Self-Organization of Lipid-Porphyrin Conjugates at the Air/Water Interface

Lipid-porphyrin conjugates are versatile compounds which can self-assemble into liposome-like structures with multifunctional properties. Most of the conjugates that have been described so far, consisted in grafting pyropheophorbide-a (Pyro-a) or other porphyrin derivatives through the esterification of the hydroxyl group in the sn-2 position of a lysophosphatidylcholine. However, despite the versatility of these conjugates, less is known about the impact of the lipid backbone structure on their 2D phase behavior at the air/water interface and more precisely on their fine structures normal to the interface as well as on their in-plane organization. Herein, we synthesized a new lipid-porphyrin conjugate (PyroLSM) based on the amide coupling of Pyro-a to a lysosphingomyelin backbone (LSM) and we compared its interfacial behavior to that of Pyro-a and Pyro-a conjugated lysophosphatidylcholine (PyroLPC) using Langmuir balance combined to a variety of other physical techniques. Our results provided evidence on the significant impact of the lipid backbone on the lateral packing of the conjugates as well as on the shape and size of the formed domains. Compared to Pyro-a and PyroLPC monolayers, PyroLSM exhibited the highest lateral packing which highlights the role of the lipid backbone in controlling their 2D organization which in turn may impact the photophysical properties of their assemblies.     

In-plane and out-of-plane defectivity in thin films of lamellar block copolymers

We investigate the ordering of poly(styrene-b-methyl methacrylate) (PS-PMMA) lamellar copolymers (periodicity L₀ = 46 nm) confined between a free surface and brushed poly(styrene-r-methyl methacrylate) silicon substrate. The processing temperature was selected to eliminate wetting layers at the top and bottom interfaces, producing approximately neutral boundaries that stabilize perpendicular domain orientations. The PS-PMMA film thickness (t = 0.5L₀ − 2.5L₀) and brush grafting density (Σ = 0.2–0.6 nm⁻²) were systematically varied to examine their impacts on in-plane and out-of-plane ordering. Samples were characterized with a combination of high-resolution microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering. In-plane order at the top of the film (quantified through calculation of orientational correlation lengths) improved with tⁿ, where the exponent n increased from 0.75 to 1 as Σ decreased from 0.6 to 0.2 nm⁻². Out-of-plane defects such as tilted domains were detected in all films, and the distribution of domain tilt angles was nearly independent of t and Σ. These studies demonstrate that defectivity in perpendicular lamellar phases is three-dimensional, comprised of in-plane topological defects and out-of-plane domain tilt, with little or no correlation between these two types of disorder. Strong interactions between the block copolymer and underlying substrate may trap both kinds of thermally generated defects. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 339–352     

Construction of Insulin 18‐mer Nanoassemblies Driven by Coordination to Iron(II) and Zinc(II) Ions at Distinct Sites

Controlled self‐assembly (SA) of proteins offers the possibility to tune their properties or to create new materials. Herein, we present the synthesis of a modified human insulin (HI) with two distinct metal‐ion binding sites, one native, the other abiotic, enabling hierarchical SA through coordination with two different metal ions. Selective attachment of an abiotic 2,2′‐bipyridine (bipy) ligand to HI, yielding HI–bipy, enabled Zn^II‐binding hexamers to SA into trimers of hexamers, [[HI–bipy]₆]₃, driven by octahedral coordination to a Fe^II ion. The structures were studied in solution by small‐angle X‐ray scattering and on surfaces with AFM. The abiotic metal ligand had a higher affinity for Fe^II than Zn^II ions, enabling control of the hexamer formation with Zn^II and the formation of trimers of hexamers with Fe^II ions. This precise control of protein SA to give oligomers of oligomers provides nanoscale structures with potential applications in nanomedicine.     

Statistical thermodynamics approach for estimation of the interaction parameters in the mixed Langmuir films at the water/air interface

The treatment of two-dimensional system of three components of molecules of different molecular sizes, adapted from statistical thermodynamics, is used to derive parameters which could be derive parameters which could be related to the interaction between molecules in the mixed Langmuir films formed at the water/air interface.     

Foam formation and stabilisation by pre-denatured ovalbumin

Various mild heat-treatments of ovalbumin solutions were applied to produce molecular species with different conformational states, and having different kinetics of adsorption to the air/water interface and different foaming properties. Molecular species with a higher degree of shear-induced deformation and a low degree of thermal conformational stability showed a slight enhancement of the rate of decrease of surface tension, 5 min after the creation of the fresh interface, and decreasing long-term values of surface tension. Solutions of ovalbumin molecular species exhibiting such initial structural patterns were shown to have enhanced foam capacity and stability against liquid drainage. Ovalbumin molecules with some degree of secondary and tertiary structural changes and increased viscosity, before adsorption at the air/water interface, were shown to be relevant to produce more or less hydrated foams with more or less stability against liquid drainage.     

