A strategy for fabricating single layer graphene sheets based on a layer-by-layer self-assembly

A novel approach to synthesize graphene nanosheet is explored on the basis of the layer-by-layer (LbL) self-assembly of polyallylamine (PAA) and poly(styrene-sulfonate) (PSS) multi-layer with a metallic dopant.     

Electrochemical behavior of Au colloidal electrode through layer-by-layer self-assembly

Electrodes formed by Au colloidal nanoparticles have been obtained by layer-by-layer self-assembly using 1,6-hexanedithiol as cross-linkers. Cyclic voltammograms show that the peak-to-peak separation decreases as the number of Au colloidal layers increases. After seven layers of Au colloidal particles have been deposited, the multilayer electrodes have the electrochemical properties of metallic Au and show ideal microelectrode behavior. An equivalent circuit for the electrochemical impedance spectroscopy was established to model the working electrode. It is evident that by increasing the layer number of Au colloidals, the interfacial electron transfer is promoted, implying the electron-transfer process changes from a kinetically limited process to a diffusionally limited process.     

2]Pseudorotaxane and [2]rotaxane molecular shuttles: self-assembly through second-sphere coordination of thiocyanate ligands

A Pd(Py)(2)(SCN)(2) complex is shown to form a [2]pseudorotaxane complex with a macrocyclic tetralactam, which binds in the solid state through an unexpected complexation geometry. The intermolecular complexation is further applied to template the formation of a [2]rotaxane. The interlocked product acts as a degenerate molecular shuttle in solution, which is consistent with the co-conformation observed in the solid state.     

Preparation and layer-by-layer self-assembly of positively charged multiwall carbon nanotubes

The report described a method of more stably dispersing oxidized carbon nanotubes (CNTs) by forming complex with polycation and the layer-by-layer self-assembly behavior of the complex with polyanion was studied. The properties of the self-assembled multilayer film containing carbon nanotubes were studied. Cyclic voltammetry, UV-vis-NIR spectroscopy, electrochemical impedance spectroscopy and scanning electron microscopy were used for characterization of film assembly. UV-vis-NIR spectroscopy and cyclic voltammetry study indicated the uniform growth of the film. Electrochemical impedance spectroscopy results showed that incorporating of carbon nanotubes in the polyelectrolyte multilayers decreased in the electron-transfer resistance R_ct, indicating more favorable electrochemical reaction interface. The electrocatalytic property of the multilayer modified electrode to NADH was investigated mainly with different numbers of the bilayers and the results showed that along with the increase of the assembled bilayers the overpotential of NADH oxidation decreased. The detection limit could reach 6 μM at a detection potential of 0.4 V.     

Molecular layer-by-layer self-assembly of water-soluble perylene diimides through pi-pi and electrostatic interactions

A layer-by-layer deposition process has been carried out for two oppositely charged water-soluble perylene diimide dyes without the use of intervening polyelectrolyte layers. The strong pi-pi interactions between the perylene moieties help stabilize the layers and simultaneously diminish the fluorescence quantum yield of the array without strongly affecting the absorption or fluorescence spectra. There is an alternation of fluorescence intensity according to which perylene species is on the outer layer, which is interpreted as the effect of facile energy transfer between the perylenes.     

Triggering a [2]rotaxane molecular shuttle through hydrogen sulfide

A novel chemically-controlled [2]rotaxane molecular shuttle was successfully designed and synthesized. A H₂S-responsive bulk barrier was introduced between the two identical recognition stations of the [2]rotaxane to prevent dynamic shuttling of the macrocycle. Upon addition of H₂S, the complete intramolecular cascade reaction occurs in a controllable manner, resulting in removal of the bulk barrier and the shuttling motion of the macrocycle between the two stations recovers.     

Living photolytic ring-opening polymerization of amino-functionalized [1]ferrocenophanes: synthesis and layer-by-layer self-assembly of well-defined water-soluble polyferrocenylsilane polyelectrolytes

