Substrate-induced modulation of the Raman scattering signals from self-assembled organic nanometric films

Raman scattering signals recorded by microscopy from organic self-assembled monolayers (thin nanometric films of calibrated thickness) on silica substrates were found to be much stronger than those obtained from identical films assembled on bulk silicon substrates. This effect, observed in the backscattering geometry, is shown to result from interferences between the direct and reflected beams (including both the excitation and scattered radiation) in front of a smooth reflecting surface. Strong dependence of the effect on the distance between the sampled monolayer and the bulk silicon substrate allows enhancement of the Raman signals of organic monolayer films on silicon by factors up to approximately 70 by using appropriate silica spacers. The dependence of the Raman signal intensity on film thickness was also studied for thicker nanometric films comprising a series of self-assembled organosilane multilayers on bulk silicon and fused silica substrates, and the predicted deviation from linearity in the case of the silicon substrate is experimentally confirmed.     

Formation of self-aggregated structures of different types in water of chiral polymerizable amphiphiles from L-tyrosine and L-phenylalanine

Sodium salts of maleamic acid derivatives from lauryl esters of L-tyrosine (MTNa) and L-phenylalanine (MPNa) were synthesized and characterized. The aggregated structures of MTNa and MPNa in water were investigated, employing several independent methods. MPNa showed secondary aggregated structures in contrast to MTNa at concentrations of >1 × 10(-3) M. The results from dynamic light scattering, transmittance, conductivity, and viscosity measurements suggested the formation of aggregated structures of different types in MTNa and MPNa solutions. The measured fluorescence anisotropy (r) at 0.180 of the fluoroprobe, 1,6-diphenyl-1,3,5-hexatriene (DPH), and the d spacing of 38 ? from small-angle X-ray diffraction (SAXD) experiments confirmed the bilayer structures in MPNa. Scanning electron microscope (SEM) images provided the morphological features. The emulsion produced using MPNa solution was more stable. The confocal fluorescence microscopy image of the emulsion from MPNa confirmed the entrapment of water-soluble dye, rhodamine. The models of MTNa and MPNa molecules and the aggregated structures are presented.     

Unraveling the mechanism of nanotube formation by chiral self-assembly of amphiphiles

The self-assembly of nanotubes from chiral amphiphiles and peptide mimics is still poorly understood. Here, we present the first complete path to nanotubes by chiral self-assembly studied with C(12)-β(12) (N-α-lauryl-lysyl-aminolauryl-lysyl-amide), a molecule designed to have unique hybrid architecture. Using the technique of direct-imaging cryo-transmission electron microscopy (cryo-TEM), we show the time-evolution from micelles of C(12)-β(12) to closed nanotubes, passing through several types of one-dimensional (1-D) intermediates such as elongated fibrils, twisted ribbons, and coiled helical ribbons. Scattering and diffraction techniques confirm that the fundamental unit is a monolayer lamella of C(12)-β(12), with the hydrophobic tails in the gel state and β-sheet arrangement. The lamellae are held together by a combination of hydrophobic interactions, and two sets of hydrogen-bonding networks, supporting C(12)-β(12) monomers assembly into fibrils and associating fibrils into ribbons. We further show that neither the "growing width" model nor the "closing pitch" model accurately describe the process of nanotube formation, and both ribbon width and pitch grow with maturation. Additionally, our data exclusively indicate that twisted ribbons are the precursors for coiled ribbons, and the latter structures give rise to nanotubes, and we show chirality is a key requirement for nanotube formation.     

High temperature oxidation of chromium with nanometric ceria sol-gel coating

Isothermal oxidation behavior of chromium with and without nanometric sol-gel CeO2 coating is studied at 1000℃ in air. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to examine the surface morphology and microstructure of their oxide films. It is found that ceria coating greatly improves the anti-oxidation property of chromium. Laser Raman spectrometer and X-ray diffraction spectrometer (XRD) are also used to study the stress level in oxide films formed on ceria-coated and ceria-free Cr. The difference in oxidation behavior is mainly attributed to the fact that ceria greatly reduces the growth speed and grain size of Cr2O3 film, and this fine grain-sized Cr2O3 film probably has better high temperature plasticity, i.e. oxide film can relieve parts of compressive stress by means of creeping. XRD and Raman testing results both show the stress declination due to nano-CeO2 application, and their deviation is analyzed concerning to the rare earth effect.     