杯芳烃-卟啉化合物及其锌、钯配合物的制备与成膜性能研究

将广泛用作分子构架和分子载体的杯芳烃和卟啉结合,合成了具有更多功能和用途的杯芳烃-卟啉化合物及其锌、钯配合物,并成功地在气/液界面得到它们的单分子膜,并对其成膜性能作了初步的探讨.结果表明,无论是杯芳烃-卟啉化合物还是它的锌、钯配合物均能形成稳定的单分子膜.     

Correlation between crystal texture and microporous structure of carbon adsorbents

A correlation of adsorption and X-ray data for a series of both initial and modified active carbons (AC) was performed. The AC were modified by thermal treatment and progressive activation. A linear correlation between the sizes of crystallites and micropore widths of AC was established. It was shown that the adsorption of water vapor results in an increase in the parameterL _aof crystallites of active carbons.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2159–2162, November, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09550).     

In situ Observation of the Photochromism in the Langmuir Monolayer of a Non—typical Amphiphilic Spiropyran Derivative at the Air／Water Interface

In situ photochromic process in the monolayer of aphotochromic spiropyran derivative without long alkyl chain,was investigated.The photochromism at the air/water interface under differnet surface pressures was studied by surface pressure-area isotherms,surface pressure-time curves,area-time curves and Brewster angle microscopy.Both forms of the compound were found to form monolayers at the air/water interface althouhg it does not have long alkyl chain.A large area expansion in the monolayer corresponding to a zreo^th order reaction was found at the initial stage of the UV light irradiation.A series of dynamic investigations revealed that at high pressure after phase transition in the monolayer,the surface pressure changes greatly umder alternative irradiation of UV and visible light.An obvious morphological change accompanying with the photochromism was observed in situ.     

微生物脂肽在气/液界面上的分子形态*

微生物脂肽是一类具有很强表面活性和生物特性的生物表面活性剂。脂肽分子由亲水的肽链和疏水的脂肪烃链两部分组成,由于其特殊的化学组成和两亲性分子结构,脂肽类生物表面活性剂在医药、食品、化妆品、环境修复和微生物采油等领域具有良好的应用潜力。表面活性素是一类典型的微生物脂肽化合物,这主要是因为它除了具有表面活性外,还具有抗菌、抗病毒等生物活性。表面活性和生物活性主要在界面处发生,并受到活性分子在亲水/疏水界面上的分子形态的影响。本文重点以表面活性素为评述对象,综述了近年来微生物脂肽在气/液界面上分子形态的研究进展。     

On the interpretation of small-angle X-ray scattering during water adsorption by carbon adsorbents

Two models accounting for the changes of shape of the small-angle X-ray scattering (SAXS) curves during water adsorption by carbon adsorbents are discussed. The first model is based on the assumption of partial filling of the pore space; the second one presumes micropore swelling during water adsorption. Analysis of the results allows one to conclude that the first model is valid. This conclusion is in agreement with adsorption investigation data.Deseased 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1220–1223, July, 1993.     

非离子表面活性剂在气液界面的分子动力学模拟

采用分子动力学方法研究了十二烷基醇聚氧乙烯醚系列非离子表面活性剂单分子层在气液界面的微观结构,并通过表面张力的计算考察了表面活性剂分子结构与性能的关系.研究结果表明,随着表面活性剂分子乙氧基基团个数的增加,模拟所得的表面张力的变化趋势与实验一致,所有分子的计算误差在5 mN·m-1以内.同时,随着乙氧基基团数目的增加,...     

氟化单元封端的不同聚合度PBMA甲苯溶液气/液界面结构

采用ATRP技术合成具有不同聚合度的末端连接甲基丙烯酸全氟辛基乙酯(FMA)单元的聚甲基丙烯酸丁酯(PBMAm-ec-PFMAn).利用和频振动光谱(SFG)和表面张力测定技术研究了各种氟化聚合物溶液的气/液界面结构.发现PBMAm-ec-PFMAn甲苯溶液的表面活性及其气/液界面的结构与两种结构单元数密切相关.当PFMA聚合度(n)大约为4和6时,聚合物溶液的表面张力随着PBMA聚合度的增加从21增加到25mN/m(该值与PBMA均聚物溶液相同).SFG的研究结果表明PBMA段较长时溶液表面被PBMA所占据.PBMA段较短时,PFMA组分吸附在溶液表面,排列比较有序且紧密堆积.当PBMA末端只有1个FMA单元时,其甲苯溶液的表面张力随PBMA段长稍有增加(从22增加到23mN/m),其值介于21与25mN/m之间.研究表明当PBMA段较短时,可能聚合物中的氟化组分吸附在溶液表面,但其排列的有序性较差.随着PBMA聚合度的增加,氟化组分与PBMA组分可能同时占据在溶液表面,这时其表面张力大约为23mN/m.     