Facile synthetic routes have been developed that provide access to cationic and anionic water-soluble polyferrocenylsilane (PFS) polyelectrolytes with controlled molecular weight and narrow polydispersity. Living photolytic ring-opening polymerization of amino-functionalized [1]ferrocenophane (fc) monomers [fcSiMe{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)}] (3), [fcSi{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)}(2)] (10), [fcSiMe(C[triple chemical bond]CCH(2)NMe(2))] (14), and [fcSiMe(p-C(6)H(4)CH(2)NMe(2))] (20) yielded the corresponding polyferrocenylsilanes [(fcSiMe{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)})(n)](5), [(fcSi{C[triple chemical bond]CCH(2)N(SiMe(2)CH(2))(2)}(2))(n)] (11), [{fcSiMe(C[triple chemical bond]CCH(2)NMe(2))}(n)] (15), and [{fcSiMe(p-C(6)H(4)CH(2)NMe(2))}(n)] (21) with controlled architectures. Further derivatization of 5, 15, and 21 generated water-soluble polyelectrolytes [(fcSiMe{C[triple chemical bond]CCH(2)N(CH(2)CH(2)CH(2)SO(3)Na)(2)})(n)] (6), [{fcSiMe(C[triple chemical bond]CCH(2)NMe(3)OSO(3)Me)}(n)] (7), and [{fcSiMe(p-C(6)H(4)CH(2)NMe(3)OSO(3)Me)}(n)] (22), respectively. The polyelectrolytes were readily soluble in water and NaCl aqueous solutions, with 6 and 22 exhibiting long-term stability in aqueous media. The PFS materials 6 and 22, have been utilized in the layer-by-layer (LbL) self-assembly of electrostatic superlattices. Our preliminary studies have indicated that films made from controlled low molecular-weight PFSs possess a considerably thinner bilayer thickness and higher refractive index than those made from PFSs that have an uncontrolled high molecular-weight. These results suggest that the structure and optical properties of LbL ultra-thin films can be tuned by varying polyelectrolyte chain length. The water-soluble low molecular weight PFSs are also useful materials for a range of applications including LbL self-assembly in highly confined spaces.     

Surface modification of cellulose fibers with layer-by-layer self-assembly of lignosulfonate and polyelectrolyte: effects on fibers wetting properties and paper strength

To convert the hydrophilic cellulose fiber into hydrophobic, multilayers composed of cationic polyacrylamide (CPAM) and lignosulfonate (LS) were constructed on cellulose fiber surface using layer-by-layer (LBL) self-assembly technique. The presence of CPAM/LS multilayers were validated by zeta potential, X-ray photoelectron spectroscopy and atomic force microscopy (AFM). It was found that potential of fiber surface inversed after deposition of each layer, the contents of characteristic elements (i.e. S and N) of CPAM/LS multilayers increased with increasing bilayer number, furthermore, the calculated surface LS content increased linearly as a function of bilayers. AFM phase images indicated that the cellulose microfibrils on fiber surface were gradually covered by LS granules, resulting in an increase in fiber surface roughness as self-assembly proceeded. The wetting properties of modified cellulose fibers were detected by dynamic contact angle measurement. The results showed that the initial water contact angle gradually increased and the attenuation rate of the contact angle gradually decreased with the number of bilayers, suggesting that the controllable hydrophobicity of cellulose fiber can be achieved depending on the number of bilayers. It also showed that the polyelectrolyte presented in the outermost layer significantly influenced the wetting properties of cellulose fibers, and a higher hydrophobicity was observed when LS was in the outermost layer. Moreover, tensile strength test was performed on the handsheet prepared from LBL modified fibers to evaluate the effect of CPAM/LS multilayers on strength property of cellulose fiber networks. The tensile index of handsheet prepared from fibers modified with a (CPAM/LS)₅ multilayer increased by 12.4% compared with that of handsheet prepared from original fibers. The print density of handsheet increased with the number of bilayers, suggesting that printability of the handsheet was improved by constructing CPAM/LS multilayers on cellulose fiber surface. This strategy will have a positive impact and potential application value in printing process control of cellulose fiber-based products.     

Iodide-catalysed self-assembly of donor-acceptor [3]catenanes

Charged donor-acceptor [3]catenanes comprising the pi-accepting cyclobis(paraquat-4,4'-biphenylene) and pi-donating aromatic crown ether macrocycles have been prepared in high yields using thermodynamically controlled dynamic nucleophilic substitution.     

Para-acyl calix[4]arenes: amphiphilic self-assembly from the molecular to the mesoscopic level

Studies of the properties of a series of amphiphilic calixarenes show that they can form stable monolayers, Langmuir-Blodgett layers and solid lipid nanoparticles, the mesostructures were investigated by atomic force microscopy and the crystal structure of one compound shows a partially interdigitated tilted bilayer structure.     

Preparation of quaternary ammonium salts with a perhydroimidazo[1,5-c]oxazolium molecular skeleton

Russian Chemical Bulletin -     

Synthesis and self-assembly of novel oxacalix[2]arene[2]triazine amphiphiles

Heteracalixaromatics are an emerging generation of macrocyclic host molecules in supramolecular chemistry. As a typical example of heteracalixaromatics, oxacalix[2]arene[2]triazine adopts a shape-persistent 1,3-alternate conformation and can be easily functionalized. Taking it as a platform, a series of oxacalix[2]arene[2]triazine-based amphiphiles bearing long alkyl chains were synthesized through post-macrocyclization functionalization or 3+1 fragment coupling protocols. The self-assembly behavior of these amphiphiles in a mixture of tetrahydrofuran (THF) and water was investigated. Dynamic light scattering (DLS) measurements revealed that the size of the self-assembled aggregates is dependent on the structure of the amphiphiles. The long alkyl chain substituents and/or intermolecular hydrogen bonds were found to promote the self-assembly.     

