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The energy storage performances of supercapacitors are expected to be enhanced by the use of nanostructured hierarchically micro/mesoporous hollow carbon materials based on their ultra-high specific surface areas and rapid diffusion of electrolyte ions through the interconnected channels of their mesoporous structures. In this work, we report the electrochemical supercapacitance properties of hollow carbon spheres prepared by high-temperature carbonization of self-assembled fullerene-ethylenediamine hollow spheres (FE-HS). FE-HS, having an average external diameter of 290 nm, an internal diameter of 65 nm, and a wall thickness of 225 nm, were prepared by using the dynamic liquid-liquid interfacial precipitation (DLLIP) method at ambient conditions of temperature and pressure. High temperature carbonization (at 700, 900, and 1100 °C) of the FE-HS yielded nanoporous (micro/mesoporous) hollow carbon spheres with large surface areas (612 to 1616 m 2 g -1 ) and large pore volumes (0.925 to 1.346 cm 3 g -1 ) dependent on the temperature applied. The sample obtained by carbonization of FE-HS at 900 °C (FE-HS_900) displayed optimum surface area and exhibited remarkable electrochemical electrical double-layer capacitance properties in aq. 1 M sulfuric acid due to its well-developed porosity, interconnected pore structure, and large surface area. For a three-electrode cell setup, a specific capacitance of 293 F g -1 at a 1 A g -1 current density, which is approximately 4 times greater than the specific capacitance of the starting material, FE-HS. The symmetric supercapacitor cell was assembled using FE-HS_900 and attained 164 F g -1 at 1 A g -1 with sustained 50% capacitance at 10 A g -1 accompanied by 96% cycle life and 98% coulombic efficiency after 10,000 consecutive charge/discharge cycles. The results demonstrate the excellent potential of these fullerene assemblies in the fabrication of nanoporous carbon materials with the extensive surface areas required for high-performance energy storage supercapacitor applications.

The fabrication of various sensing devices and the ability to harmonize materials for a higher degree of organization is essential for effective sensing systems. Materials with hierarchically micro- and mesopore structures can enhance the sensitivity of sensors. Nanoarchitectonics allows for atomic/molecular level manipulations that create a higher area-to-volume ratio in nanoscale hierarchical structures for use in ideal sensing applications. Nanoarchitectonics also provides ample opportunities to fabricate materials by tuning pore size, increasing surface area, trapping molecules via host-guest interactions, and other mechanisms. Material characteristics and shape significantly enhance sensing capabilities via intramolecular interactions, molecular recognition, and localized surface plasmon resonance (LSPR). This review highlights the latest advancements in nanoarchitectonics approaches to tailor materials for various sensing applications, including biological micro/macro molecules, volatile organic compounds (VOC), microscopic recognition, and the selective discrimination of microparticles. Furthermore, different sensing devices that utilize the nanoarchitectonics concept to achieve atomic-molecular level discrimination are also discussed.

Nanoarchitectonics integrates nanotechnology with numerous scientific disciplines to create innovative and novel functional materials from nano-units (atoms, molecules, and nanomaterials). The objective of nanoarchitectonics concept is to develop functional materials and systems with rationally architected functional units. This paper explores the progress and potential of this field using biomass nanoarchitectonics for supercapacitor applications as examples of energetic materials and devices. Strategic design of nanoporous carbons that exhibit ultra-high surface area and hierarchically pore architectures comprising micro- and mesopore structure and controlled pore size distributions are of great significance in energy-related applications, including in high-performance supercapacitors, lithium-ion batteries, and fuel cells. Agricultural wastes or natural biomass are lignocellulosic materials and are excellent carbon sources for the preparation of hierarchically porous carbons with an ultra-high surface area that are attractive materials in high-performance supercapacitor applications due to high electrical and ion conduction, extreme porosity, and exceptional chemical and thermal stability. In this review, we will focus on the latest advancements in the fabrication of hierarchical porous carbon materials from different biomass by chemical activation method. Particularly, the importance of biomass-derived ultra-high surface area porous carbons, hierarchical architectures with interconnected pores in high-energy storage, and high-performance supercapacitors applications will be discussed. Finally, the current challenges and outlook for the further improvement of carbon materials derived from biomass or agricultural wastes in the advancements of supercapacitor devices will be discussed.

The electrical double-layer supercapacitance performance of the nanoporous carbons prepared from the Phyllanthus emblica (Amala) seed by chemical activation using the potassium hydroxide (KOH) activator is reported. KOH activation was carried out at different temperatures (700-1000 °C) under nitrogen gas atmosphere, and in a three-electrode cell set-up the electrochemical measurements were performed in an aqueous 1 M sulfuric acid (H 2 SO 4 ) solution. Because of the hierarchical pore structures with well-defined micro- and mesopores, Phyllanthus emblica seed-derived carbon materials exhibit high specific surface areas in the range of 1360 to 1946 m 2 g -1 , and the total pore volumes range from 0.664 to 1.328 cm 3 g -1 . The sample with the best surface area performed admirably as the supercapacitor electrode-material, achieving a high specific capacitance of 272 F g -1 at 1 A g -1 . Furthermore, it sustained 60% capacitance at a high current density of 50 A g -1 , followed by a remarkably long cycle-life of 98% after 10,000 subsequent charging/discharging cycles, demonstrating the electrode's excellent rate-capability. These results show that the Phyllanthus emblica seed would have significant possibilities as a sustainable carbon-source for the preparing high-surface-area activated-carbons desired in high-energy-storage supercapacitors.

Biomass-derived activated carbon materials with hierarchically nanoporous structures containing nitrogen functionalities show excellent electrochemical performances and are explored extensively in energy storage and conversion applications. Here, we report the electrochemical supercapacitance performances of the nitrogen-doped activated carbon materials with an ultrahigh surface area prepared by the potassium hydroxide (KOH) activation of the Nelumbo nucifera (Lotus) seed in an aqueous electrolyte solution (1 M sulfuric acid: H 2 SO 4 ) in a three-electrode cell. The specific surface areas and pore volumes of Lotus-seed-derived carbon materials carbonized at a different temperatures, from 600 to 1000 °C, are found in the range of 1059.6 to 2489.6 m 2 g -1 and 0.819 to 2.384 cm 3 g -1 , respectively. The carbons are amorphous materials with a partial graphitic structure with a maximum of 3.28 atom% nitrogen content and possess hierarchically micro- and mesoporous structures. The supercapacitor electrode prepared from the best sample showed excellent electrical double-layer capacitor performance, and the electrode achieved a high specific capacitance of ca. 379.2 F g -1 at 1 A g -1 current density. Additionally, the electrode shows a high rate performance, sustaining 65.9% capacitance retention at a high current density of 50 A g -1 , followed by an extraordinary long cycle life without any capacitance loss after 10,000 subsequent charging/discharging cycles. The electrochemical results demonstrate that Nelumbo nucifera seed-derived hierarchically porous carbon with nitrogen functionality would have a significant probability as an electrical double-layer capacitor electrode material for the high-performance supercapacitor applications.

A constructed wetland (CW) is a low-cost, eco-friendly, easy-to-maintain, and widely applicable technology for treating various pollutants in the waste landfill leachate. This study determined the effects of the selection and compiling strategy of substrates used in CWs on the treatment performance of a synthetic leachate containing bisphenol A (BPA) as a representative recalcitrant pollutant. We operated five types of lab-scale vertical-flow CWs using only gravel (CW1), a sandwich of gravel with activated carbon (CW2) or brick crumbs (CW3), and two-stage hybrid CWs using gravel in one column and activated carbon (CW4) or brick crumbs (CW5) in another to treat synthetic leachate containing BPA in a 7-d sequential batch mode for 5 weeks. CWs using activated carbon (CW2 and CW4) effectively removed ammonium nitrogen (NH 4 -N) (99-100%), chemical oxygen demand (COD) (93-100%), and BPA (100%), indicating that the high adsorption capacity of activated carbon was the main mechanism involved in their removal. CW5 also exhibited higher pollutant removal efficiencies (NH 4 -N: 94-99%, COD: 89-98%, BPA: 89-100%) than single-column CWs (CW1 and CW3) (NH 4 -N: 76-100%, COD: 84-100%, BPA: 51-100%). This indicates the importance of the compiling strategy along with the selection of an appropriate substrate to improve the pollutant removal capability of CWs.