Dilational Rheology at Air/Water Interface and Molecular Dynamics Simulation Research of Hydroxyl Sulfobetaine Surfactant

Hydroxyl sulfobetaines with hexadecyl-, octadecyl-hydrophobic chain and an industrial product hydroxyl sulfobetaine were synthesized from analytical-grade and industrial-grade tertiary amine, respectively. The dilational properties and surface tension of the three surfactants at the water-air interface were investigated by drop shape analysis and ring method. The influences of oscillating frequency and bulk concentration on dilational properties were explored. The experimental results show that the dilational module of octadecyl-hydroxyl sulfobetaine was higher than hexadecyl hydroxyl sulfobetaine and the dilational elastic component of the three surfactants were higher than dilational viscous component. Furthermore, the dilational elastic component of mixed surfactant system shows two maxima in a lower concentration than that of single surfactant system. As a result, the surface tension of mixed surfactant system reaches to minimum value in a lower concentration compared with single surfactant system. The simulation results show that the hydrophobic chains in the mixed betaine solution were more curled than in single-component betaine solution ascribed to stronger interaction among different hydrophobic chains, resulting to a more compact interfacial film.     

Surface Chemistry Studies of Quantum Dots (QDs) Modified with Surfactants

Since luminescent CdSe quantum dots (QDs) have shown great potential in biological labeling, the surface chemistry behavior of QDs at interfaces is of great research interest. In the present study, CdSe QDs with green luminescence were modified with hydrophobic chains of varying lengths [from C6 to C18]. These modified QDs can be utilized to form stable monolayers at the air/water interface. Surface pressure-area isotherms of modified QDs have been measured and limiting molecular areas have also been extrapolated in order to analyze the size of the QDs. UV absorption spectra of modified QDs at various surface pressures were also determined. Surface chemistry, as well as the topographic properties, of modified QDs in Langmuir and L-B films was discussed.     

液液萃取中半挥发性有机物正辛醇/水分配系数与回收率相关性分析

该文讨论了水中目标有机物的回收率与正辛醇/水分配系数之间的联系,结果表明半挥发性有机污染物在水中的回收率与正辛醇/水分配系数(lg Kow)间存在一定的规律:当lg Kow5时,回收率为16.1%~56.1%,当lg Kow5时,回收率为59.5%~124.9%;用溶解度(lg S)与89种有机污染物的回收率进行分析,得出与正辛醇/水分配系数(lg Kow)一致的结论:当lg S-0.60时,回收率为59.5%~124.9%,当lg S-0.6时,回收率为16.1%~56.1%;采用实际水样的实验室空白加标结果对所得结论进行验证,其结果显示与上述结论一致,即当污染物的lg Kow5,或者lg S-0.6时,其液液萃取的回收率为85.3%~115.9%。     

Charge reversal at the air/water interface as inferred from the thickness of foam films

Experiments are reported with foam films from aqueous solutions with increasing concentration of a cationic surfactant. A correlation is established between the foam film thickness and the possible variation of diffuse electric layer potential at the air/water interface from a negative value in absence of surfactant to positive values at higher surfactant concentrations. It is concluded that a charge reversal at the air/water interface is expected to occur under increasing concentration of cationic surfactants in aqueous solutions.     

Quantitative Analysis of Prometrine Herbicide by Liquid–Liquid Extraction Procedures Coupled to Electrochemical Measurements

A sensitive method is proposed for the preconcentration and quantification of the herbicide Prometrine (PROM) at a liquid‐liquid interface employing square‐wave voltammetry. The preconcentration stage was based on liquid‐liquid extraction methodology and the PROM quantification was carried out from the peak current of square‐wave voltammograms. Under the experimental conditions employed, linear calibration curves in the concentration range 1.0×10^?6 M–5.0×10^?5 M, with detection limit equal to 1.5×10^?6 M were obtained without pretreatment of the samples. This linear range, as well as detection limit could be extended towards lower concentrations when a pretreatment procedure was employed. In this way, linearity of calibration curves between 8.0×10^?8 M and 2.4×10^?7 M and detection limit of 1.0×10^?7 M, were observed. On the other hand, the standard addition method was also used as an alternative and an appropriated quantification technique for this system. A linear concentration range between 1.0×10^?6 M and 2.7×10^?5 M, with a correlation coefficient of 0.997, was obtained. This procedure has also a promising application in the separation of herbicides from other interferents, present in real samples, previous to their quantification.     

Host–Guest Complexation of Amphiphilic Molecules at the Air–Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen

The oxidation of antioxidants by oxidizers imposes great challenges to both living organisms and the food industry. Here we show that the host–guest complexation of the carefully designed, positively charged, amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A-12C) and negatively charged oleic acid (OA), a well-known cell membrane antioxidant, prevents the oxidation of the complex monolayers at the air–water interface from two potent oxidizers hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field-induced droplet ionization mass spectrometry results have demonstrated that the host–guest complexation achieves steric shielding and prevents both types of oxidation as a result of the tight and “sleeved in” physical arrangement, rather than the chemical reactivity, of the complexes.