A rigid bicyclo[3.3.0]octane (octahydropentalene): a heavily constrained novel aliphatic template for molecular self-assembly

This Letter reports the utility of a heavily constrained cis-fused bicyclo[3.3.0]octane (octahydropentalene) aliphatic template for effecting molecular self-assembly. An attractive feature of this system is its heavily constrained alicyclic backbone that would allow for the exploration of self-assembling systems with conformationally ordered features.     

Recognition through self-assembly. A quadruply-hydrogen-bonded, strapped porphyrin cleft that binds dipyridyl molecules and a [2]rotaxane

Quadruply-hydrogen-bonded porphyrin homodimer Zn1.Zn1 has been designed, assembled, and evaluated as a supramolecular cleft-featured receptor for its ability to bind dipyridyl guests in chloroform-d. Monomer Zn1 consists of a 2-ureidopyrimidin-4(1H)-one unit, which was initially reported by Meijer et al., and a zinc porphyrin unit. The zinc porphyrin is strapped with an additional aliphatic chain for controlling the atropisomerization of porphyrin. The 2-ureidopyrimidin-4(1H)-one unit dimerizes exclusively in chloroform even at the dilute concentration of 10(-)(4) M, while the two "strapped" zinc porphyrin units of the homodimer provide additional binding sites for selective guest recognition. (1)H NMR studies indicate that the new homodimer Zn1.Zn1 adopts an S-type conformation due to strong donor-acceptor interaction between the electron-rich porphyrin units and the electron-deficient 2-ureidopyrimidin-4(1H)-one unit. (1)H NMR, UV-vis, and vapor pressure osmometry investigations reveal that Zn1.Zn1 could function as a new generation of assembled supramolecular cleft, to be able to not only efficiently bind linear dipyridyl molecules 14-17, resulting in the formation of stable termolecular complexes, with K(aasoc) values ranging from 3.8 x 10(6) to 8.9 x 10(7) M(-)(1), but also strongly complex a hydrogen-bond-assembled [2]rotaxane, 18, which consists of a rigid fumaramide thread and a pyridine-incorporated tetraamide cyclophane, with K(aasoc) = 1.2 x 10(4) M(-)(1). (1)H NMR competition experiments reveal that complexation to the dipyriyl guests also promotes the stability of the quadruply-hydrogen-bonded dimeric receptor.     

Preparation of Au/Ag multilayers via layer-by-layer self-assembly in spherical polyelectrolyte brushes and their catalytic activity

Spherical polyelectrolyte brushes(SPBs) consisting of polystyrene(PS) core and poly(2-aminoethyl methacrylate hydrochloride)(PAEMH) shell were prepared by photo-emulsion polymerization. Au nanoparticles(Au-NPs) with controlled size and size distribution were synthesized in situ using SPBs as nanoreactors. Via layer-by-layer deposition technique on the surface of SPBs, nano-composite particles with Au/Ag-NPs bilayer and Au/Ag/Au-NPs trilayer were prepared. The structures of the as-prepared Au/Ag multilayer SPBs were characterized by UV-Vis spectroscopy, TEM, ICP-AES and DLS. The charge reversal of the nano-composite particles observed by zeta potential confirmed the success of layer-by-layer assembly. The Au/Ag-NPs bilayer nano-composite particles showed high catalytic efficiency with an apparent activation energy of about 41.2 k J/mol in the reduction reaction of 4-nitrophenol to 4-aminophenol in the existence of sodium borohydride monitored. The catalytic activity of Au/Ag-NPs multilayer SPBs close to that of Au-NPs SPBs and much higher than that of Ag-NPs SPBs reveals its potential applications in cost-effective catalysts with high-performance.     

Synthesis and self-assembly of novel calix[4]arenocrowns: formation of calix[4]areno[2]catenanes

A series of novel calix[4]arenocrowns 1a-c were efficiently synthesized by a one-pot reaction of calix[4]monohydroquinone diacetate 5 with ditosylate 6 and its analogues in the presence of sodium hydroxide. It was found that the calix[4]arenocrowns could form stable pseudorotaxane-type complexes 2a-c with paraquat, and further self-assemble into calix[4]areno[2]catenanes 3a-c with dicationic salt 8 and p-bis(bromomethyl)benzene.