高分子表面活性剂的分子设计

简要讨论高分子表面活性剂的俣成和表征方法，分析了在水溶液中两亲性聚合分子形态与表面活性的关系，单分子／多分子胶束多的形成是导致聚合物表面活性变差的主要因素，提出了高分子表面活性剂的分子设计原则，设计了多种在高分子量下将能够优质优良表面活性的高分子表面活性剂分子结构模型。     

用分子自由振动固有频率预测阴离子表面活性剂临界胶束浓度

用分子自由振动固有频率预测阴离子表面活性剂临界胶束浓度;CMC;QSPR     

Electroactive Benzothiazole Hydrazones and Their [Mo6O19]2− Derivatives: Promising Building Blocks for Conducting Molecular Materials

The electroactive benzothiazole hydrazone AMBTH–H₂, a new member of the 2,2′‐azino‐bis(N‐alkylbenzothiazole) family, was synthesised in a five‐step procedure and characterised by using X‐ray diffraction along with two intermediates and the N‐methylbenzothiazole hydrazone MBTH–H₂. Both AMBTH–H₂ and MBTH–H₂ were coupled to [Mo₆O₁₉]^2? in acetonitrile in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine to give two new diazoalkane–hexamolybdates, which were isolated as tetrabutylammonium salts and characterised by using IR, UV/Vis and NMR spectroscopies, cyclic voltammetry and, for one of them, X‐ray diffraction. The packing arrangement molecules in crystals of AMBTH–H₂, the redox features of the AMBTH–hexamolybdate hybrid together with a good electronic communication between the organic π system and the molybdenum centres make these compounds very promising blocks for the synthesis of conducting molecular materials.     

Cashew Nut Shell Liquid (CNSL) as a Source of Drugs for Alzheimer’s Disease

Alzheimer’s disease (AD) is a complex neurodegenerative disorder with a multifaceted pathogenesis. This fact has long halted the development of effective anti-AD drugs. Recently, a therapeutic strategy based on the exploitation of Brazilian biodiversity was set with the aim of discovering new disease-modifying and safe drugs for AD. In this review, we will illustrate our efforts in developing new molecules derived from Brazilian cashew nut shell liquid (CNSL), a natural oil and a byproduct of cashew nut food processing, with a high content of phenolic lipids. The rational modification of their structures has emerged as a successful medicinal chemistry approach to the development of novel anti-AD lead candidates. The biological profile of the newly developed CNSL derivatives towards validated AD targets will be discussed together with the role of these molecular targets in the context of AD pathogenesis.     

Development of Sustainable Chemistry in Madagascar: Example of the Valuation of CNSL and the Use of Chromones as an Attractant for Mosquitoes

This article describes a part of the results obtained from the cooperation between the University of Lyon1 (France) and the University of Antananarivo (Madagascar). It shows (among others) that useful research can be carried out in developing countries of the tropics if their social, technical, and economic conditions are taken into account. The concepts and methods associated with so-called “green chemistry” are particularly appropriated for this purpose. To illustrate this approach, two examples are shown. The first deals with industrial ecology and concerns waste transformation from the production of cashew nut into an amphiphilic product, oxyacetic derivatives. This product was obtained with a high yield and in a single step reaction. It exhibited an important surfactant property similar to those of the main fossil-based ones but with a much lower ecological impact. The second talks about chemical ecology as an alternative to insecticides and used to control dangerous mosquito populations. New substituted chromones were synthesized and showed biological activities toward Aedes albopictus mosquito species. Strong repellent properties were recorded for some alkoxylated products if others had a significant attractant effect (Kairomone) depending on their stereochemistry and the length of the alkyl chain.     

Prediction on Critical Micelle Concentration of Nonionic Surfactants in Aqueous Solution： Quantitative Structure-Property Relationship Approach

IntroductionCriticalmicelleconcentration (cmc)ofsurfactantsinaqueoussolutionisoneofthemostusefulparametersforcharacterizingthepropertiesofsurfactants.Overaverynarrowconcentrationrangearoundthecmctransitionsoftheexistenceofsurfactantsoccurfrommonomer ,premicel lartomicellar .Andcompanyingthesetransitions ,manyotherimportantpropertiesofsurfactantsolution ,suchassurfacetension ,interfacialtension ,conductivity ,osmoticpressure ,detergency ,emulsification ,foamingandsoon ,alsochangesharplyatthepoi…     

Titration of Anionic Surfactants in a Mixture,Using a Surfactant Exthactive Electrode

Abstract

Mixtures of sodium octylsulfate with sodium dodecyl-benzenesulfonate or sodium di-2-ethylhexglsulfosuccinate (Aerosol OT) were determined potentiometrically. The titration curve permits the simultaneous determination of both components with en accuracy of 1.0%.     

