On the possibility of nonradiative energy transfer between hydrophobic quantum dots in solutions

The Förster resonance energy transfer between CdSe quantum dots with two different sizes has been studied in an organic solvent upon the formation of close-packed aggregates of quantum dots, with the aggregation being both spontaneous and induced by a precipitating solvent. The addition of a precipitant has been established to noticeably increase the efficiency of the energy transfer. It has been shown that the sizes and numbers of resulting aggregates may be controlled by varying the experimental conditions.     

Effect of solvent polarity on the aggregation of fullerenes: a comparison between C60 and C70

Effect of solvent polarity on the aggregation behaviour of C₇₀ has been investigated in several mixed solvents using optical absorption, fluorescence, dynamic light scattering and scanning electron microscopic measurements and compared with those observed for the other fullerene analogue, C₆₀. It is seen that similar to C₆₀, aggregation of C₇₀ also requires the solvent polarity to exceed some critical value. In terms of solvent dielectric constant the critical solvent polarity, required for C₇₀ aggregation is found to be in the range of 27–31, which is much higher than that required for C₆₀ aggregation (12–14). The large difference in the critical solvent polarity required for C₆₀ and C₇₀ aggregation has been rationalized on the basis of the molecular shapes and the polarizabilities of two fullerene molecules.     

Impact of Chirality on Hydrogen-Bonded Supramolecular Assemblies and Photoconductivity of Diketopyrrolopyrrole Derivatives

Hydrogen bonds can efficiently guide the self-assembly of organic materials, enabling to tune the properties of the aggregation processes. In the case of π-conjugated materials, several parameters such as temperature, concentration and solvent can be used to modify the aggregation state while tuning the optoelectronic properties. Chirality can be included within the impacting parameters due to the differences in molecular packing. Here, chiral and achiral thiophene-capped diketopyrrolopyrrole derivatives were designed and synthesized containing amide bonds, with the aim to study the interplay between chiral assemblies and their stabilization through hydrogen-bonding. Differences in aggregation properties were observed with spectroscopy and microscopy, and a contactless microwave-based technique was used to study their intrinsic charge carrier mobility. The positive role of hydrogen-bonding has been highlighted and the differences between chiral and achiral compounds have been elucidated.     

Bis(merocyanine) Homo-Folda-Dimers: Evaluation of Electronic and Spectral Changes in Well-Defined Dye Aggregate Geometries

A series of three bis(merocyanine) dyes comprising chromophores of different conjugation lengths has been synthesized and the intramolecular aggregation process was investigated by UV/Vis absorption spectroscopy. The spectral changes observed upon variation of the solvent polarity reveal a folding process resulting in a cofacial π-stack of two chromophores with a decrease of the aggregation tendency with increasing chromophore length and solvent polarity. Solvent-dependent UV/Vis studies of the monomeric reference dyes show a significant increase of the polyene-like character for dyes with longer polymethine chains in nonpolar solvents, which is reversed upon aggregation due to the polarizability effect of the adjacent chromophore within the dye stack. The pronounced hypsochromic shift of the absorption band observed upon aggregation indicates strong coupling of the dyes’ transition dipole moments, which was confirmed by quantum-chemical analysis.     

Effect of solvent quality on aggregate structures of common surfactants

Aggregate structures of two model surfactants, AOT and C12E5 are studied in pure solvents D2O, dioxane-d8 (d-diox) and cyclohexane-d12 (C6D12) as well as in formulated D2O/d-diox and d-diox/C6D12 mixtures. As such these solvents and mixtures span a wide and continuous range of polarities. Small-angle neutron scattering (SANS) has been employed to follow an evolution of the preferred aggregate curvature, from normal micelles in high polarity solvents, through to reversed micelles in low polarity media. SANS has also been used to elucidate the micellar size, shape as well as to highlight intermicellar interactions. The results shed new light on the nature of aggregation structures in intermediate polarity solvents, and point to a region of solvent quality (as characterized by Hildebrand Solubility Parameter, Snyder polarity parameter or dielectric constant) in which aggregation is not favored. Finally these observed trends in aggregation as a function of solvent quality are successfully used to predict the self-assembly behavior of C12E5 in a different solvent, hexane-d14 (C6D14).     