Asymmetric synthesis of (alpha-amino)phosphonic acid amphiphiles using chiral P-H spirophosphoranes

Chiral P-H spirophosphoranes reacted with long-chain prochiral aldimines and, after selective hydrolysis, afforded (alpha-amino)phosphonic acid amphiphiles in both enantiopure forms.     

Chiral mesoporous silica: chiral construction and imprinting via cooperative self-assembly of amphiphiles and silica precursors

Fabrication of chiral materials and revealing the mechanisms involved in their formation are crucial issues in scientific research. The combination of cooperative self-assembly routes and the chiral templating process favors the formation of inorganic chiral materials with highly ordered mesostructures. This tutorial review highlights the recent research on chiral mesoporous silica (CMS) of hierarchical helical constructions transcribed from organic templates. The rules and mechanisms involved in the synthesis of CMS and related materials, especially the novel expression of chirality and imprinting of helical micellar superstructure by the functional groups immobilized on the mesopore surface, provide us with a deeper insight into the chiral self-assembly process and new strategies for the design and application of chiral materials. This review is addressed to researchers and students interested in chiral chemistry, supramolecular chemistry and mesoporous materials (53 references).     

Counterion condensation on charged spheres, cylinders, and planes

We use the framework of counterion condensation theory, in which deviations from linear electrostatics are ascribed to charge renormalization caused by collapse of counterions from the ion atmosphere, to explore the possibility of condensation on charged spheres, cylinders, and planes immersed in dilute solutions of simple salt. In the limit of zero concentration of salt, we obtain Zimm-Le Bret behavior: a sphere condenses none of its counterions regardless of surface charge density, a cylinder with charge density above a threshold value condenses a fraction of its counterions, and a plane of any charge density condenses all of its counterions. The response in dilute but nonzero salt concentrations is different. Spheres, cylinders, and planes all exhibit critical surface charge densities separating a regime of counterion condensation from states with no condensed counterions. The critical charge densities depend on salt concentration, except for the case of a thin cylinder, which exhibits the invariant criticality familiar from polyelectrolyte theory.     

Design, synthesis and characterisation of guanosine-based amphiphiles

A small library of sugar-modified guanosine derivatives has been prepared, starting from a common intermediate, fully protected on the nucleobase. Insertion of myristoyl chains and of diverse hydrophilic groups, such as an oligoethylene glycol, an amino acid or a disaccharide chain, connected through in vivo reversible ester linkages, or of a charged functional group provided different examples of amphiphilic guanosine analogues, named G1-G7 herein. All of the sugar-modified derivatives were positive in the potassium picrate test, showing an ability to form G-tetrads. CD spectra demonstrated that, as dilute solutions in CHCl(3), distinctive G-quadruplex systems may be formed, with spatial organisations dependent upon the structural modifications. Two compounds, G1 and G2, proved to be good low-molecular-weight organogelators in polar organic solvents, such as methanol, ethanol and acetonitrile. Ion transportation experiments through phospholipid bilayers were carried out to evaluate their ability to mediate H(+) transportation, with G5 showing the highest activity within the investigated series. Moreover, G3 and G5 exhibited a significant cytotoxic profile against human MCF-7 cancer cells in in vitro bioassays.     

Synthesis, characterization, and applications of hemifluorinated dibranched amphiphiles

Here we describe the synthesis and the physicochemical and preliminary pharmaceutical assessment of a novel class of hemifluorinated dibranched derivatives: M(1)diH(x)F(y). These compounds have the remarkable ability to completely stop the Ostwald ripening commonly associated with nanoemulsions. The developed synthesis is modular and allows easy incremental structural variations in the fluorophilic (fluorous chains), lipophilic (alkyl spacer head), and hydrophilic (polar head) domains. Furthermore, the synthesis can be easily scaled up and highly pure compounds can be readily obtained through silica gel and fluoro-silica gel column chromatography, without any need to use HPLC or other time-consuming techniques. Surface properties such as micelle formation, critical aggregation concentration (CAC), and emulsion stability studies demonstrated the different behavior of the dibranched hemifluorinated surfactant M(1)diH(x)F(y) with respect to that of single-chain semifluorinated analogues M(z)F(y). Remarkably, the new polymer M(1)diH(3)F(8) drastically slowed the ripening of nanoemulsions of the commonly used fluorinated anesthetic sevoflurane over a period of more than 1 year. During this time, the nanodroplet size did not increase to more than 400 nm. This result is very promising for inducing and maintaining general anesthesia through intravenous delivery of volatile anesthetics, eliminating the need for the use of large and costly vaporizers in the operating room.     