Effective Drug Therapies from Functional,Macromolecular Building Blocks with a Biomimetic Design

Summary: The development of suitable delivery systems for intracellular delivery of proteins, peptides and other bioactive materials opens the possibility to establish refined strategies for small drug delivery, gene delivery and vaccination. We present the assembly of advanced drug delivery systems from tailored building blocks to scaffolds and bioactive cargos to afford targeting and transport across biological barriers. In particular, the utilization of novel molecular transporter will advance the bioavailability of small and macromolecular drugs that show targeted intracellular delivery.     

Molecular Dynamics Simulation of Sulfobetaine-Type Zwitterionic Surfactants at the Decane/Water Interface: Structure,Interfacial Properties

Molecular dynamics simulations of interfacial properties of new sulfobetaine-type zwitterionic surfactants were performed using a united atomistic model, and a detailed analysis of hydrophilicity, temperature sensitivity, and salt resistance of surfactants was carried out. The new model was parameterized to reproduce the density and showed good agreement with experimental values. The results showed that the surfactant will not cease to be effective with the increase of the temperature from 300 to 373 K but as it rises, the interfacial tension will have a reduction. This kind of surfactant can be proved to remain an activity at high concentration of monovalent and divalent cations. It has commendable salt tolerance.     

Building Blocks for High-Efficiency Organic Photovoltaics: Interplay of Molecular,Crystal, and Electronic Properties in Post-Fullerene ITIC Ensembles

Accurate single-crystal X-ray diffraction data offer a unique opportunity to compare and contrast the atomistic details of bulk heterojunction photovoltaic small-molecule acceptor structure and packing, as well as provide an essential starting point for computational electronic structure and charge transport analysis. Herein, we report diffraction-derived crystal structures and computational analyses on the n-type semiconductors which enable some of the highest efficiency organic solar cells produced to date, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC ) and seven derivatives (including three new crystal structures: 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-propylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC-C3 ), 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( m -ITIC-C6 ), and 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-butylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene ( ITIC-C4-4F ). IDTT acceptors typically pack in a face-to-face fashion with π–π distances ranging from 3.28–3.95 Å. Additionally, edge-to-face packing is observed with S⋯π interactions as short as 3.21–3.24 Å. Moreover, ITIC end group identities and side chain substituents influence the nature and strength of noncovalent interactions (e. g. H-bonding, π–π) and thus correlate with the observed packing motif, electronic structure, and charge transport properties of the crystals. Density functional theory (DFT) calculations reveal relatively large nearest-neighbor intermolecular π-π electronic couplings (5.85–56.8 meV) and correlate the nature of the band structure with the dispersion interactions in the single crystals and core–end group polarization effects. Overall, this combined experimental and theoretical work reveals key insights into crystal engineering strategies for indacenodithienothiophene (IDTT) acceptors, as well as general design rules for high-efficiency post-fullerene small molecule acceptors.     

Transition Metal Complexes of Cyanoisocyanoarenes as Building Blocks for One-, Two-, and Three-Dimensional Molecular Solids

The complexes trans-[MI(2)(CNC(6)H(4)-CN-4)(2)], (M = Pd and Pt), trans-[FeI(2)L(4)] (L = CNC(6)H(4)-CN-4 and CNC(6)H(2)-Me(2)-2,6-CN-4), and [Mn(CNC(6)H(4)-CN-4)(6)][SO(3)CF(3)] were prepared. The compounds are thermally stable up to 230 degrees C or higher. The molecular structure of trans-[FeI(2)(CNC(6)H(4)-CN-4)(4)] was determined by X-ray crystallography: monoclinic, space group P2(1)/n, a = 11.570(2) ?, b = 10.1052(8) ?, c = 28.138(7) ?, beta = 92.034(9) degrees, Z = 4, 3464 unique reflections, R = 0.074, R(w) = 0.089. The complexes contain the peripheral cyano groups in linear, planar, and octahedral dispositions, respectively. Solids were obtained by combining solutions of [PdI(2)(CNC(6)H(4)-CN-4)(2)] and [Cu(hfacac)(2)], [FeI(2)(CNC(6)H(4)-CN-4)(4)] and AgSO(3)CF(3), [FeI(2)(CNC(6)H(2)-Me(2)-2,6-CN-4)(4)] and [Rh(2)(O(2)CCF(3))(4)], and [Mn(CNC(6)H(4)-CN-4)(6)][SO(3)CF(3)] and [Rh(2)(O(2)CCF(3))(4)]. [PdI(2)(CNC(6)H(4)-CN-4)(2)] and [Cu(hfacac)(2)] in a ratio of 1:2 form a crystalline, one-dimensional solid: monoclinic, space group P2(1)/c, a = 8.317(2) ?, b = 13.541(1) ?, c = 22.568(5) ?, beta = 100.45(1) degrees, Z = 2, 3279 unique reflections, R = 0.037, R(w) = 0.047.     

