Close-packed Molecules Research Articles

Photoswitching of 5-phenylazopyrimidines in crystalline powders and thin films

Solid-state photoswitching enables the development of smart materials. However, the close packing of molecules and the lack of free volume in this state prevent sterically demanding structural changes induced by irradiation, thereby precluding the use of azobenzene photoswitches. Nevertheless, we report here the solid-state photoswitching of their derivatives, 5-phenylazopyrimidines, in crystalline powders and in amorphous thin layers. After identifying trans-cis photoisomerization by NMR spectroscopy, we demonstrated the applicability of 5-phenylazopyrimidines for future all-optical switching applications. For this purpose, we prepared thin films by spin-coating and confirmed their solid-state optical switching by optical transmission spectroscopy and their favorable surface topography by atomic force microscopy. Therefore, thin films of 5-phenylazopyrimidines are suitable for on-chip integration for emerging all-optical technologies.

Macroscale Superlubricity and Polymorphism of Long-Chain n-Alcohols

Simple n-alcohols, such as 1-dodecanol, show anomalous film-forming and friction behaviors under elastohydrodynamic lubrication (EHL) conditions, as found inside bearings and gears. Using tribometer, diamond anvil cell (DAC), and differential scanning calorimetry (DSC) experiments, we show that liquid 1-dodecanol undergoes a pressure-induced solidification when entrained into EHL contacts. Different solid polymorphs are formed inside the contact depending on the temperature and pressure conditions. Surprisingly, at a moderate temperature and pressure, 1-dodecanol forms a polymorph that exhibits robust macroscale superlubricity. The DAC and DSC experiments show that superlubricity is facilitated by the formation of lamellar, hydrogen-bonded structures of hexagonally close-packed molecules, which promote interlayer sliding. This novel superlubricity mechanism is similar to that proposed for the two-dimensional materials commonly employed as solid lubricants, but it also enables the practical advantages of liquid lubricants to be maintained. When the pressure is increased, 1-dodecanol undergoes a polymorphic transformation into a phase that gives a higher friction. The DAC and DSC experiments indicate that the high-friction polymorph is an orthorhombic crystal. The polymorphic transformation pressure coincides with the onset of a dimple formation in the EHL films, revealing that the anomalous film shapes are caused by the formation of rigid orthorhombic crystals inside the contact. This is the first demonstration of a macroscale superlubricity in an EHL contact lubricated by a nonaqueous liquid that arises from bulk effects rather than tribochemical transformations at the surfaces. Since the superlubricity observed here results from phase transformations, it is continuously self-replenishing and is insensitive to surface chemistry and topology. This discovery creates the possibility of implementing superlubricity in a wide range of machine components, which would result in enormous improvements in efficiency and durability.

Phototriggered Guest Release from a Nonporous Organic Crystal: Remarkable Single-Crystal-to-Single-Crystal Transformation of a Binary Cocrystal Solvate to a Ternary Cocrystal.

The development of organic solids for applications in materials science requires a fundamental understanding of how close packing of molecules can affect structure and function. We report here nonporous organic crystals that release entrapped guest molecules upon application of UV light. We show components of binary cocrystal solvates to undergo an intermolecular photoreaction to generate ternary cocrystals that results in release of entrapped solvent molecules. The phototriggered guest release occurs in a single-crystal-to-single-crystal transformation that is in the absence pores and channels in the solid. The cocrystals are composed of a tetratopic hydrogen-bond-acceptor molecule synthesized in the solid state. The UV-light results in [2 + 2] photodimerization of an isocoumarin to generate a ternary cocrystal with cyclobutane molecules that support guest release.

Photochemically Induced Solid State Dimerisation of Resveratrol Analogues: A Greener Synthetic Process

The photochemical dimerisation of resveratrol analogues in the solid state to generate chiral phenyl substituted cyclobutanes is described. NMR spectroscopic and X-ray crystallographic methods have confirmed that the dimerisation leads to the head to tail orientation of the phenyl group substituents in the cyclobutane derivative. Interestingly, the parent compound, resveratrol, in the solid state, did not form a cyclobutane dimer, but the O-acetyl analogues gave the corresponding cyclobutane dimers in high yield, suggesting that the close packing of molecules together with the electron density through the conjugated double bond of the resveratrol structure are important determinants for photodimerisation to occur in the solid state.