Gemini imidazolium amphiphiles for the synthesis, stabilization, and drug delivery from gold nanoparticles

Gold nanoparticles (AuNPs) are considered useful vehicles for medical therapy and diagnosis. Despite the progress made in this field, there is need to find direct, reliable, and versatile synthetic procedures for their preparation as well as new multifunctional coating agents. In this sense, we have explored the use of imidazolium amphiphiles to prepare new AuNPs designed for anion recognition and transport. Thus, in this work we describe (a) the synthesis, by a phase transfer method, of new gold nanoparticles using gemini-type surfactants as ligands based on imidazolium salts, those ligands acting as transfer agents into organic media and also as nanoparticle stabilizers, (b) the examination of their stability in solution, (c) the chemical and physical characterization of the nanoparticles, using a variety of techniques, including UV-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), (d) toxicity data concerning both the imidazolium ligands and the imidazolium coated nanoparticles, (e) the assessment of their molecular recognition ability toward molecules of biological interest, such as anions and carboxylate containing model drugs, such as ibuprofen, (f) the study of their toxicity and those of their coating ligands, as well as their ability for cell internalization, and (g) the study of their ability for delivering anionic pharmaceuticals. The structurally governed triple role of those new gemini-type surfactants is responsible for the preparation, remarkable stability, and delivery properties of these functional AuNPs.     

High temperature oxidation of chromium with nanometric ceria sol–gel coating

Isothermal oxidation behavior of chromium with and without nanometric sol-gel CeO2 coating is studied at 1000℃ in air. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） are used to examine the surface morphology and microstructure of their oxide films. It is found that ceria coating greatly improves the anti-oxidation property of chromium. Laser Raman spectrometer and X-ray diffraction spectrometer （XRD） are also used to study the stress level in oxide films formed on ceria-coated and ceria-free Cr. The difference in oxidation behavior is mainly attributed to the fact that ceria greatly reduces the growth speed and grain size of Cr2O3 film, and this fine grain-sized Cr2O3 film probably has better high temperature plasticity, i.e. oxide film can relieve parts of compressive stress by means of creeping. XRD and Raman testing results both show the stress declination due to nano-CeO2 application, and their deviation is analyzed conceming to the rare earth effect.     

Elasticity of syndiotactic polypropylene: Insights from temperature and time dependence

The origin of the unusual and puzzling elasticity of drawn sPP samples was investigated. The mechanism responsible of the elasticity was studied for drawn samples characterized by a very simple structural organization, where there are no involvements of crystallographic modifications with different chain conformation. The elastic behavior of the drawn samples, valued through the hysteresis cycles, was determined at different temperatures. At room temperature the samples show remarkable elastic properties, whereas decreasing the temperature the elastic behavior becomes worse and worse, disappearing at temperatures lower than 0 °C. The elasticity also disappears in drawn samples after a long aging under tension. Thermomechanical and structural investigations, as well as shrinkage as a function of temperature and aging at room temperature of the fixed drawn samples, support the idea that the elastic behavior of sPP can be explained by the model of the plastic deformation of semicrystalline polymers. The interpretation is based on the presence of “tie” molecules axially connecting the crystals in the oriented samples, whose extension, chain conformation and/or crystallization determine the retractive stress of the oriented sample, as well as other mechanical properties. We show that many experiments on the drawn samples, either fixed or relaxed, are strictly connected to the morphology of the drawn sample, derived by the transition between the lamellar initial and the fibrillar final structure. By applying the model we can answer the questions derived from the experimental facts not yet well clarified, giving a new insight into the interesting elasticity of sPP.     

Stereospecific polymerization and chiral initiation,chiral crystallization and chiral nucleation

Helical macromolecules which are configurationally and conformationally specific can now be synthesized. Monomer structures must be selected that demand spacial restriction for monomer addition. High specificity of monomer addition during polymerization has parallels in crystallization of some inorganic salts from aqueous solution. Initiation of highly specific polymerizations with chiral initiators give helical polymers with substantial one-handedness. Nucleation of certain inorganic salts with chiral nucleating agents, the enantiomers of the salts produce enantiomerically pure chiral salts.     

