The effect of ion pairs on coacervate-driven self-assembly of block polyelectrolytes

2021 ◽  
Vol 154 (14) ◽  
pp. 144903
Author(s):  
Jiadi Jiang ◽  
Er-Qiang Chen ◽  
Shuang Yang
Keyword(s):  
2010 ◽  
Vol 288 (14-15) ◽  
pp. 1351-1357 ◽  
Author(s):  
Kadla R. Rosholm ◽  
Alfredo González-Pérez ◽  
Ole G. Mouritsen

2001 ◽  
Vol 79 (5-6) ◽  
pp. 964-976 ◽  
Author(s):  
Kamaluddin Abdur-Rashid ◽  
Alan J Lough ◽  
Robert H Morris

The hexahydridobis(phosphine)rhenate anions, [ReH6(PR3)2]- (PR3 = PCy3, P-i-Pr3, PPh3, PMe3) were generated by potassium hydride deprotonation of the neutral heptahydride conjugate acids (ReH7(PR3)2), isolated as their [K(18-crown-6)]+ and [K(1,10-diaza-18-crown-6)]+ salts, and characterized by NMR and IR spectroscopy and elemental analyses. Structures from single crystal X-ray diffraction were obtained for the [K(1,10-diaza-18-crown-6)]+salts and these indicate the presence of short protonic—hydridic bonds involving the hydrides of the anions and the proton donor NH moieties of the cations. The structure of [K(1,10-diaza-18-crown-6)][ReH6(P-i-Pr3)2] adopts a one-dimensional zigzag chain with alternating cations and anions connected and held together by inter-ion N-H···Hx-Re interactions (x = 1 or 2). Short distances between the NH protons of the cations and hydrides of the anion ranging from 1.6 to 1.9 Å are estimated for this complex. A different kind of chain structure is observed for [K(1,10-diaza-18-crown-6)][ReH6(PMe3)2] in which the combined effects of inter-ion protonic—hydridic bonding (N-H···Hx-Re) and inter-ion electrostatic interactions (ReH-x···K+···H-xRe), result in one-dimensional networks of alternating cations and anions, with the metals and hydrides occupying the interior and the organic moieties of the phosphine ligands and crown ether lining the exterior of cylindrical supramolecular assemblies. A combination of intra- and inter-ion protonic-hydridic and intra-ion-pair electrostatic interactions in [K(1,10-diaza-18-crown-6)][ReH6(PPh3)2] result in the formation of discrete two-dimensional {[K(1,10-diaza-18-crown-6)][ReH6(PPh3)2]}4 tetramers. The PCy3 salt is disordered but appears to consist of isolated 1:1 ion pairs containing strong intra-ion-pair NH···HRe bonding. The solid-state IR spectra of the [K(1,10-diaza-18-crown-6)]+ salts show low-frequency shifts for the NH bands relative to [K(1,10-diaza-18-crown-6)][BPh4], and perturbed Re-H bands relative to those in the [K(18-crown-6)]+ salts. The magnitude of ΔνNH is related to the basicity of the anion as indicated by the pKαTHF of the conjugate acid form (ReH7(PR3)2), which increases as PPh3 < < PMe3 < P-i-Pr3 < PCy3. Solution 1H NMR, NOE, and T1 relaxation measurements of [K(1,10-diaza-18-crown-6)][ReH6(PPh3)2] indicate that these interactions also persist in toluene solutions of this compound.Key words: rhenium, hydride, phosphine, hydrogen bonding, self-assembly.


2014 ◽  
Vol 53 (19) ◽  
pp. 10039-10041 ◽  
Author(s):  
Marie-Pierre Santoni ◽  
Amlan K. Pal ◽  
Daniel Chartrand ◽  
Garry S. Hanan ◽  
Pierre Ménard-Tremblay ◽  
...  
Keyword(s):  

2017 ◽  
Vol 53 (79) ◽  
pp. 10934-10937 ◽  
Author(s):  
J. S. McNally ◽  
X. P. Wang ◽  
C. Hoffmann ◽  
A. D. Wilson

Select tertiary ammonium bicarbonates self-assemble assisted by the first bicarbonate like-charge hydrogen-bonded ion pairs documented in an aqueous solution.


Author(s):  
D. Reis ◽  
B. Vian ◽  
J. C. Roland

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.


Author(s):  
M. Kessel ◽  
R. MacColl

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.


Author(s):  
Alan S. Rudolph ◽  
Ronald R. Price

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.


Author(s):  
M. Sarikaya ◽  
J. T. Staley ◽  
I. A. Aksay

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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