Effect of adsorption of catanionic surfactant mixtures on wettability of quartz surface

The adsorption behaviors of dodecyl trimethyl ammonium bromide (C12TAB) and the catanionic mixtures of C12TAB with sodium dodecyl sulfate (SDS), sodium dodecyl sulfonate (SDDS) and sodium dodecanoate (DAS) on quartz surface have been investigated. Physicochemical parameters such as the critical micelle concentration (CMC), surface tension, contact angle, adhesional tension and work of adhesion have been estimated. At the interface of quartz and aqueous solution of catanionic mixture, there is a competition between anionic surfactants and quartz surface in attracting cationic surfactants. SDDS and DAS fail to inhibit the adsorption of C12TAB because of the smaller size and less negative charge of the head-groups, even the amount of anionic surfactants well surpasses that of C12TAB. Instead the anionic surfactants are dragged by cationic surfactants to quartz surface and form a mixed monolayer on the quartz surface. The insert of anionic surfactants reduces the repulsion between the cationic molecules and results in closer packing of molecules in adsorption layers. Thus, SDDS-C12TAB and DAS-C12TAB have displayed stronger hydrophobic modification at quartz surface than pure C12TAB. However, the electrostatic attraction between excessive SDS and C12TAB is strong enough to constrain C12TAB and decreases the adsorption on quartz surface. Only a small amount of catanionic complexes with the structure like zwitterionic surfactant adsorb on quartz through the interaction between the positive sites of surfactant complexes and negative sites of quartz. Over CMC, bilayers are formed on quartz surface in the systems of SDDS-C12TAB and DAS-C12TAB, while micelle structures are adsorbed on quartz surface for SDS-C12TAB.

The effect of polar end of long-chain fluorocarbon oligomers in promoting the superamphiphobic property over multi-scale rough Al alloy surfaces

Rough structures with re-entrant property and their subsequent surface energy reduction with long-chain fluorocarbon oligomers are both critical in developing superamphiphobic (SAP, i.e. both super hydrophobic and superoleophobic) surfaces. However, morphology of the low-surface energy layer on a rough re-entrant substrate can strongly depend on the fluorocarbon oligomers used. In this study, the effect of polar end of different kinds of long-chain fluorocarbon oligomers in promoting a self-assembled monolayer with close packed molecules and robust adhesion on multi-scale rough Al alloy surfaces was investigated. Hierarchical Al alloy surfaces with microgrooves and nanograss structures were developed by a simple combination of one-directional mechanical sanding and post treatment in boiling de-ionized water (DIW). Three types of long-chain fluorocarbon oligomers of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTS), 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (PFDCS), and perfluorooctanoic acid (PFOA) were chemically vaporized onto these rough Al alloy surfaces. The PFDCS exhibited the lowest surface free energy of less than 10mN/m. The contact angle and sliding angle measurements for water, ethylene glycol, and peanut oil verified the SAP property of hierarchical rough Al alloy surfaces treated with alkylsilane oligomers (PFDTS, PFDCS). However, the hierarchical surfaces treated with fluorocarbon oligomer with polar acidic tail (PFOA) showed highly amphiphobic properties but could not reach the threshold for SAP. Chemical stability of the hierarchical Al alloy surfaces treated with the fluorocarbon oligomers was tested under the harsh conditions of ultra-sonication in acetone and annealing at high temperature after different treatment times. Contact angle measurements revealed the robustness of the alkylsilane oligomers and deterioration of the PFOA coating particularly for low surface tension liquids. The robust adhesion and close-packing of the alkylsilane molecules as well as their vertical orientation with exposure of more CF3 groups instead of CF2 groups due to the polar silane-based tail are believed to be the main reasons behind their improved chemical stability. The selection of fluorocarbon oligomer with proper polar tail which can promote a self-assembled monolayer with close-packed molecules could make it possible for utilizing shorter fluorocarbon oligomers, which is environmentally favorable, to develop high surface energy materials with SAP properties.

Crystal structure of cis-diamminebis(nitrito-κN)platinum(II).

Single crystals of cis-[Pt(NO2)2(NH3)2], were obtained by means of hyper-saturation directly out of a plating electrolyte. The square-planar coordination environment of the divalent Pt(II) atom is formed by four N atoms belonging to two ammine and two monodentate nitrite ligands. The ligands adopt a cis configuration. The crystal structure contains stacks of close-packed mol-ecules which run parallel to [001]. There are nine crystallographically independent inter-molecular N-H⋯O hydrogen bonds, resulting in a hydrogen-bonded hxl-type framework in which each mol-ecule serves as an eight-connected node. Four of the nine distinct hydrogen bonds connect complexes which belong to the same close-packed column parallel to [001]. In contrast to the previously reported crystal structure of the trans isomer, the title structure does not display intra-molecular hydrogen bonding.