Conformation and Counterion Distribution of Polyelectrolyte in Solution as Viewed from Dielectric Approach

Polyelectrolyte solutions are more variable than uncharged macromolecule due to electrical interaction between charged molecules and surrounding counterions.Therefore,the subject of polyelectrolyte solutions has attracted a wide range of interests in both basic and applied research,and has also been extensively explored.However,the understanding of the molecular dynamics and conformation of polyelectrolytes in solution remains to be deepened,and universal consensus on some key issues have not been reached.Many methods have contributed to solving the above problems in different ways,including dielectric relaxation spectroscopy(DRS).In this perspective,we briefly reviewed the his-tory of dielectric spectroscopic research on polyelectrolyte solution,with emphasis on summarizing our efforts.In particular,we expound the characteristics of DRS and its ability to obtain the internal information of the system of interest.Finally,we evaluate the advantages and limita-tions of the dielectric method and discussed future prospects of this field.     

One-pot synthesis of chiral azetidines from chloroaldehyde and chiral amines

A variety of chiral azetidinepiperidines have been synthesized utilizing an expedient one-pot union of piperidine chloroaldehyde with chiral amines. This two step one-pot procedure provides access to an interesting set of compounds that retain the chiral purity of the starting chiral amine.     

A temperature and pH double sensitive cholesteric polymer film from a photopolymerizable chiral hydrogen-bonded assembly

In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal (Ch-LC) monomers mixture containing a photopolymerizable chiral H-bonded assembly (PCHA). The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased, which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film. Additionally, the selective reflection band (SRB) of the cholesteric polymer film in solution with pH > 7 showed an obvious red shift with increasing pH values. While the SRB of the cholesteric polymer film in solutions with pH = 7 and pH < 7 hardly changed. This pH sensitivity in solutions with pH > 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by―OH and―K + ions in the alkaline solution. In contrast, it couldn’t happen in the neutral and acidic solutions. The cholesteric polymer film in this study can be used as optical/photonic papers, optical sensors and LCs displays, etc.     

Effect of alcohols and temperature on the direct chiral resolutions of fipronil, isocarbophos and carfentrazone-ethyl

The enantiomeric separations of three pesticides fipronil (asymmetric nitrogen), isocarbophos (asymmetric phosphorus) and carfentrazone-ethyl (asymmetric carbon) were studied on cellulose-tri(3,5-dimethylphenylcarbamate) chiral stationary phase using high-performance liquid chromatography under normal phase. The mobile phase was n-hexane with alcohols including ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol as polar modifiers. The flow rate was 1.0 mL/min with UV detection at 280, 225 and 230 nm for fipronil, isocarbophos and carfentrazone-ethyl respectively. The influence of the modifiers and their volume content and temperature from 0 to 50 degrees C on the separations was investigated. The chiral stationary phase showed excellent stereoselectivity for the two enantiomers of fipronil and isocarbophos and certain chiral recognition for carfentrazone-ethyl. Iso-propanol was more suitable for the chiral separation of isocarbophos and carfentrazone-ethyl, and iso-butanol was better for fipronil. The resolutions increased with the decreasing modifier content and temperature for all the three chiral pesticides.     

Interrelations between charging, structure and electrokinetics of nanometric polyelectrolyte films

Streaming current, surface conductivity and swelling data of poly(acrylic acid) (PAA) and poly(ethylene imine) (PEI) thin films are analyzed on the basis of the theory for diffuse soft interfaces (J.F.L. Duval, R. Zimmermann, A. L. Cordeiro, N. Rein, C. Werner, Langmuir 25 (2009) 10691). Focus is put on ways to unravel the electroosmotic and migration contributions of the measured surface conductivity, which is crucial for appropriate electrokinetic analysis of films carrying high densities of dissociable groups. Results demonstrate that the osmotically-driven swelling of the PAA films with increasing pH is accompanied by an increase in diffuseness for the interphasial polymer segment density distribution. This heterogeneity is particularly marked at low ionic strength with a non-monotonous dependence of the streaming current on pH and the presence of a maximum at pH～6.5. The analysis of the PEI films evidences heterogeneous swelling with lowering pH, i.e. upon protonation of the amine groups. The characteristic decay length in the interphasial PEI segment density distribution is found to be nearly independent of the pH, which is in line with the moderate swelling determined by ellipsometry. A critical discussion is given on the strengths and limitations of electrokinetics/surface conductivity for quantifying the coupled electrohydrodynamic and structural properties of moderately to highly swollen polyelectrolyte thin films.