Of the available environmentally friendly energy storage devices, supercapacitors are the most promising because of their high energy density, ultra-fast charging-discharging rate, outstanding cycle life, cost-effectiveness, and safety. In this work, nanoporous carbon materials were prepared by applying zinc chloride activation of lotus seed powder from 600 °C to 1000 °C and the electrochemical energy storage (supercapacitance) of the resulting materials in aqueous electrolyte (1M H 2 SO 4 ) are reported. Lotus seed-derived activated carbon materials display hierarchically porous structures comprised of micropore and mesopore architectures, and exhibited excellent supercapacitance performances. The specific surface areas and pore volumes were found in the ranges 1103.0-1316.7 m 2 g -1 and 0.741-0.887 cm 3 g -1 , respectively. The specific capacitance of the optimum sample was ca. 317.5 F g -1 at 5 mV s -1 and 272.9 F g -1 at 1 A g -1 accompanied by high capacitance retention of 70.49% at a high potential sweep rate of 500 mV s -1 . The electrode also showed good rate capability of 52.1% upon increasing current density from 1 to 50 A g -1 with exceptional cyclic stability of 99.2% after 10,000 cycles demonstrating the excellent prospects for agricultural waste stuffs, such as lotus seed, in the production of the high performance porous carbon materials required for supercapacitor applications.

Ionic self-assembly is a simple yet powerful method to obtain robust nanostructures. Herewith, we use mixtures of oppositely-charged porphyrins that can act as mesogens to form chromonic liquid crystals in water, i.e., molecular stacks with orientational (nematic) or positional (hexagonal) order. Electrostatic locking coupled with π-π interactions between aromatic groups within the stacks, together with inter-stack hydrogen bonding induce formation of all-organic crystalline nanofibers with high aspect ratio (a few tenths of nanometers in width but several tenths of micrometers in length) and that display branching. The nanofibers prepared from metal-free porphyrin units feature interesting optical properties, including an absorption spectrum that is different from the simple sum of the individual spectra of the components, which is attributed to a striking aggregation-induced chromism. When in contact with some polar organic solvents the materials become fluorescent, as a result of disaggregation. In a proof-of-concept, the obtained self-assembled one-dimensional (1D) materials were carbonized (yield ca. 60%) to produce nitrogen-doped carbon nanofibers that can be used as active electrode materials for energy storage applications.

Sacrococcygeal teratoma is rare and happens in 1:35,000 to 40,000 live births. It is more common in girls than boys with the reported ratio of 3:1 to 4:1. We herein report an unusual case of a huge sacrococcygeal teratoma, which was more than half of the size and weight of the baby which was terminated at 24 weeks of gestation.

We have demonstrated a highly sensitive moisture sensor that can detect water molecules, in addition to water droplets, and therefore, can predict dew condensation with high accuracy and high speed before the formation of water droplets, showing a better performance than a commercial hygrometer. Additionally, the dependence of the output response from the sensor on factors, such as the cooling rate of the sensor's surface and the vapor pressure in the chamber, that affect the performance of the moisture sensor has been clarified. The output response showed a clear dependence on the variation in cooling rate, as well as the vapor pressure. The higher the cooling rate and vapor pressure, the higher the output response. The output response showed a linear response to the change in the above-mentioned parameters. The higher sensitivity and accuracy of the moisture sensor, as a function of the physical parameters, such as cooling rates, vapor pressure, enables the sensor to perform in advanced detection applications. The sensor can be modified to the actual target regarding the surface nature and the heat capacity of the target object, making it more suitable for wide applications.

Nanoporous activated carbons-derived from agro-waste have been useful as suitable and scalable low-cost electrode materials in supercapacitors applications because of their better surface area and porosity compared to the commercial activated carbons. In this paper, the production of nanoporous carbons by zinc chloride activation of Washnut seed at different temperatures (400-1000 °C) and their electrochemical supercapacitance performances in aqueous electrolyte (1 M H 2 SO 4 ) are reported. The prepared nanoporous carbon materials exhibit hierarchical micro- and meso-pore architectures. The surface area and porosity increase with the carbonization temperature and achieved the highest values at 800 °C. The surface area was found in the range of 922-1309 m 2 g -1 . Similarly, pore volume was found in the range of 0.577-0.789 cm 3 g -1 . The optimal sample obtained at 800 °C showed excellent electrochemical energy storage supercapacitance performance. Specific capacitance of the electrode was calculated 225.1 F g -1 at a low current density of 1 A g -1 . An observed 69.6% capacitance retention at 20 A g -1 indicates a high-rate capability of the electrode materials. The cycling stability test up to 10,000 cycles revealed the outstanding stability of 98%. The fascinating surface textural properties with outstanding electrochemical performance reveal that Washnut seed would be a feasible agro-waste precursor to prepare nanoporous carbon materials as a low-cost and scalable supercapacitor electrode., Competing Interests: The authors declare no conflict of interest.

Nanoporous activated carbon materials derived from agro-wastes could be suitable low-cost electrode materials for high-rate performance electrochemical supercapacitors. Here we report high surface area nanoporous carbon materials derived from Lapsi seed agro-waste prepared by zinc chloride (ZnCl 2 ) activation at 700 °C. Powder X-ray diffraction (pXRD) and Raman scattering confirmed the amorphous structure of the resulting carboniferous materials, which also incorporate oxygen-containing functional groups as confirmed by Fourier transform infrared (FTIR) spectroscopy. Scanning and transmission electron microscopy (SEM and TEM) analyses revealed the granular, nanoporous structures of the materials. High-resolution TEM (HR-TEM) confirmed a graphitic carbon structure containing interconnected mesopores. Surface areas and pore volumes of the materials were found, respectively, in the ranges from 931 to 2272 m 2 g -1 and 0.998 to 2.845 cm 3 g -1 , and are thus superior to commercially available activated carbons. High surface areas, large pore volumes and interconnected mesopore structures of these Lapsi seed-derived nanoporous carbon materials lead to their excellent electrochemical supercapacitance performance in aqueous electrolyte (1 M H 2 SO 4 ) with a maximum specific capacitance of 284 F g -1 at a current density of 1 A g -1 . Furthermore, the electrodes showed high-rate capability sustaining 67.7% capacity retention even at high current density of 20 A g -1 with excellent cycle stability achieving 99% capacitance retention even after 10,000 charge-discharge cycles demonstrating the potential of Lapsi seed derived nanoporous carbons as suitable electrode materials in high-performance supercapacitor devices.

High surface area and large pore volume carbon materials having hierarchical nanoporous structure are required in high performance supercapacitors. Such nanoporous carbon materials can be fabricated from organic precursors with high carbon content, such as synthetic biomass or agricultural wastes containing cellulose, hemicellulose, and lignin. Using recently developed unique concept of materials nanoarchitectonics, high performance porous carbons with controllable surface area, pore size distribution, and hierarchy in nanoporous structure can be fabricated. In this review, we will overview the recent trends and advancements on the synthetic methods for the production of hierarchical porous carbons with one- to three-dimensional network structure with superior performance in supercapacitors applications. We highlight the promising scope of accessing nanoporous graphitic carbon materials from: (i) direct conversion of single crystalline self-assembled fullerene nanomaterials and metal organic frameworks, (ii) hard- and soft-templating routes, and (iii) the direct carbonization and/or activation of biomass or agricultural wastes as non-templating routes. We discuss the appealing points of the different synthetic carbon sources and natural precursor raw-materials derived nanoporous carbon materials in supercapacitors applications.