Morphological transition of a conductive molecular organization with non-covalent from nanonetwork to nanofiber

The formation of nanofiber morphology at a mesoscopic scale, and molecular level stacking of a tetrathiafulvalene (TTF) derivative with a chiral group were investigated by the one-dimensional growth method in interfacial molecular films. Monomolecular films of a TTF derivative with a chiral borneol group display a two-dimensional phase transition at the air/water interface. At high surface pressures, nanonetwork domains are formed, where the TTF molecular planes are densely packed with an interlayer distance of 4.1Å. The formation of this network is attributed to the organized aggregation of the TTF derivatives, which is a result of strong intermolecular interactions. Subsequently, the growth of morphology is encouraged by the application of the one-dimensional growth method at low surface pressure conditions, varying compression speeds, and subphase temperatures. At low surface pressure and a subphase temperature of 15°C, the TTF derivatives aggregated as nanofibers with close packing of molecules. Upon raising the subphase temperature, the thickness of the nanofibers was found to increase and hence, spontaneous morphogenesis at the air/water interface was achieved.

High-energy, stable and recycled molecular solar thermal storage materials using AZO/graphene hybrids by optimizing hydrogen bonds.

An important method for establishing a high-energy, stable and recycled molecular solar heat system is by designing and preparing novel photo-isomerizable molecules with a high enthalpy and a long thermal life by controlling molecular interactions. A meta- and ortho-bis-substituted azobenzene chromophore (AZO) is covalently grafted onto reduced graphene oxide (RGO) for solar thermal storage materials. High grafting degree and close-packed molecules enable intermolecular hydrogen bonds (H-bonds) for both trans-(E) and cis-(Z) isomers of AZO on the surface of nanosheets, resulting in a dramatic increase in enthalpy and lifetime. The metastable Z-form of AZO on RGO is thermally stabilized with a half-life of 52 days by steric hindrance and intermolecular H-bonds calculated using density functional theory (DFT). The AZO-RGO fuel shows a high storage capacity of 138 Wh kg(-1) by optimizing intermolecular H-bonds with a good cycling stability for 50 cycles induced by visible light at 520 nm. Our work opens up a new method for making advanced molecular solar thermal storage materials by tuning molecular interactions on a nano-template.

Effect of molecular packing of zinc(II) porphyrins on the performance of field-effect transistors

The charge-transport phenomena of organic conjugated materials have been intensively investigated because of the potential applications of these materials in electronics and optoelectronics. Among these applications, organic field-effect transistors (OFETs) fabricated from either thin films or well-defined single crystals as charge-transporting layers are the most promising electronic devices. In this work, the effect of molecular packing on the performance of OFETs is investigated through the fabrication and characterization of devices based on zinc(II) porphyrins TPZ and TBPZ. The field-effect mobility of the transistors is found to increase with decreasing intermolecular distance, attributable to greater overlap of π orbitals among close-packed molecules and thereby enhance the charge transport.

Acoustical and Compressibility Parameters of Glycylglycine−FeCl3in Aqueous Ethanol Mixture atT= (293.15, 303.15, and 313.15) K

Ultrasonic velocity measurement is a reliable procedure that allows quick and easy determination of solvent concentrations in mixtures. This paper presents data of ultrasonic velocities and isentropic compressibilities of (glycylglcyine−FeCl3) in aqueous ethanol mixture at T = (293.15, 303.15, and 313.15) K. Various acoustical parameters were calculated, because of their importance in the study of specific molecular interactions. A less-compressible phase of the fluid and a closer packing of molecules is observed with changes in the intermolecular free length. Quantitative investigation suggests that the mixing of ethanol with an aqueous glycylglycine−FeCl3 solution causes the rupture of hydrogen bonds, with increasing δκS and Lf values (where the former represents the change in isentropic compressibility and the latter represents the intermolecular free length). Theoretically computed values of isentropic compressibility in the studied mixture using different models indicate the superiority of the very complex procedure.

