Synthesis and Photo-responsive Self-Assembly of Azobenzene-Containing Molecular Brushes

Three-component molecular brushes with a polyimide backbone and amphiphilic block copolymer side chains with different contents of the “inner” hydrophilic (poly(methacrylic acid)) and “outer” hydrophobic (poly(methyl methacrylate)) blocks were synthesized and characterized by molecular hydrodynamics and optics methods in solutions of chloroform, dimethylformamide, tetrahydrofuran and ethanol. The peculiarity of the studied polymers is the amphiphilic structure of the grafted chains. The molar masses of the molecular brushes were determined by static and dynamic light scattering in chloroform in which polymers form molecularly disperse solutions. Spontaneous self-assembly of macromolecules was detected in dimethylformamide, tetrahydrofuran and ethanol. The aggregates size depended on the thermodynamic quality of the solvent as well as on the macromolecular architectural parameters. In dimethylformamide and tetrahydrofuran, the distribution of hydrodynamic radii of aggregates was bimodal, while in ethanol, it was unimodal. Moreover, in ethanol, an increase in the poly(methyl methacrylate) content caused a decrease in the hydrodynamic radius of aggregates. A significant difference in the nature of the blocks included in the brushes determines the selectivity of the used solvents, since their thermodynamic quality with respect to the blocks is different. The macromolecules of the studied graft copolymers tend to self-organization in selective solvents with formation of a core–shell structure with an insoluble solvophobic core surrounded by the solvophilic shell of side chains.

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Synthesis of Hetero-Grafted Amphiphilic Diblock Molecular Brushes and Their Self-Assembly in Aqueous Medium

Macromolecules ◽

10.1021/ma902513n ◽

2010 ◽

Vol 43 (3) ◽

pp. 1182-1184 ◽

Cited By ~ 114

Author(s):

Zhou Li ◽

Jun Ma ◽

Chong Cheng ◽

Ke Zhang ◽

Karen L. Wooley

Keyword(s):

Aqueous Medium ◽

Self Assembly ◽

Molecular Brushes

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Synthesis and Self-assembly of Amphiphilic Hetero-arm Molecular Brushes

Australian Journal of Chemistry ◽

10.1071/ch11213 ◽

2011 ◽

Vol 64 (8) ◽

pp. 1100 ◽

Cited By ~ 8

Author(s):

Waled Hadasha ◽

Mpho Mothunya ◽

Niels Akeroyd ◽

Bert Klumperman

Keyword(s):

Self Assembly ◽

Ring Opening ◽

Alkyl Chain ◽

Ring Closure ◽

Molecular Brushes ◽

Alkyl Amines ◽

Ring Opening Reaction ◽

Grafting From ◽

Chain Lengths

We report the synthesis of amphiphilic hetero-arm molecular brushes (AMBs), which were prepared by a combination of ‘grafting from’ and ‘grafting onto’ methodologies. First, styrene-terminated polyethylene glycol macromonomer (VB-PEG12, ∼666 g mol–1) was copolymerized with maleic anhydride (MAnh) to yield a polymer containing hydrophilic PEG chains and reactive (MAnh) groups. Subsequently, the reactive MAnh units in the obtained polymer were modified via a ring-opening reaction using primary alkyl amines, with different alkyl chain lengths, as the nucleophile. In situ ring closure yielded the styrene–maleimide-based AMB. The amphiphilic character of the AMBs was used for their self-assembly in different solvents. The effect of the ratio in hydrophilic to hydrophobic graft length on the morphology of the assemblies was studied using scanning electron microscopy.