A moisture sensor has been reported that detects invisibly small water droplets and distinguishes their particle size with high accuracy and high speed. This sensor uses narrow lines of dissimilar metals as electrodes, arranged with gaps of 0.5 to 10 μm. The working principle for this sensor is that it measures the galvanic current generated when a water droplet forms a bridge-like structure between the electrodes. In addition, the surface of the sensor was controlled by using hydrophilic polymer, GL, and hydrophobic polymer, PMMA. The study of the relationship between the contact angle, projected area of water droplets and current response from the sensor with a modified surface showed that in the case of GL, the contact angle was small (wettability increased) and the average value and distribution of the projected water droplet area and the sensor's response increased. This enhanced the sensor's sensitivity. On the other hand, in the case of PMMA, the contact angle was large (wettability decreased), the area of the water droplet and its distribution became small and the accuracy of discriminating the water droplet's diameter by the sensor enhanced. Therefore, by rendering sensor's surface hydrophilic and hydrophobic, the sensitivity and accuracy of the sensor could be enhanced.

Here we report the aromatic vapor sensing performance of bitter melon shaped nanoporous fullerene C 60 crystals that are self-assembled at a liquid-liquid interface between isopropyl alcohol and C 60 solution in dodecylbenzene at 25 °C. Average length and center diameter of the crystals were ca. 10 μm and ~2 μm, respectively. Powder X-ray diffraction pattern (pXRD) confirmed a face-centered cubic ( fcc ) structure with cell dimension ca. a = 1.4272 nm, and V = 2.907 nm³, which is similar to that of the pristine fullerene C 60 . Transmission electron microscopy (TEM) confirmed the presence of a nanoporous structure. Quartz crystal microbalance (QCM) results showed that the bitter melon shaped nanoporous C 60 performs as an excellent sensing system, particularly for aromatic vapors, due to their easy diffusion through the porous architecture and strong π⁻π interactions with the sp ²-carbon.

Arcobacter spp. are emerging pathogens associated with gastroenteritis in humans. The objective of this study was to develop a highly sensitive and broadly reactive quantitative PCR (qPCR) assay for Arcobacter spp. and to apply the developed assay to different water sources in the Kathmandu Valley, Nepal. Fifteen samples to be analyzed by next-generation sequencing were collected from 13 shallow dug wells, a deep tube well, and a river in the Kathmandu Valley in August 2015. Among the 86 potential pathogenic bacterial genera identified, Acinetobacter, Pseudomonas, Flavobacterium, and Arcobacter were detected with relatively high abundance in 15, 14, 12, and 8 samples, respectively. A primer pair was designed with maximal nucleotide homologies among Arcobacter spp. by comparing the sequences of 16S rRNA genes. These primers were highly specific to most of the known species of Arcobacter and quantified between 1.0×10 1 and 6.4×10 6 copies reaction -1 and sometimes detected as few as 3 copies reaction -1 . The qPCR assay was used to quantify Arcobacter spp. in bacterial DNA in not only the above 15 water samples, but also in 33 other samples collected from 15 shallow dug wells, 6 shallow tube wells, 5 stone spouts, 4 deep tube wells, and 3 springs. Thirteen (27%) out of 48 samples tested were positive for Arcobacter spp., with concentrations of 5.3-9.1 log copies 100 mL -1 . This qPCR assay represents a powerful new tool to assess the prevalence of Arcobacter spp. in environmental water samples.

A hierarchical heterostructure composed of silver nanoparticles (Ag-NPs: average diameter ∼10 nm) on fullerene nanorods (FNRs: average length ∼11 μm and average diameter ∼200 nm) was fabricated using a simple solution route. It was used as an effective single particle freestanding surface enhanced Raman scattering (SERS) substrate for the detection of target molecules (Rhodamine 6G: R6G). FNRs were formed ultra-rapidly (formation process completed in a few seconds) at a liquid-liquid interface of methanol and C60/mesitylene solution then Ag-NPs were grown directly on the surfaces of the FNRs by treatment with a solution of silver nitrate in ethanol. This unique hierarchical heterostructure allows efficient adsorption of target molecules also acting as an effective SERS substrate capable of detecting the adsorbed R6G molecules in the nanomolar concentration range. In this study, SERS spectra are acquired on an isolated single Ag-FNR for the detection of the absorbed molecule rather than from a bulk, large area film composed of silver/gold nanoparticles as used in conventional methods. Thus, this work provides a new approach for the design and fabrication of freestanding SERS substrates for molecular detection applications.

This report describes the controlled viscosity changes of photoresponsive reverse wormlike micellar systems formed by soybean lecithin (SoyPC), d-ribose, and azobenzene derivatives in decane. UV light irradiation produces a significant (150-fold) decrease in solution viscosity by triggering a structural transformation of the wormlike micelles. Subsequent visible light irradiation leads to recovery of the initial micellar structure and elevated solution viscoelasticity. This dramatic, reversible variation in solution viscosity by light irradiation can be applied to cosmetics, personal care products, and device components., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Fullerene C 60 microbelts were fabricated using the liquid-liquid interfacial precipitation method and converted into quasi 2D mesoporous carbon microbelts by heat treatment at elevated temperatures of 900 and 2000 °C. The carbon microbelts obtained by heat treatment of fullerene C 60 microbelts at 900 °C showed excellent electrochemical supercapacitive performance, exhibiting high specific capacitances ca. 360 F g -1 (at 5 mV s -1 ) and 290 F g -1 (at 1 A g -1 ) because of the enhanced surface area and the robust mesoporous framework structure. Additionally, the heat-treated carbon microbelt showed good rate performance, retaining 49% of capacitance at a high scan rate of 10 A g -1 . The carbon belts exhibit super cyclic stability. Capacity loss was not observed even after 10 000 charge/discharge cycles. These results demonstrate that the quasi 2D mesoporous carbon microbelts derived from a π-electron-rich carbon source, fullerene C 60 crystals, could be used as a new candidate material for electrochemical supercapacitor applications.

A method for controlling the self-assembly of fullerene C 60 molecules into nanotubules in the fcc phase, devoid of entrapped solvent, has been established in a thin film microfluidic device. The micron length C 60 nanotubules, with individual hollow diameters of 100 to 400 nm, are formed under continuous flow processing during high shear micromixing of water and a toluene solution of the fullerene, in the absence of surfactant, and without the need for further down-stream processing. TEM revealed pores on the surface of the nanotubes, and the isolated material has a much higher response to small molecule sensing than that for analogous material formed using multistep batch processing., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Here, we report the structural and morphological modulation of fullerene C 60 crystals induced by nonionic surfactants diglycerol monolaurate (C 12 G 2 ) and monomyristate (C 14 G 2 ). C 60 crystals synthesized at a liquid-liquid interface comprising isopropyl alcohol (IPA) and a saturated solution of C 60 in ethylbenzene (EB) exhibited a one-dimensional (1D) morphology with well-defined faceted structure. Average length and diameter of the faceted rods were ca. 4.8 μm and 747 nm, respectively. Powder X-ray diffraction pattern (pXRD) confirmed a hexagonal-close packed (hcp) structure with cell dimensions ca. a = 2.394 nm and c = 1.388 nm. The 1D rod morphology of C 60 crystals was transformed into "Konpeito candy-like" crystals (average diameter ca. 1.2 μm) when the C 60 crystals were grown in the presence of C 12 G 2 or C 14 G 2 surfactant (1%) in EB. The pXRD spectra of "Konpeito-like" crystals could be assigned to the face-centered cubic (fcc) phase with cell dimensions ca. a = 1.4309 nm (for C 12 G 2 ) and a = 1.4318 nm (for C 14 G 2 ). However, clusters or aggregates of C 60 lacking a uniform morphology were observed at lower surfactant concentrations (0.1%), although these crystals exhibited an fcc crystal structure. The self-assembled 1D faceted C 60 crystals and "Konpeito-like" C 60 crystals exhibited intense photoluminescence (PL) (∼35 times greater than pC 60 ) and a blue-shifted PL intensity maximum (∼15 nm) compared to those of pC 60 , demonstrating the potential use of this method for the control of the optoelectronic properties of fullerene nanostructures. The "Konpeito-like" crystals were transformed into high surface area nanoporous carbon with a graphitic microstructure upon heat-treatment at 2000 °C. The heat-treated samples showed enhanced electrochemical supercapacitance performance (specific capacitance is ca. 175 F g -1 , which is about 20 times greater than pC 60 ) with long cyclic stability demonstrating the potential of the materials in supercapacitor device fabrication.

