developed a new process involving self-assembly and optimization of GO nanoplatelets physicochemical properties. The process produced a highly organized mosaic of nanoplatelets enabling ultra-high permeability and selectivity with only three layers of GO. Performance of the membrane has been evaluated in a simulated hemodialysis application, where it presents a great value proposition. The membrane has a precise molecular cut-off size of 5 nm, adjusted using a molecular interlinker, designed to prevent loss of critical blood proteins. Urea, cytochrome-c, and albumin are used as representative test molecules. Urea and cytochrome-c sieving coefficients of 0.5 and 0.4 were achieved under physiological pressure conditions, while retaining 99% of albumin. Hemolysis, complement activation, and coagulation studies exhibit a performance on par or superior to the existing hemodialyzer materials.

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