Solvent replacement (decane → hexane) in concentrated silver organosols stabilized with sodium bis(2-ethylhexyl) sulfosuccinate

The structure-related properties of silver nanoparticles synthesized in reverse micellar solutions of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) have been studied in the processes of electrophoretic concentraton of nanoparticles, drying of concentrates, and redispersion in n-hexane and n-decane. It has been shown that the dispersity of nanoparticles and stability of organosols to aggregation remain preserved upon the replacement of a low-volatile solvent (decane) by a high-volatile solvent (hexane). The developed procedures enable one to easily regulate important technological characteristics of metal-based inkjet “nanoinks,” such as concentration and size of particles, as well as viscosity and drying rate of the inks.     

Solvent‐Induced Helical Assembly and Reversible Chiroptical Switching of Chiral Cyclic‐Dipeptide‐Functionalized Naphthalenediimides

Understanding the roles of various parameters in orchestrating the preferential chiral molecular organization in supramolecular self‐assembly processes is of great significance in designing novel molecular functional systems. Cyclic dipeptide (CDP) chiral auxiliary‐functionalized naphthalenediimides (NCDPs 1 – 6 ) have been prepared and their chiral self‐assembly properties have been investigated. Detailed photophysical and circular dichroism (CD) studies have unveiled the crucial role of the solvent in the chiral aggregation of these NCDPs. NCDPs 1 – 3 form supramolecular helical assemblies and exhibit remarkable chiroptical switching behaviour (M‐ to P‐type) depending on the solvent composition of HFIP and DMSO. The strong influence of solvent composition on the supramolecular chirality of NCDPs has been further corroborated by concentration and solid‐state thin‐film CD studies. The chiroptical switching between supramolecular aggregates of opposite helicity (M and P) has been found to be reversible, and can be achieved through cycles of solvent removal and redissolution in solvent mixtures of specific composition. The control molecular systems (NCDPs 4 – 6 ), with an achiral or D ‐isomer second amino acid in the CDP auxiliary, did not show chiral aggregation properties. The substantial roles of hydrogen bonding and π–π interactions in the assembly of the NCDPs have been validated through nuclear magnetic resonance (NMR), photophysical, and computational studies. Quantum chemical calculations at the ab initio, semiempirical, and density functional theory levels have been performed on model systems to understand the stabilities of the right (P‐) and left (M‐) handed helical supramolecular assemblies and the nature of the intermolecular interactions. This study emphasizes the role of CDP chiral auxiliaries on the solvent‐induced helical assembly and reversible chiroptical switching of naphthalenediimides.     

Tuning aggregation of microemulsion droplets and silica nanoparticles using solvent mixtures

The effect of solvent on stability of water-in-oil microemulsions has been studied with AOT (sodium bis(2-ethylhexyl)sulfosuccinate) and different solvent mixtures of n-heptane, toluene and dodecane. Dynamic light scattering DLS was used to monitor the apparent diffusion coefficient D(A) and effective microemulsion droplet diameter on changing composition of the solvent. Interdroplet attractive interactions, as indicated by variations in D(A), can be tuned by formulation of appropriate solvent mixtures using heptane, toluene, and dodecane. In extreme cases, solvent mixtures can be used to induce phase transitions in the microemulsions. Aggregation and stability of model AOT-stabilized silica nanoparticles in different solvents were also investigated to explore further these solvent effects. For both systems the state of aggregation can be correlated with the effective molecular volume of the solvent V(mol)(eff) mixture.     

Effects of addition of polar organic solvents on micellization

Micellization of several surfactants in water-organic solvent mixtures has been investigated. Only solvents localized mainly in the bulk phase of the micellar solutions (they do not incorporate into the micelles) were studied, with either higher or lower permittivity than that of pure water. Results show that the influence of organic solvent addition on the aggregation process can be approximately accounted for by considering the changes in the bulk phase cohesive energy density, described by the Gordon parameter, G. To our knowledge, this is the first time that, for a given surfactant, the Gibbs energies of micellization, Delta G M degrees , obtained in several water-organic solvent mixtures have been fitted together. It is worth noting that data from different research groups have been considered. The Delta G M degrees versus G correlation will permit the estimation of the variations in the Gibbs energy of micellization upon addition of known quantities of a given polar organic solvent. Speaking in a general way, organic solvent addition results in the bulk phase becoming a better solvent for the surfactant molecules. This would make the hydrophobic tail transfer from the bulk phase into the micelles less favorable and, as a consequence, Delta G M degrees increases (becomes less negative), making the aggregation process less spontaneous.     