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Synthesis and self-assembly of amphiphilic heterografted molecular brushes prepared by telomerization

European Polymer Journal ◽

10.1016/j.eurpolymj.2020.110080 ◽

2020 ◽

Vol 141 ◽

pp. 110080 ◽

Cited By ~ 1

Author(s):

Coralie Teulère ◽

Chirine Ben-Osman ◽

Christine Barry ◽

Renaud Nicolaÿ

Keyword(s):

Self Assembly ◽

Molecular Brushes

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Synthesis and self-assembly behavior of organic–inorganic macrocyclic molecular brushes composed of macrocyclic oligomeric silsesquioxane and poly(N-isopropylacrylamide)

RSC Advances ◽

10.1039/c4ra02624a ◽

2014 ◽

Vol 4 (54) ◽

pp. 28439-28450 ◽

Cited By ~ 6

Author(s):

Yulin Yi ◽

Sixun Zheng

Keyword(s):

Self Assembly ◽

Molecular Brushes ◽

Assembly Behavior ◽

Oligomeric Silsesquioxane

Macrocyclic molecular brushes composed of macrocyclic oligomeric silsesquioxanes and poly(N-isopropylacrylamide) were synthesized via the ATRP approach; they displayed self-assembly behavior.

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In vitro and in vivo polysaccharides assembly: ultrastructural and cytochemical study of growing plant cell wall components.

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100083035 ◽

1978 ◽

Vol 36 (2) ◽

pp. 434-435

Author(s):

D. Reis ◽

B. Vian ◽

J. C. Roland

Keyword(s):

Cell Wall ◽

Self Assembly ◽

Plant Cell Wall ◽

Higher Plants ◽

Three Dimensional ◽

Cytochemical Study ◽

Wall Components

Wall morphogenesis in higher plants is a problem still open to controversy. Until now the possibility of a transmembrane control and the involvement of microtubules were mostly envisaged. Self-assembly processes have been observed in the case of walls of Chlamydomonas and bacteria. Spontaneous gelling interactions between xanthan and galactomannan from Ceratonia have been analyzed very recently. The present work provides indications that some processes of spontaneous aggregation could occur in higher plants during the formation and expansion of cell wall.Observations were performed on hypocotyl of mung bean (Phaseolus aureus) for which growth characteristics and wall composition have been previously defined.In situ, the walls of actively growing cells (primary walls) show an ordered three-dimensional organization (fig. 1). The wall is typically polylamellate with multifibrillar layers alternately transverse and longitudinal. Between these layers intermediate strata exist in which the orientation of microfibrils progressively rotates. Thus a progressive change in the morphogenetic activity occurs.

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The Nature of Rapidly Extracted Phycocyanin from the Blue-Green Alga Plectonema Boryanum

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100065870 ◽

1971 ◽

Vol 29 ◽

pp. 366-367

Author(s):

M. Kessel ◽

R. MacColl

Keyword(s):

Self Assembly ◽

Analytical Ultracentrifugation ◽

Uranyl Acetate ◽

The Self ◽

Major Protein ◽

Subunit Structure ◽

Blue Green Alga ◽

Thin Sections ◽

Blue Green Algae ◽

Cacodylate Buffer

The major protein of the blue-green algae is the biliprotein, C-phycocyanin (Amax = 620 nm), which is presumed to exist in the cell in the form of distinct aggregates called phycobilisomes. The self-assembly of C-phycocyanin from monomer to hexamer has been extensively studied, but the proposed next step in the assembly of a phycobilisome, the formation of 19s subunits, is completely unknown. We have used electron microscopy and analytical ultracentrifugation in combination with a method for rapid and gentle extraction of phycocyanin to study its subunit structure and assembly.To establish the existence of phycobilisomes, cells of P. boryanum in the log phase of growth, growing at a light intensity of 200 foot candles, were fixed in 2% glutaraldehyde in 0.1M cacodylate buffer, pH 7.0, for 3 hours at 4°C. The cells were post-fixed in 1% OsO4 in the same buffer overnight. Material was stained for 1 hour in uranyl acetate (1%), dehydrated and embedded in araldite and examined in thin sections.