Carbon nanofibers (CNFs) with high surface area (820 m 2 /g) have been successfully prepared by a nanocasting approach using silica nanofibers obtained from chromonic liquid crystals as a template. CNFs with randomly oriented graphitic layers show outstanding electrochemical supercapacitance performance, exhibiting a specific capacitance of 327 F/g at a scan rate of 5 mV/s with a long life-cycling capability. Approximately 95% capacitance retention is observed after 1000 charge-discharge cycles. Furthermore, about 80% of capacitance is retained at higher scan rates (up to 500 mV/s) and current densities (from 1 to 10 A/g). The high capacitance of CNFs comes from their porous structure, high pore volume, and electrolyte-accessible high surface area. CNFs with ordered graphitic layers were also obtained upon heat treatment at high temperatures (>1500 °C). Although it is expected that these graphitic CNFs have increased electrical conductivity, in the present case, they exhibited lower capacitance values due to a loss in surface area during thermal treatment. High-surface-area CNFs can be used in sensing applications; in particular, they showed selective differential adsorption of volatile organic compounds such as pyridine and toluene. This behavior is attributed to the free diffusion of these volatile aromatic molecules into the pores of CNFs accompanied by interactions with sp 2 carbon structures and other chemical groups on the surface of the fibers.

We have investigated the textural properties, electrochemical supercapacitances and vapor sensing performances of bamboo-derived nanoporous carbon materials (NCM). Bamboo, an abundant natural biomaterial, was chemically activated with phosphoric acid at 400 °C and the effect of impregnation ratio of phosphoric acid on the textural properties and electrochemical performances was systematically investigated. Fourier transform-infrared (FTIR) spectroscopy confirmed the presence of various oxygen-containing surface functional groups (i.e. carboxyl, carboxylate, carbonyl and phenolic groups) in NCM. The prepared NCM are amorphous in nature and contain hierarchical micropores and mesopores. Surface areas and pore volumes were found in the range 218-1431 m 2 g -1 and 0.26-1.26 cm 3 g -1 , respectively, and could be controlled by adjusting the impregnation ratio of phosphoric acid and bamboo cane powder. NCM exhibited electrical double-layer supercapacitor behavior giving a high specific capacitance of c .256 F g -1 at a scan rate of 5 mV s -1 together with high cyclic stability with capacitance retention of about 92.6% after 1000 cycles. Furthermore, NCM exhibited excellent vapor sensing performance with high sensitivity for non-aromatic chemicals such as acetic acid. The system would be useful to discriminate C 1 and C 2 alcohol (methanol and ethanol).

Conjugated polymers with strong photophysical properties are used in many applications. A homopolymer (P1) and five new low band gap copolymers based on 4,4'-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) and acceptors 3,6-dithienyldiketopyrrolopyrrole (P2), phthalimide (P3), benzotriazole (P4), 4,7-dithienyl[1,2,3]triazolo[4,5g]quinoxaline (P5), and 2,5-dithienylthieno[3,4-b]pyrazine (P6) were prepared by means of Sonogashira polymerization. The characterization of polymers by using (1) H NMR, absorption, and emission spectroscopy is discussed. All polymers with high molecular weights (Mn ) of 16 000 to 89 000 g mol(-1) showed absorption maxima in the deep-red region (λ=630-760 nm) in solution and exhibited significant redshifts (up to 70 nm) in thin films. Polymers P2, P5, and P6 showed narrow optical band gaps of 1.38, 1.35, and 1.38 eV, respectively, which are significantly lower than that of P1 (1.63 eV). The HOMO and LUMO energy levels of the polymers were calculated by using cyclic voltammetry measurements. The LUMO energy levels of BODIPY-based alternating copolymers were independent of the acceptors; this suggests that the major factor that tunes the LUMO energy levels of the polymers could be the BODIPY core. All polymers showed selective and reproducible detection of volatile organic solvents, such as toluene and benzene, which could be used for developing sensors., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Bacterial meningitis in children is a life-threatening problem resulting in severe morbidity and mortality. For the prompt initiation of antibacterial therapy, rapid and reliable diagnostic methods are of utmost importance. Therefore, this study was designed to find out the rate of bacterial pathogens of meningitis from suspected cases by performing conventional methods and latex agglutination., Methods: A descriptive type of study was carried out from May 2012 to April 2013. Cerebrospinal fluid (CSF) specimens from 252 suspected cases of meningitis were subjected for Gram staining, bacterial culture and latex agglutination test. The identification of growth of bacteria was done following standard microbiological methods recommended by American Society for Microbiology. Antibiotic sensitivity testing was done by modified Kirby-Bauer disk diffusion method., Results: From the total 252 suspected cases, 7.2 % bacterial meningitis was revealed by Gram staining and culture methods whereas latex agglutination method detected 5.6 %. Gram-negative organisms contributed the majority of the cases (72.2 %) with Haemophilus influenzae as the leading pathogen for meningitis. Overall, 33.3 % mortality rate was found., Conclusions: In conclusion, a significant rate of bacterial meningitis was found in this study prompting concern for national wide surveillance.

Amphiphiles, molecules that possess both hydrophilic and hydrophobic moieties, are architecturally simple molecules that can spontaneously self-assemble into complex hierarchical structures from lower to higher dimensions either in the bulk phase or at an interface. Recent developments in multifunctional nanostructure design using the advanced concept of nanoarchitectonics utilize this simple process of assembly. Amphiphilic self-assemblies involving lipids or proteins mimic the structure of biological systems, thus highlighting the necessity of a fundamental physical understanding of amphiphilic self-assembly towards a realization of the complex mechanisms operating in nature. Herein, we describe self-assembled microstructures of biocompatible and biodegradable tetraglycerol lauryl ether (C12G4) nonionic surfactant in an aqueous solvent system. Temperature-composition analyses of equilibrium phases identified by using small-angle x-ray scattering (SAXS) provide strong evidence of various spontaneously self-assembled mesostructures, such as normal micelles (Wm), hexagonal liquid crystal (H1), and reverse micelles (Om). In contrast to conventional poly(oxyethylene) nonionic surfactants, C12G4 did not exhibit the clouding phenomenon at higher temperatures (phase separation was not observed up to 100 °C), demonstrating the greater thermal stability of the self-assembled mesophases. Generalized indirect Fourier transformation (GIFT) evaluation of the SAXS data confirmed the formation of core-shell-type spherical micelles with a maximum dimension ca. 8.7 nm. The shape and size of the C12G4 micelles remained apparently unchanged over a wide range of concentrations (up to 20%), but intermicellar interactions increased and could be described by the Percus-Yevick (PY) theory (after Carnahan and Starling), which provides a very accurate analytical expression for the osmotic pressure of a monodisperse hard sphere.