Molecular-packing-enhanced charge transport in organic field-effect transistors based on semiconducting porphyrin crystals

The effect of semiconductor crystal structure on the performance of organic field-effect transistors is investigated through the fabrication and characterization of devices based on single porphyrin crystals with different center metals. The field-effect mobility of the transistors is found to increase with decreasing intermolecular distance, attributable to greater overlap of π orbitals among close-packed molecules and the consequent promotion of charge transport.

Fabrication of Organic Thin Film Transistor(OTFT) Array by Using Nanoprinting Process

The flexible organic thin film transistor(OTFT) array to use as a switching device for an organic light emitting diode(OLED) was designed and fabricated in the nanocontact printing and low-temperature process. The gate, source, and drain electrode patterns of OTFT were fabricated by nanocontact printing process. And dielectric layer of parylene and organic active semiconductor layer of pentacene formed at room temperature or at a temperature lower than 40. The nanocontact printing process using SAM and PDMS stamp made it possible to fabricate OTFT arrays with channel lengths down to even submicron size, and reduced the fabrication process by 10 steps compared with photolithography. Since the process was done in room temperature, there was no pattern shrinkage, transformation, and bending problem appeared. Also, it was possible to improve electric field mobility, to decrease contact resistance, to increase close packing of molecules by SAM, and to reduce threshold voltage by using a parylene.

Light induced polymerization of resin composite restorative materials

Dimensional stability of polymer-based dental materials is compromised by polymerization reaction of the monomer. The conversion into a polymer is accompanied by a closer packing of molecules, which leads to volume reduction called curing contraction or polymerization shrinkage. Curing contraction may break the adhesion between the adhesive system and hard tooth tissues forming microgaps which may result in marginal deterioration, recurrent caries and pulp injury. POLYMERIZATION SHRINKAGE OF RESIN-BASED RESTORATIVE DENTAL MATERIALS: Polymerization of the organic phase (nonomer molecules) of resin-based dental materials causes shrinkage. The space occupied by filler particles is not associated with polymerization shrinkage. However, high filler loading within certain limits, can contribute to a lesser curing contraction. Polymerization shrinkage stress of polymer-based dental resins can be controlled in various ways. The adhesive bond in tooth-restoration interface guides the contraction forces to cavity walls. If leakage occurs, complications like secondary caries and pulpal irritation may jeopardize the longevity of a restoration. Stress relieve can be obtained by modifications of the monomer and photoinitiator, or by specially designed tooth preparation and application of bases and liners of low modulus of elasticity. The polymerization contraction can be compensated by water absorption due to oral cavity surrounding. The newest approach to stress relief is based on modulation of polymerization initiation. This work deals with polymerization contraction and how to achieve leak-proof restoration. Restorative techniques that may reduce the negative effect of polymerization shrinkage stress need further research in order to confirm up-to-date findings.

Comparative estimation of the efficiency of structure formation and dispersion interactions in organic solvents of varying nature and polarity

The solubilities of n-tetracosane and dotriacontane in more than 50 solvents (aliphatic and aromatic hydrocarbons, their halo derivatives, alcohols, ethers, ketones, amines, etc.) miscible with liquid aliphatic hydrocarbons were determined at 293±1 K. The increments of the methylene group in hypothetical extraction systems n-octane — solvent and the free energies of methylene group transfer from solvent to n-octane were calculated. The values were found to vary within wide limits. For the overwhelming majority of polar and low-polar solvents, the energies are negative due to self-association of solvents according to the type of spatial structure. Positive energies are due to the closer packing of some low-polar solvent molecules (carbon tetrachloride and cyclohexane) in the structure compared to octane and to the absence of molecular self-association. The closer packing of these molecules leads to higher efficiency of dispersion interactions between the solvents and paraffins compared to octane.

An X-ray reflectivity study of monolayers and bilayers of archae lipids on a solid substrate

Membranes of archaebacteria show some very interesting features, the most prominent being their stability at high temperatures. This property seems to be caused by the bipolar nature of the membrane lipids. The configuration of the lipid molecules in a monolayer of a native mixture of lipids extracted from Sulfolobus solfataricus has been studied by X-ray reflectivity of samples on solid substrates. Films on substrate were prepared by Langmuir–Blodgett techniques. We used both pure silicon (hydrophilic) and silicon covered by dimethyldichlorosilane, rendering the surface hydrophobic. Data were analysed using a box-model and the recursion scheme of Parratt. The results for the samples on hydrophobic substrate are interpreted by a stretched horizontal configuration. The electron densities and thickness of the layers are in good agreement with a model of close-packed molecules lying flat on the surface. Samples on pure silicon show a U-shape form of the molecules.