Aggregates of poly-functional amphiphilic molecules in water and oil phases

The solvation and aggregate formation of complex amphiphilic molecules such as tetra-acids in polar and nonpolar phases are studied via Molecular Dynamics simulations. The nonpolar core of tetra-acid molecules is found to be effectively impermeable for water molecules resulting in a low solubility in the polar solvent, while nonpolar solvent molecules sufficiently solvate the amphiphilic molecules considered, enabling an open conformation of their molecular structure. The rigidity of the core region of the tetra-acid molecules has been found to play a crucial role in their behavior in both polar and nonpolar phases. In the polar phase, simulations have shown that tetra-acids form micelle-like structures with a small aggregation number, confirming previous experimental work. The identification of a case of study in which micelle-like structures can form only with a small aggregation number enables the study via Molecular Dynamics of micelle-micelle interactions. Micelle stability and dispersion in the polar phase under different conditions can be therefore investigated. In the nonpolar phase, the preferential interactions between carboxyl groups, the affinity of the tetra-acids with the solvent molecules, and the structural characteristics of the central core moiety of the tetra-acids have been found to possibly induce a web like array, or network.     

Electrochemical characterization of Co(II) and Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents

In this study, electrochemical behaviors of Co(II) and Pd(II) phthalocyanines carrying tetrakisdiethoxymalonyl and Pd(II) phthalocyanine carrying tetrakiscarboxymethyl substituents at the peripheral positions are investigated by cyclic voltammetry and applied potential chronocoulometry techniques. Cyclic voltammetric studies show that, while Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents give up to three common phthalocyanine ring reductions, Co(II) phthalocyanine carrying diethoxymalonyl substituents gives a metal-centered oxidation and a metal-centered reduction and three ligand-centered reduction and a ligand-centered oxidation processes. First reduction processes of both the PdPc complexes have shoulders. This different voltammetric behaviors of Pd(II) phthalocyanines carrying carboxymethyl and diethoxymalonyl substituents results from interaction of this distinctive substituents with the phthalocyanine ring π electron system and interaction with the different solvent systems. Observation of the splitting of the first reduction process of Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents suggests the aggregation of the complex. Very small diffusion coefficient of the complexes with respect to Co(II) phthalocyanine also confirms the existence of the aggregation of the complex during the electrochemical studies. Effects of the substituents and the solvent media are clearly observed from the differences of the voltammograms of Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents in DMSO and THF solvent media, respectively. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 1, pp. 36–43. The text was submitted by the authors in English.     

Controlled aggregation of peptide-substituted perylene-bisimides

Controlled aggregation of perylene bisimides in multiple modes has been achieved via symmetric substitution with peptides. Using optical probes of aggregation, the balance of hydrophobic and electrostatic forces are found to play a key role in directing self assembly and are exploited via solvent, pH, and specific extrinsic ion effects.     

胆固醇酯类化合物在混合溶剂中的簇集及其荧光光谱的特征

近年来,人们对长链脂肪族、芳香族化合物分子在二甲基亚砜/水(DMSO/H₂O)混合溶剂中发生簇集,形成聚集体进行了广泛研究指出:簇集的驱动力是疏水作用。     

Monitoring the Aggregation of Dansyl Chloride in Acetone through Fluorescence Measurements

The aggregation of dansyl chloride (DNS-Cl) in acetone has been studied in detail by steady-state fluorescence techniques.It has been demonstrated that DNS-Cl is stable in acetone during purification and aggregation study processes.The aggregates are not solvolyzed in acetone,and do not take part n any chemical reactions either.It has been found that DNS-Cl tends to aggregate even when its concentration is much lower than its solubility in acetone.The aggregation is reversible,and both the aggregation and the deaggregation are very slow processes.Introduction of SDS has a positive effect upon the formation and stabilization of the aggregates.     