Here we present self-assembled nanostructure of functional molecule fullerene (C60) at liquid-liquid interface. The nanostructured nanocrystals were grown at liquid-liquid interface of isopropyl alcohol (IPA) and C60 solution in butylbenzene under ambient condition of temperature and pressure, and characterized by Raman scattering, power X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The crystal formation mechanism is driven by supersaturation related to the low solubility of C60 in IPA. A slow diffusion of IPA towards the C60 solution causes unsaturation of C60 at the liquid-liquid interface and consequently small clusters of C60 is formed at the interface, which acts as the nucleation site. Further diffusion of IPA supplies the C60 molecules from bulk to the interface promoting the crystal growth. Based on SEM and TEM observation, the average size of the individual hexagonal bipyramid nanocrystal is found to be ca. 1.4 µm and the average size of their assembly is found to be approximately 2 µm. XRD measurements have shown that these materials are crystalline with mixed face-centered cubic (cell dimension: a = 1.352 nm, and V = 2.475 nm3) and hexagonal (cell dimension: a = 1.452 nm, c = 1.207 nm, c/a = 0.831, and V = 2.475 nm3) structures. Raman scattering measurements showed two Ag and six Hg vibration bands, which are similar to those obtained in the pristine C60.

Here we report the thermal conversion of one-dimensional (1D) fullerene (C60) single-crystal nanorods and nanotubes to nanoporous carbon materials with retention of the initial 1D morphology. The 1D C60 crystals are heated directly at very high temperature (up to 2000 °C) in vacuum, yielding a new family of nanoporous carbons having π-electron conjugation within the sp(2)-carbon robust frameworks. These new nanoporous carbon materials show excellent electrochemical capacitance and superior sensing properties for aromatic compounds compared to commercial activated carbons., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We demonstrate ultrarapid interfacial formation of one-dimensional (1D) single-crystalline fullerene C60 nanorods at room temperature in 5 s. The nanorods of ∼ 11 μm in length and ∼ 215 nm in diameter are developed in a hexagonal close-pack crystal structure, contrary to the cubic crystal structure of pristine C60. Vibrational and electronic spectroscopy provide strong evidence that the nanorods are a van der Waals solid, as evidenced from the preservation of the electronic structure of the C60 molecules within the rods. Steady state optical spectroscopy reveals a dominance of charge transfer excitonic transitions in the nanorods. A significant enhancement of photogenerated charge carriers is observed in the nanorods in comparison to pristine C60, revealing the effect of shape on the photovoltaic properties. Due to their ultrarapid, large-scale, room-temperature synthesis with single-crystalline structure and excellent optoelectronic properties, the nanorods are expected to be promising for photosensitive devices applications.

In this paper, we report the one-step synthesis of metallic silver nanoparticles (Ag NP) using nonionic surfactant reverse micelle as nanoreactors. Diglycerol monolaurate (C12G2) spontaneously self-assemble into spheroid reverse micelles having size 10-12 nm in cyclohexane under ambient conditions of temperature and pressure. The spheroid C12G2 reverse micelles swell with water. Swollen reverse micelles having size - 20 nm are formed upon incorporation of 1% water. We used C12G2 reverse micelles as nanoreactors for making ordered nanostructure of Ag-NP by replacing water with aqueous silver nitrate solution. The diglycerol moiety of the surfactant reduces silver ions into metallic silver and thereby stabilizes the generated Ag NP. We found that shape and size of the Ag NP is closely related to the structure of nanoreactor. Similar results have been observed in linear chain alkane n-octane. We found bigger Ag NP from the C12G2/octane reverse micelle system as the size of the micelle in this system is bigger than that of the C12G2/cyclohexane system. This simple approach based on in-situ reduction of metal ions (without the need of reducing agent) opens a new possibility for the development of controlled synthesis of nanostructured noble metallic nanoparticles.

We studied the effects of the spacer chain length of amino acid-based gemini surfactants on the formation of wormlike micelles in aqueous solutions. The surfactants used were synthesized by reacting dodecanoylglutamic acid anhydride with diamine compounds (ethylenediamine, pentanediamine, and octanediamine), and were abbreviated as 12-GsG-12 (s: the spacer chain length of 2, 5, and 8 methylene units). These surfactants yielded viscoelastic wormlike micellar solutions at pH 9 upon mixing with a cationic monomeric surfactant, hexadecyltrimethylammonium bromide (HTAB). We found that the rheological behavior was strongly dependent on the spacer chain length and HTAB concentration. When the shortest spacer chain analogue (12-G2G-12) was used, an increased HTAB concentration resulted in the following structural transformations of the micelles: (i) spherical or rodlike micelles; (ii) anionic wormlike micelles exhibiting a transient network structure; (iii) anionic wormlike micelles with a micellar branching or interconnected structure; and (iv) cationic wormlike micelles. Similarly, when the middle spacer chain analogue (12-G5G-12) was used, a structural transformation from anionic to cationic wormlike micelles occurs; however, molecular aggregates with a lower positive curvature were also formed in this transition region. When the longest spacer analogue (12-G8G-12) was used, the formation of cation-rich molecular aggregates was not observed. These transition behaviors were attributed to the packing geometry of the gemini surfactants with HTAB. Additionally, as the spacer chain length increased, the zero-shear viscosity in the anionic wormlike micellar region decreased, suggesting limited one-dimensional micellar growth of spherical, rodlike, or anionic wormlike micelles.

The principles, occurrence, structure and properties of worm-like micellar solutions in nonionic surfactant systems is reviewed, with focus in certain experimental methods used to characterize such soft nanostructured systems. Formulation plays a critical role in the design of worm-like micellar systems and derived viscoelastic networks. Micellar growth in one dimension, and hence formation of worm-like aggregates, is favoured by an increase in the average surfactant molecular packing parameter. Such an increase can be induced by addition of cosurfactant or amphiphilic oil that tends to penetrate in the surfactant palisade layer and reduce the specific surface area. On the other hand, long and bulky oils prone to be solubilized in the micellar core, cause a rod-sphere transition and therefore a decrease in viscosity. Salts have a small effect on the behaviour of nonionic worm-like micelles, contrary to what is found for ionic surfactant systems. The effect of raising temperature on worm-like micellar solutions is the result of a balance between the dehydration of the surfactant head groups, which favors elongation, the kinetics of micellar disruption and the formation of structures with nearly zero curvature. Therefore, a viscosity maximum as a function of temperature is found in many systems. Reverse worm-like micelles with a hydrophilic core can also be formed in organic solvents, even in the absence of ionic components or water. Worm-like micelles are useful as templates for the formation of ordered mesoporous oxides. The interaction of micelles with silica species results in the formation of silica-surfactant complexes that later precipitate as hexagonal phase via a cooperative mechanism.