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Video real-time imaging of artificial membranes during freeze-drying by cryo-electron microscopy

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s042482010010216x ◽

1988 ◽

Vol 46 ◽

pp. 16-17

Author(s):

Alan S. Rudolph ◽

Ronald R. Price

Keyword(s):

Real Time ◽

Self Assembly ◽

Freeze Drying ◽

Video Capture ◽

Drying Process ◽

Artificial Membranes ◽

The Past ◽

Cryo Electron Microscopy ◽

Spherical Structures ◽

Capture Techniques

We have employed cryoelectron microscopy to visualize events that occur during the freeze-drying of artificial membranes by employing real time video capture techniques. Artificial membranes or liposomes which are spherical structures within internal aqueous space are stabilized by water which provides the driving force for spontaneous self-assembly of these structures. Previous assays of damage to these structures which are induced by freeze drying reveal that the two principal deleterious events that occur are 1) fusion of liposomes and 2) leakage of contents trapped within the liposome [1]. In the past the only way to access these events was to examine the liposomes following the dehydration event. This technique allows the event to be monitored in real time as the liposomes destabilize and as water is sublimed at cryo temperatures in the vacuum of the microscope. The method by which liposomes are compromised by freeze-drying are largely unknown. This technique has shown that cryo-protectants such as glycerol and carbohydrates are able to maintain liposomal structure throughout the drying process.

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Biomimetic materials: An introduction

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100129735 ◽

1992 ◽

Vol 50 (2) ◽

pp. 1020-1021 ◽

Cited By ~ 1

Author(s):

M. Sarikaya ◽

J. T. Staley ◽

I. A. Aksay

Keyword(s):

Self Assembly ◽

Structural Control ◽

Hierarchical Structures ◽

Ceramic Composites ◽

Advanced Materials ◽

Length Scale ◽

Spider Webs ◽

Biomimetic Materials ◽

Synthetic Materials ◽

All Ceramic

Biomimetics is an area of research in which the analysis of structures and functions of natural materials provide a source of inspiration for design and processing concepts for novel synthetic materials. Through biomimetics, it may be possible to establish structural control on a continuous length scale, resulting in superior structures able to withstand the requirements placed upon advanced materials. It is well recognized that biological systems efficiently produce complex and hierarchical structures on the molecular, micrometer, and macro scales with unique properties, and with greater structural control than is possible with synthetic materials. The dynamism of these systems allows the collection and transport of constituents; the nucleation, configuration, and growth of new structures by self-assembly; and the repair and replacement of old and damaged components. These materials include all-organic components such as spider webs and insect cuticles (Fig. 1); inorganic-organic composites, such as seashells (Fig. 2) and bones; all-ceramic composites, such as sea urchin teeth, spines, and other skeletal units (Fig. 3); and inorganic ultrafine magnetic and semiconducting particles produced by bacteria and algae, respectively (Fig. 4).

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Interrelationship of the cellular distribution and secretion of regular structure (RS) protein in Bacillus licheniformis nm 105

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100123969 ◽

1992 ◽

Vol 50 (1) ◽

pp. 712-713

Author(s):

Xiaorong Zhu ◽

Richard McVeigh ◽

Bijan K. Ghosh

Keyword(s):

Alkaline Phosphatase ◽

Bacillus Licheniformis ◽

Self Assembly ◽

Gel Electrophoresis ◽

Culture Supernatant ◽

Regular Structure ◽

The Self ◽

Cellular Distribution ◽

Structural Protein ◽

Laboratory Cultures

A mutant of Bacillus licheniformis 749/C, NM 105 exhibits some notable properties, e.g., arrest of alkaline phosphatase secretion and overexpression and hypersecretion of RS protein. Although RS is known to be widely distributed in many microbes, it is rarely found, with a few exceptions, in laboratory cultures of microorganisms. RS protein is a structural protein and has the unusual properties to form aggregate. This characteristic may have been responsible for the self assembly of RS into regular tetragonal structures. Another uncommon characteristic of RS is that enhanced synthesis and secretion which occurs when the cells cease to grow. Assembled RS protein with a tetragonal structure is not seen inside cells at any stage of cell growth including cells in the stationary phase of growth. Gel electrophoresis of the culture supernatant shows a very large amount of RS protein in the stationary culture of the B. licheniformis. It seems, Therefore, that the RS protein is cotranslationally secreted and self assembled on the envelope surface.

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