煤的缔合结构研究 Ⅰ 溶液缔合动力学

研究了煤可溶组分——吡啶不溶物（PI）在溶液中的缔合动力学，该PI系二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂可溶组分。结果表明PI在NMP溶液中的缔合属于反应控制机理，并提出了二步动力学反应过程，即基本缔合单元的生成和缔合单元之间的缔合。通过实验获得了有关缔合的动力学参数，PI在NMP溶液中二步缔合的活化能分别为73.3 kJ/mol和21.6 kJ/mol。温度对缔合速率的影响显著，随着温度的升高，缔合速率增加。由于PI分子在CS2/NMP混合溶剂中相对NMP具有较高的扩散性，因而其在CS2/NMP混合溶剂中缔合速率较NMP快。此外，还讨论了PI在溶液中的缔合机理。     

Antisolvent precipitation of hydrophobic functionalized multiwall carbon nanotubes in an aqueous environment

The possibility of antisolvent precipitation of hydrophobic, organic soluble functionalized carbon nanotubes (f-CNTs), where water acts as an antisolvent is presented. Octadecylamine functionalized multiwall carbon nanotubes (MWCNT-ODA) was used as the model compound and was found to form highly stable dispersions in different water/solvent systems, and the particle sizes ranged from 170 to 400 nm. Colloidal behavior was studied using dynamic light scattering and particle aggregation was found to increase with the addition of electrolytes, with tetrahydrofuran (THF) and ethanol showing the maximum effect. The aggregation behavior of the antisolvent precipitated system did not follow the conventional Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, which was different from what has been reported previously for hydrophilic, water soluble f-CNTs. Based on this study, it is evident that hydrophobic f-CNTs are potential water pollutants.     

Nano-enabled microtechnology: polysulfone nanocomposites incorporating cellulose nanocrystals

Microchannel devices hold the potential to transform many separation processes. This preliminary study investigated the feasibility of incorporating cellulose nanocrystals (CNXLs) into polysulfone, a commonly used ultrafiltration membrane polymer. Incorporating CNXLs into non-water soluble polymers without aggregation has been problematic. A solvent exchange process was developed that successfully transferred an aqueous CNXL dispersion into the organic solvent N-methylpyrrolidone (NMP), which is a solvent for polysulfone (PSf). Films were prepared from the solution of PSf in NMP with dispersed CNXLs by a phase inversion process. Films were then examined by scanning electron microscopy and tested for their transport and mechanical properties. The interaction between the polymer matrix and the CNXL filler was studied by means of thermogravimetric analysis (TGA), which suggested a close interaction between the polymer and filler at the 2% filler loading. The tensile modulus showed a large increase beyond 1% filler loading, which could be due to a percolation effect. The water vapor transport rate increased with increase in filler loading. Agglomeration of the CNXLs seemed to be taking place at filler loadings >7%.     

Approaches to molecular composites from fluorine-containing bis-maleimides: Part I

Previous work in our laboratory has shown that covalent bonding of a semiflexible polymer in a bis-imide matrix prior to thermal polymerization is a promising, although structure-dependent, approach to the synthesis of molecular composites from organic solvents in thermosets. In the present investigation, the focus has been on the rapid amine-catalyzed anionic polymerization and crosslinking of fluorine-containing bis-maleimides. The objective has been to provide physical entrapment of rigid polymer prior to aggregation. Results have shown that gelation of fluorine-containing bis-maleimides initiated by tertiary amines in organic solvent can occur in seconds at moderate temperatures, and thus affords a means of preventing aggregation of rigid polymer prior to crosslinking.     

离子对的聚集作用(Ⅰ)——溶剂和卤负离子对聚集度的影响

用沸点升高法测定了卤化四丁铵在有机溶剂中的平均聚集度。发现溴化四丁铵在苯中的聚集度远大于在氯仿中的。说明溶剂的极性起着首要作用。在氯仿中聚集度的大小顺序为碘化四丁铵>溴化四丁铵>氰化四丁铵。 还测定了溴化与碘化四丁铵混合溶液的聚集度。测得值显著大于它们单独存在时的值。认为存在离子对的渔合聚集体。     

Molecular Daisy Chains: Synthesis and Aggregation Studies of an Amphiphilic Molecular Rod

A water‐soluble cyclophane as the loop subunit, monofunctionalized with a molecular rod, has been synthesized to introduce a new binding motif for mechanically interlinked oligomers. It has been demonstrated that this hermaphroditic compound forms [c2]daisy chains in polar solvent over a wide range of concentrations. Furthermore, evidence for the formation of higher mechanically interlinked oligomers above the critical aggregation concentration has been obtained.