Qualitative and quantitative analysis of the secondary structure of cytochrome C Langmuir-Blodgett films.

A qualitative and quantitative analysis of the conformation of Langmuir-Blodgett (LB) dried films of cytochrome C on silicon wafers was performed by Fourier transform ir (FTIR) spectroscopy. A deconvolution procedure was applied to the amide I band analysis, in order to determine the percentage of the different secondary structures. Qualitative analysis was performed by examining difference spectra. Films obtained by spreading protein solutions at pH 7.4 and 1, dried at 25 and 100 degrees C, on silicon wafers were also examined in order to detect spectral components associated with denatured protein domains, and to compare them with cytochrome C LB films. FTIR spectroscopy showed that the following important changes characterise LB film spectra: (a) the alpha-helix component is higher (its percentage is 57 and 54%) than the one estimated in dried film obtained by spreading the solutions at pH 7.4 on a silicon substrate (43%), (b) there is an increase in the intensity of bands attributed to protonated carboxy group bands, involved and not involved in the formation of hydrogen bonds, and a decrease in those attributed to deprotonated carboxy groups, (c) the intensity of several bands attributed to aromatic amino acids and aliphatic chains increases, and (d) bands due to O-H stretching vibrations of crystallization water are present. These conformational changes could be induced by protein-protein interaction caused by the close packing of molecules that occurs during LB film formation; it cannot be excluded that they may be accompanied by partial changes in the tertiary structure of the protein. A preferential orientation of protein molecules in LB films is also a possibility.

A vibrational study of chemisorbed 3-thiophene carboxylate on Cu{110}

The chemisorption of 3-thiophene carboxylate (C 4 H 3 SCO 2 − ) on Cu{110} following room temperature exposure of the metal to the parent carboxylic acid has been investigated by ultra-high resolution electron energy loss spectroscopy. By taking advantage of improvements in spectrometer design and the application of maximum entropy based, data analysis techniques, it has been possible to determine almost all of the vibrational frequencies associated with this chemisorbed species. Spectra were measured at a resolution of 23 cm −1 and a further improvement by about a factor 2 was obtained by subsequent data processing. As anticapted, the molecule adopts an upright orientation at saturation coverage and modes with their dipole moment change polarised predominantly parallel to the ring-CO 2 bond are the most intense in specular scattering. Modes of CH bending character are strongly enhanced in off-specular scattering. A strong, dipole active mode at 297 cm −1 is tentatively assigned to a collective mode of the close-packed molecules based on the out-of-plane bending of the aromatic ring relative to the carboxylate plane.

Synthesis and crystal structure of 1,3,5-tris [4-(phenylethynyl)phenyl]benzene

The crystal structure of 1,3,5-tris[4-(phenylethynyl)phenyl]benzene (1) has been investigated. Compound1 represents a model of the repeating unit of the most typical polyphenylene, which contains 1,3,5-trisubstituted benzene rings (chain centers) and acetylenic groups (complex-forming and cross-linking centers) in the main chain. The acetylene groups of neighboring molecules have a tendency to close mutual arrangement, which is favorable for their topochemical interaction. However, the relative conformational rigidity of molecules1 restricts not only the possibility of the optimal adjustment of the reactive sites of neighboring molecules to one another, but also hampers the close packing of molecules in the crystal, which contains channels filled by the solvent molecules (chloroform).

Molecular close-packing method and its application to crystal structure determination of deshexapeptide (B25-B30) insulin.

Based on the molecule-packing theory, we defined a molecule-packing function expressing the compatibility of packing among the symmetry-related molecules in a unit cell. A computer program imitating the close-packing of molecules in the objective crystal lattice and giving the function value of each rotation and translation of the molecule in the unit cell was performed, and it therefore made the close-packing of molecules express quantitatively. This method not only could judge a correct solution from several peaks of the rotation or translation function but it may also independently, quantitatively and quickly solve some specific problems of rotation and translation. Using known structure of despentapeptide (B26-B30) insulin as an example, the effectiveness of this method and its program was inspected, and this method was successfully applied to solving the translation problem of the unknown structure of deshexapeptide (B25-B30) insulin. The molecular close-packing method proved by the results of R-search and electron density maps is relatively independent of the molecular replacement method, though an effective complement of it.