Recently, we have reported a new cinnamic acid-type photocleavable surfactant, C4-C-N-PEG9 that experiences a photocleavage through UV-induced cyclization in aqueous solution, yielding a coumarin derivative (7-butoxy-2H-chromen-2-one) and an aminated polyoxyethylene compound. Here, we have studied the effects of C4-C-N-PEG9 on the photorheological behavior of viscoelastic wormlike micelles formed by aqueous mixture of nonionic surfactants, polyoxyethylene phytosterol ether (PhyEO20) and tetraoxyethylene dodecyl ether (C12EO4). The 4.9 wt % PhyEO20/H2O + 2.4 wt % C12EO4 solution forms wormlike micelles, and its viscosity is ~10 Pa·s. We have found that the addition of C4-C-N-PEG9 into this viscous, non-Newtonian fluid system decreases the viscosity. Viscosity decreased in parallel to the C4-C-N-PEG9 concentration reaching ~0.003 Pa·s at 2.5 wt % of C4-C-N-PEG9. However, viscosity of the C4-C-N-PEG9 incorporated system increased significantly (~200 times at 1.5 wt % of C4-C-N-PEG9 system) upon UV irradiation. Small-Angle X-ray scattering studies have shown that addition of C4-C-N-PEG9 favors wormlike-to-sphere type transition in the micellar structure. However, UV irradiation in the C4-C-N-PEG9 incorporated system causes one-dimensional micellar growth. Since C4-C-N-PEG9 has relatively bigger headgroup size compared to the C12EO4, addition of C4-C-N-PEG9 into wormlike micelles reduces the critical packing parameter resulting in the formation of spherical aggregates. UV irradiation induced one-dimensional micellar growth is caused due to photocleavage of the C4-C-N-PEG9 into a less surface-active coumarin derivative and an aminated polyoxyethylene compound, as confirmed by UV-vis spectrometry and HPLC measurements. The hydrophobic coumarin derivative formed after cleavage of C4-C-N-PEG9 goes to the micellar core and is responsible for decreasing the viscosity. However, the hydrophilic aminated polyoxyethylene prefers to reside at the vicinity of headgroup of PhyEO20 reducing the interhead repulsion, increasing the critical packing parameter and the viscosity as well.

This review briefly summarizes recent developments in fabrication techniques of shape-controlled nanostructures of fullerene crystals across different length scales and the self-assembled mesostructures of functionalized fullerenes both in solutions and solid substrates.

We report shape, size, and internal cross-sectional structure of diglycerol monomyristate (C₁₄G₂) reverse micelles in n-hexadecane near the critical point using small-angle X-ray scattering (SAXS). Pair-distance distribution function, p(r), which gives structural information in real-space, was obtained by indirect Fourier transformation (IFT) method. The p(r) showed a clear picture of rodlike micelles at higher temperatures well above the critical point (micellar solution phase separates into two immiscible liquids at ~ 48°C). At a fixed surfactant concentration (5% C₁₄G₂), decrease in temperature increases the micellar size monotonously and surprisingly shape of the p(r) curve at 50°C; close to the critical point, mimics the shape of the two dimensional disk-like micelles indicating the onset of critical fluctuations (attractive interactions among rodlike micelles forming a weak network). A similar behavior has been observed with normal micelles in aqueous system near the critical point. When the system is heated to 60°C, shape of the p(r) curve regains rodlike structure. At fixed temperature of 60°C, increase in C₁₄G₂ concentration induced one dimensional micellar growth. Maximum length of micelles increases from ca. 23.5 to 46.0 nm upon increasing concentration from 1 to 12% keeping cross section diameter apparently unchanged at ca. 4.0 nm.

Rheological properties of alkyl dicarboxylic acid-alkylamine complex systems have been characterized. The complex materials employed in this study consist of an amino acid-based surfactant (dodecanoylglutamic acid, C12Glu) and a tertiary alkylamine (dodecyldimethylamine, C12DMA) or a secondary alkylamine (dodecylmethylamine, C12MA). (1)H NMR and mass spectroscopic data have suggested that C12Glu forms a stoichiometric 1:1 complex with C12DMA and C12MA. Rheological measurements have suggested that the complex systems yield viscoelastic wormlike micellar solutions and the rheological behavior is strongly dependent on the aqueous solution pH. This pH-dependent behavior results from the structural transformation of the wormlike micelles to occur in the narrow pH range 5.5-6.2 (in the case of C12Glu-C12DMA system); i.e., positive curved aggregates such as spherical or rodlike micelles tend to be formed at high pH values. Our current study offers a unique way to obtain viscoelastic wormlike micellar solutions by means of alkyl dicarboxylic acid-alkylamine complex as gemini-like amphiphiles.

Aqueous binary phase behavior of a peptide-based gemini amphiphile with glutamic acid and lysine as spacer group, acylglutamyllysilacylglutamate (m-GLG-m where m = 12, 14, and 16), has been reported over a wide range of concentration and temperature. Lauroylglutamyllysillauroylglutamate, 12-GLG-12, self-assembles into spherical micelles above critical micelle concentration (CMC). The micellar region extends up to 32 wt %, and an ordering of spherical micelles into micellar cubic phase, I(1), takes place at 33 wt % at 25 °C. The phase transition, I(1) - hexagonal liquid crystal, (H(1)) - lamellar liquid crystal, (L(α)) has been observed with further increase in concentration; moreover, mixed phases are also observed between the pure liquid crystal domains. Similar phases were observed with 16-GLG-16 above 50 °C (Krafft temperature). The partial ternary phase behavior shows that the micellar solutions of m-GLG-m can solubilize a large amount of cationic amphiphile, alkyltrimethylammonium bromide, C(n)TAB, (where n = 14 (TTAB) and 16 (CTAB)) at 25 °C. An addition of C(n)TAB to the aqueous solutions of 16-GLG-16 in a dilute region forms a transparent solution of viscoelastic wormlike micelles at very low concentration (0.25 wt %) even at ambient condition. A mixture of oppositely charged amphiphiles, m-GLG-m and C(n)TAB, exhibits synergism as a result the amphiphile layer curvature, becomes less positive, and favors the transition from sphere to rod to transient networks (wormlike micelles). The gemini amphiphile, 16-GLG-16, forms wormlike micelles at relatively low concentrations compared to others reported so far. Viscosity increases by six orders of magnitude compared to that of pure solvent. The hydrophobic chain length of m-GLG-m and coamphiphile affects the rheology; the maximum viscosity achieved with 16-GLG-16/H(2)O/CTAB is higher than that of 14-GLG-14/H(2)O/CTAB, 12-GLG-12/H(2)O/CTAB, and 16-GLG-16/H(2)O/TTAB systems. These temperature-sensitive systems exhibited viscoelastic behavior described by the Maxwell mechanical model with a single stress relaxation mode.

Using small-angle X-ray scattering (SAXS) we have investigated the shape and size of diglycerol monomyristate (designated as C14G2) nonionic surfactant reverse micelles in aromatic solvent ethylbenzene as a function of surfactant concentration, temperature, and water. When C14G2 is added into ethylbenzene globular type reverse micelles with maximum core diameter ca. 4.5 nm are formed under ambient conditions. The micellar structure (shape and size) did not change with the surfactant concentration. However, an increase in temperature decreased the micellar size due to an increase in the critical packing parameter (cpp). Surfactant becomes more lipophilic upon heating and the micellar curvature tends to become more negative at higher temperature. Addition of a small amount of water caused a significant micellar growth. For instance, incorporation of 0.3% water in the 5% C14G2/ethylbenzene system resulted in the formation of 2.1 time bigger micelles with a small water pool in the micellar core. Besides the micellar shape is modified into an ellipsoidal prolate, whose scenario can be understood in terms of hydration of the surfactant's headgroup. Hydration decreases the cpp and favors micellar growth. An increase of temperature of a water incorporated system decreased the micellar size due to dehydration, which is equivalent to rod-to-sphere type transition.