Industrial Applications of Dimeric Surfactants: A Review

Dimeric surfactants also known as gemini surfactants have received lots of attention for high performance formulations in the various scientific and commercial products. Due to the greater amount of hydrocarbon per molecule, the critical micelle concentrations (CMC) of dimeric are typically one order of magnitude lower than the corresponding monomeric surfactant. They are ten to hundred times more efficient at reducing the surface tension of water and the interfacial tension of the oil-water interface than conventional surfactants. Besides, the Krafft temperatures of gemini surfactants with hydrophilic spacers are generally very low giving these surfactants the capacity to be used in cold water. These surfactants display a range of interesting properties, including elevated surface activity, extremely low CMC and extraordinary rheology and self-assimilation aspect. As a consequence of these properties, they have many potential applications include detergents and cleaning agents, cosmetics, textile, and dyeing, dispersion stabilization and emulsion polymerization, genetics science, pharmaceutical, and biological applications.      

Controlled Synthesis and Molecular Structures of Methoxy-, Amino-, and Chloro-Functionalized Disiloxane Building Blocks

Functionalized disiloxane units with defined structures are interesting molecular models for investigating the reactivity and chemoselectivity in transformations that are of interest in synthesis, surface chemistry, and materials science. (Mes)PhSi(OMe)₂ ( 1 ) (Mes = mesityl) and (Mes)PhSiCl₂ ( 5 ) were chosen as starting compounds for the controlled synthesis of methoxy-, amino-, and chloro-functionalized unsymmetric disiloxanes. Two synthesis routes towards (Mes)PhSi(OMe)(OSiPh₃) ( 3 ) were followed, one via the aminomethoxysilane (Mes)PhSi(OMe)(NC₄H₈) ( 2 ) and the other via the chlorodisiloxane (Mes)PhSiCl(OSiPh₃) ( 6 ). The amino-substituted disiloxane (Mes)PhSi(NC₄H₈)(OSiPh₃) ( 4 ) was obtained from the chloro derivative 6 with N-pyrrolidinyllithium, but the same reaction starting from compound 3 was not successful. All provided disiloxanes were structurally characterized by X-ray crystallography.     

聚合物与表面活性剂相互作用的分子模拟研究进展

聚合物与表面活性剂复配体系已广泛应用于医药、生物、石油石化等领域。从微观上认识其相互作用机理对指导其生产实际有着重要作用,因而此方面的研究倍受关注。随着分子模拟技术的发展,聚合物与表面活性剂在分子水平上的相互作用机理研究已经被广泛开展,并获得了大量有用的信息。本文综述了耗散粒子动力学(DPD)和粗粒度分子动力学(CG-MD)在聚合物与表面活性剂相互作用方面的应用,分别对中性聚合物与离子型表面活性剂,以及带相反电荷的聚电解质和表面活性剂在溶液相和界面相的相互作用进行了阐述,并揭示了聚合物/表面活性剂聚集体结构形态的变化规律。     

Synthesis,Properties, and Applications of Amino Acids Based Surfactants: A Review

Amino acids based surfactants belong to the class of surfactants with high biodegradability, low toxicity and excellent surface active properties. They possess excellent emulsifying, detergency properties and form fine lather. These surfactants are environment friendly, mild to skin and eyes, and have hard water tolerance. This article reviews types, synthesis, various surface properties such as cmc (critical micelle concentration), surface tension, phase behavior, Krafft temperature, and interfacial adsorption of these surfactants. The biological properties such as antimicrobial activity, aquatic toxicity, biodegradability and hemolytic activity have also been focused. The various applications of amino acid based surfactants in the area of life sciences such as gene transfection, formation of liposomes, and drug delivery systems have also been reviewed.     

Synthesis of Tetraalkenylmethane: Building Blocks for Three-Dimensional Hydrocarbon Networks

In this paper, we show a common strategy to synthesize tetraalkenylmethanes, a cross-linker series for building three-dimensional hydrocarbon networks. To demonstrate the feasibility of this method, we have synthesized tetrapentenylmethane. Attempts to synthesize this cross-linker from pentaerythrityl tetrabromide using substitution reactions resulted in the formation of a spiro compound due to intramolecular cyclization. We also show that the difficulty in reactions at the neopentyl carbon site is due to the neopentyl carbanion stability, not the sterics.