Reverse micelles formulation requires an inclusion of water or other polar molecules in the binary mixture of ionic surfactant and oil and generally exhibit spheroid geometry with a small aggregation number. Here, we report structure and rheology of charge-free (nonionic) reverse micelles in surfactant/oil systems. We have systematically investigated intrinsic parameters for the shape, size, and internal cross section structure control of such micelles using small-angle X-ray scattering (SAXS) and the rheometry. We found that diglycerol monomyristate (C14G2) when added into an aromatic organic liquid phenyloctane, spontaneously self-assembles into spheroid micelles with maximum diameter ca. 6.7 nm. Decrease in surfactant chain length favors globular-to-rod type transition and micellar aggregation number (N(agg)) increases significantly. On the other hand, increase in surfactant weight fraction induces one-dimensional (1-D) micellar growth; N(agg) increases in parallel to the surfactant concentration. Reverse micelles shrink with the rise of temperature, which is close to the rod-to-sphere type transition. However, water causes a significant micellar growth; N(agg) increases drastically, which shows that water not only increase reverse micellar size but also increases the number of surfactant molecules per micelle. All these microstructure transitions could be understood in terms of the modification of the critical packing parameter (cpp). The SAXS results are very well supported by the geometrical model fittings and rheometry.

Water induced microstructure transitions of diglycerol monolaurate (C(12)G(2)) reverse micelles in aromatic liquid ethylbenzene have been investigated using small-angle X-ray scattering (SAXS) and rheometry. The SAXS data have been evaluated by generalized indirect Fourier transformation (GIFT) and geometrical model fittings. We found that the C(12)G(2) spontaneously self-assembles into ellipsoidal prolate micelles in ethylbenzene under ambient conditions. The maximum diameter of the micellar core is ca. 5.0 nm. We noted that 5% C(12)G(2)/ethylbenzene solubilize 0.8% water and the water causes micellar growth; micellar size is ~ 3 times bigger than the empty micelles. Rheology data showed that viscosity of 5% C(12)G(2)/ethylbenzene increases with increase in the water concentration sustaining the SAXS results that the viscosity increase is caused due to micellar growth. We found that increase in temperature of the water incorporated system decreases micellar size, which is equivalent to a rod-to-sphere type transition. The water induced microstructure transformations can be explained in terms of critical packing parameter, cpp. Water hydrates hydrophilic headgroup of surfactant so that effective cross-sectional area of surfactant increases. As a result the cpp decreases and micelles grow. On the other hand, increasing temperature promotes interpenetration of solvent and surfactant chain as a result cpp increases due to decrease in the effective cross-sectional area of surfactant. Moreover dehydration may occur and micelles with more curved interface are formed due to increases in the cpp.

In this article, we provide direct evidence for 1-D micellar growth and the formation of a network structure in an aqueous system of poly(oxyethylene) cholesteryl ether (ChEO(20)) and lauryl diethanolamide (L-02) by rheometry, small-angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (cryo-TEM). The ChEO(20) self-assembles into spheroid micelles above the critical micelle concentration and undergoes a 1-D microstructural transition upon the incorporation of L-02, which because of its lipophilic nature tends to be solubilized into the micellar palisade layer and reduces the micellar curvature. The elongated micelles entangle with each other, forming network structures of wormlike micelles, and the system shows viscoelastic properties, which could be described by the Maxwell model. A peak observed in the zero-shear viscosity (η(0)) versus L-02 concentration curve shifted toward higher L-02 concentrations and the value of maximum viscosity (η(0 max)) increased with the increasing ChEO(20) mixing fraction with water. We observed that η(0 max) increased by 2 to 4 orders of magnitude as a function of the ChEO(20) concentration. The Maxwell relaxation time (τ(R)) shows a maximum value at a concentration corresponding to η(0 max) (i.e., τ(R) increases with L-02 concentration and then decreases after attaining a maximum value, whereas the plateau modulus (G(0)) shows monotonous growth). These observations demonstrate microstructural transitions in two different modes: L-02 first induces 1-D micellar growth and as a result the viscosity increases, and finally after the system attains its maximum viscosity, L-02 causes branching in the network structures. The microstructure transitions are confirmed by SAXS and cryo-TEM techniques.

We have investigated the microstructural transformations of nonionic surfactant reverse micelles induced by surfactant molecular architecture, surfactant concentration, and temperature in nonaqueous media. The investigations were based on small-angle X-ray scattering (SAXS) and rheometry techniques. Polyglycerol polyoleic acid esters spontaneously self-assembled into reverse micelle in n-decane under ambient conditions, whose shape, size, and internal structure could be controlled by the surfactant molecular architecture, concentration, and temperature. The maximum size of the micelles was found to increase with an increase in the hydrophilic headgroup size of the surfactant. On the other hand, an opposite trend was observed with an increase in the number of oleate chain per surfactant molecules, which was well supported by rheology data; viscosity decreased with the number of oleate chain per surfactant molecule. The SAXS and rheology data have shown a clear evidence of one dimensional micellar growth with increase in the surfactant concentration. The relative viscosity, eta(r), of the reverse micelle exhibited steeper concentration dependence behavior than those predicted for a dispersion of spherical particles based on the Krieger-Dougherty relation which provided a clear evidence of the presence of elongated micelles at higher concentration. An ellipsoidal prolate-to-sphere type transition was observed upon heating.

Structure of diglycerol monomyristate (designated as C14G2) nonionic surfactant reverse micelles in aromatic solvent styrene has been investigated as a function of surfactant concentration, temperature, and water addition by using small-angle X-ray scattering (SAXS) technique. Structure of micelles in real-space so called pair-distance distribution function, p(r), was obtained by the generalized indirect fourier transformation (GIFT) evaluation of SAXS data. It was found that C14G2 spontaneously self-assembles into spheroid reverse micelles with maximum diameter approximately 3.0 nm when added into styrene under ambient condition. The micellar shape and size remained essentially the same despite a wide variation in surfactant concentration (5 to 30%) but an opposite trend was observed with the rise of temperature; size decreased by approximately 25% with increase in temperature from 25 to 75 degrees C. Addition of traces water favored micellar growth and eventually ellipsoid prolate type micelles were formed, whose scenario is understood in terms of decrease in the critical packing parameter (cpp); water hydrates the surfactant's headgroup and decreases cpp. At a particular concentration of water, increasing temperature decreased the micellar size due to dehydration of headgroup. It is interesting to note that size of 1.57% water incorporated micelle is approximately 2.5 times bigger than the empty micelles.

This paper describes a facile route to the shape, size, and structure control of reversed micelles by surfactant and solvent molecular architecture and water addition. Nonionic reverse micellar size is found to increase with increase in hydrophilic headgroup size of surfactant, whose scheme is understood in terms of decrease in the critical packing parameter (cpp). On the other hand, an opposite trend is observed with increase in lipophilicity of the surfactant. This is caused by the repulsive excluded volume interactions, which increases with the volume of lipophilic moiety of surfactant; as a result, the micelle interface tends to become more curved and micelles shrink. Solvent molecular structure has played a crucial role; increasing hydrocarbon chain length of alkanes favored one dimensional micellar growth. We note that long chain oil has a poor penetration tendency to lipophilic tail of surfactant and decreases the cpp. Solvent polarity is also crucial; globular micelles are formed in short chain oil cyclohexane. We note that decreasing chain length of oil mimic the decrease in the headgroup size of surfactant; rod-to-sphere type transition in the micellar structure. Addition of trace water favors micellar growth; maximum dimension and micellar cross section increases with increase in water concentration. The sizes of the water incorporated reverse micelles (or w/o microemulsion) are much bigger than the empty micelles. Micellar structure was confirmed by small angle X-ray scattering (SAXS) and supported by rheology.

Shape, size, and internal structure of nonionic reverse micelle in styrene depending on surfactant chain length, concentration, temperature, and water addition have been investigated using a small-angle X-ray scattering (SAXS) technique. The generalized indirect Fourier transformation (GIFT) method has been employed to deduce real-space structural information. The consistency of the GIFT method has been tested by the geometrical model fittings, and the micellar aggregation number (N(agg)) has been determined. It was found that diglycerol monocaprate (C(10)G(2)), diglycerol monolaurate (C(12)G(2)), and diglycerol monomyristate (C(14)G(2)), spontaneously self-assemble into reverse micelles in organic solvent styrene under ambient conditions. The micellar size and the N(agg) decrease with an increase in surfactant chain length, a scenario that could be understood from the modification of the critical packing parameter (cpp). A clear picture of one-dimensional (1-D) micellar growth was observed with an increase in surfactant weight fraction (W(s)) in the C(10)G(2) system, which eventually formed rodlike micelles at W(s) ≥ 15%. On the other hand, micelles shrunk favoring a rod-to-sphere type transition upon heating. Reverse micelles swelled with water, forming a water pool at the micellar core; the size of water-incorporated reverse micelles was much bigger than that of the empty micelles. Model fittings showed that water addition not only increase the micellar size but also increase the N(agg). Zero-shear viscosity was found to decrease with surfactant chain but increase with W(s), supporting the results derived from SAXS.

Polyoxyethylene cholesteryl ether (ChEO(20)) nonionic surfactant self-assembles into spherical micelles above the critical micelle concentration in water. An ordering of micelles takes place with an increase in surfactant concentration and forms a micellar cubic phase with the space group Pm3n at ∼30%. Cocamid methyl MEA (designated as C-11S) cosurfactant is soluble at the palisade layer of the ChEO(20) micelle as a result; the curvature of the aggregates tends to decrease and favors sphere-to-rod transition. The axial length of the rod increases with C-11S concentration, and after a certain concentration, elongated micelles entangle with each other, forming a transient network of wormlike micelles. Viscosity increases by 5 orders of magnitude. The zero-shear viscosity (η(0)) versus C-11S concentration curve shows a peak, and the position of the peak shifts toward the right (at higher concentration of C-11S) when the concentration of ChEO(20) in water is increased from 10 to 15%. On the other hand, the peak position shifts toward the left with a decrease in the ethylene oxide (EO) chain of the surfactant, i.e., in the ChEO(15) system. Viscosity increases only slightly with a longer EO chain ChEO(30) system, and it does not show any viscoelastic properties. These wormlike micelles exhibited viscoelastic behavior and could be described by the Maxwell mechanical model with a single stress relaxation mode that is sensitive to temperature. Viscosity and relaxation time were first increased and then decreased, but the plateau modulus increased continuously upon heating. These observations revealed that micelles first grew with temperature and then branched. Dynamic rheology and small-angle X-ray scattering (SAXS) further support the rheology data.

We report the formation of reverse rod-like micelles and their rheological properties in novel nonionic surfactant, dipentaerythrityl tri-(12-hydroxystearate) (designated as WO-6)/oil systems without external water addition. Small-angle X-ray scattering (SAXS) was used to investigate the structure of the micelles and their flow properties were studied by rheological measurements. We found that WO-6 spontaneously self-assembles into reverse micelles in a variety of organic solvents at ambient conditions, their structure depending on solvent molecular architecture, surfactant concentration, and temperature. Rod-like micelles with a maximum length of ca. 12 nm and a cross section diameter of ca. 2 nm were observed in cyclohexane. When cyclohexane was replaced with a linear chain octane, the length and the cross section diameter were simultaneously increased. With a further increase of hydrocarbon chain length of solvent oils from octane to hexadecane, the rod-like micelles grew axially, keeping the cross section diameter (ca. 3 nm) virtually constant. Increasing surfactant concentration also favored one-dimensional micellar growth. On the other hand, micelles shrunk with the rise of temperature, which is similar to a rod-to-sphere transition, and is essentially the opposite temperature dependence to that often observed in aqueous micellar systems. A structural picture drawn by SAXS is well supported by rheology; the relative (zero-shear) viscosity of the WO-6/oil systems was found to be markedly greater than that expected for a dispersion of spherical particles due to the elongated micellar structure, despite quantitative inconsistency with semi-empirically predicted values for rigid rod-like particles.

The amino acid-based anionic surfactant, N-dodecanoylglutamic acid (designated as LAD), when neutralized with 2-aminoethanol (MEA), 2,2'-iminodiethanol (DEA), or 2,2',2''-nitrilotriethanol (TEA) forms globular type of micelles in aqueous system at 25 °C, and the viscosity of each solution is very close to that of pure water. Addition of cationic surfactants, e.g., tetradecyltrimethylammonium bromide (TTAB) or hexadecyltrimethylammonium bromide (CTAB), induced a sphere-to-rod transition, and the micelles grew axially, resulting in formation of viscoelastic wormlike micelles that could be described by a Maxwell model. The viscosity was ca. 5 orders of magnitude as large as that of water. The viscosity maximum was observed in zero-shear viscosity (η0) curves, and there was a phase separation to liquid crystal phase at higher cosurfactants concentration. The η0 curve shifted toward lower cosurfactant concentration, and the value of maximum viscosity (η0(max)) decreased by reducing lipophilic moiety of cosurfactant. Furthermore, the value of η0(max) decreased with decreasing the number of ethanol content per molecule of neutralizing agent. The η0 decays exponentially with the rise of temperature, following the Arrhenius type of behavior. However, addition of dodecyltrimethylammonium bromide (DTAB) increases viscosity only slightly; viscoelastic wormlike micelles are not formed.

We have investigated the structure and rheology of diglycerol monolaurate (C(12)G(2)) reverse micelles in styrene using small-angle X-ray scattering (SAXS) and rheometry techniques. The SAXS data have been evaluated by generalized indirect Fourier transformation (GIFT) method and further supported by geometrical model fittings. We found that the C(12)G(2) when added into styrene spontaneously self-assemble into ellipsoidal prolate type reverse micelles under ambient conditions. Micelles grew and micellar aggregation number (N(agg)) increased with the increase in surfactant concentration demonstrating concentration induced one dimensional micellar growth, which was further supported by rheology data; the relative viscosity, η(r), for the C(12)G(2)/styrene mixtures exhibit far steeper concentration dependence behavior than those predicted for a dispersion of spherical particles based on the Krieger-Dougherty relation, due to the elongated micellar structures. On the other hand, a distinct modulation in the shape and size of micelles favoring ellipsoidal prolate-to-sphere type transition was observed upon heating, whose scheme could be attributed to the enhanced penetration tendency of oil into the lipophilic shell of the surfactant at the higher temperatures. As anticipated reverse micelles swelled with water causing two dimensional micellar growth; both the maximum dimension and maximum core radius increase with water., (Copyright © 2011 by Japan Oil Chemists' Society)

We have developed hybrid amphiphilic polymers consisting of a silicone backbone modified with hydrocarbon chains and hydrolyzed silk peptides. These polymers are molecularly soluble neither in water nor in most of organic solvent, but are attractive with these solvents. We assume that this property enables the polymers to form "an independent third phase" between immiscible two liquid phases and stabilize the emulsion system, based on a fundamentally distinguishable mechanism from the approach by conventional surfactants. We have named these amphiphilic polymers "active interfacial modifier (AIM)" and studied physicochemical properties of AIM-stabilized water-in-silicon oil emulsions. The addition of AIM to a mixture of water and decamethylcyclopentasiloxane (D(5)) has achieved preparation of stable W/O emulsions (droplet size = ca. 1 microm) in a wide range of the three components, even under relatively gentle vortex mixing. Interestingly, the prepared W/O emulsions are found to be nearly genuine or quasi Newtonian fluid with low viscosity when water content is in the range from 0 to 36 wt % for the fixed weight ratio of AIM/D(5) = 6/4. This is a good piece of evidence that AIM forms the independent third phase, where the Newtonian shear occurs at the D(5)/AIM interface. The presence of AIM as third phase has also been confirmed by fluorescence probe method with confocal laser scanning microscopy. As such, AIM can activate interfaces by the least amount to cover interfaces as an independent third phase, and hence, this provides a new concept achieving a precise control of interfacial properties.