Plasmonic Liquid Marbles: A Miniature Substrate‐less SERS Platform for Quantitative and Multiplex Ultratrace Molecular Detection

Inspired by aphids, liquid marbles have been studied extensively and have found application as isolated microreactors, as micropumps, and in sensing. However, current liquid‐marble‐based sensing methodologies are limited to qualitative colorimetry‐based detection. Herein we describe the fabrication of a plasmonic liquid marble as a substrate‐less analytical platform which, when coupled with ultrasensitive SERS, enables simultaneous multiplex quantification and the identification of ultratrace analytes across separate phases. Our plasmonic liquid marble demonstrates excellent mechanical stability and is suitable for the quantitative examination of ultratrace analytes, with detection limits as low as 0.3 fmol, which corresponds to an analytical enhancement factor of 5×10⁸. The results of our simultaneous detection scheme based on plasmonic liquid marbles and an aqueous–solid–organic interface quantitatively tally with those found for the individual detection of methylene blue and coumarin.     

Effect of volume concentration and temperature on viscosity and surface tension of graphene–water nanofluid for heat transfer applications

In the present study, the effect of volume concentration (0.05, 0.1 and 0.15 %) and temperature (10–90 °C) on viscosity and surface tension of graphene–water nanofluid has been experimentally measured. The sodium dodecyl benzene sulfonate is used as the surfactant for stable suspension of graphene. The results showed that the viscosity of graphene–water nanofluid increases with an increase in the volume concentration of nanoparticles and decreases with an increase in temperature. An average enhancement of 47.12 % in viscosity has been noted for 0.15 % volume concentration of graphene at 50 °C. The enhancement of the viscosity of the nanofluid at higher volume concentration is due to the higher shear rate. In contrast, the surface tension of the graphene–water nanofluid decreases with an increase in both volume concentration and temperature. A decrement of 18.7 % in surface tension has been noted for the same volume concentration and temperature. The surface tension reduction in nanofluid at higher volume concentrations is due to the adsorption of nanoparticles at the liquid–gas interface because of hydrophobic nature of graphene; and at higher temperatures, is due to the weakening of molecular attractions between fluid molecules and nanoparticles. The viscosity and surface tension showed stronger dependency on volume concentration than temperature. Based on the calculated effectiveness of graphene–water nanofluids, it is suggested that the graphene–water nanofluid is preferable as the better coolant for the real-time heat transfer applications.     

Jetting liquid marbles: study of the Taylor instability in immersed marbles

The behavior of liquid marbles encapsulated with various powders, immersed in oil, and exposed to a uniform DC field was investigated. At some critical value of the electric field, the Taylor instability of the marble shape took place, accompanied by the appearance of a cone and jetting a small droplet. The squared critical electric field was linear dependent on inverse of the size parameter of the marble. In some cases, the extrapolation of this linear dependence to the zero field gave the finite value of the spherical marble radius corresponding to the Rayleigh limit that meant that the marbles were charged. Lycopodium-coated marbles remained neutral under the action of a DC field, as well as a pure water droplet. Therefore, charging marbles is determined by their powder coverage. The data on effective surface tension at marble–oil interfaces were extracted from the above linear dependence for the uncharged marble. The effective surface tension was measured in parallel by the capillary rise method.     

Graphene Grown from Flat and Bowl Shaped Polycyclic Aromatic Hydrocarbons on Cu(111)

The growth of carbon layers, defective graphene, and graphene by deposition of polycyclic aromatic hydrocarbons (PAHs) on Cu(111) is studied by scanning tunneling microscopy and X-ray photoelectron spectroscopy. Two different PAHs are used as starting materials: the buckybowl pentaindenocorannulene (PIC) which contains pentagonal rings and planar coronene (CR). For both precursors, with increasing sample temperature during deposition, porous carbon aggregates (350 °C), dense carbon layers (400–450 °C), disordered defective graphene (500 °C–550 °C), and extended graphene (≥600 °C) are obtained. No significant differences for defective graphene grown from PIC and CR are observed. C 1s X-ray photoelectron spectra of PIC and CR derived samples grown at 350–550 °C exhibit a characteristic C−Cu low binding energy component. Preparation at ≥600 °C eliminates this C−Cu species and only C−C bonded carbon remains.     

Kinetics of the conversion reaction of gypsum with ammonium carbonate

The reactivity of flue gas desulphurization gypsum with ammonium carbonate has been studied in the temperature range (20–50) °C. Mechanism of this reaction was suggested and the kinetics parameters characterizing the reaction were determined. A mathematical model suitable for the prediction of the conversion of gypsum was proposed. The reaction is of the second order. Influence of the size of gypsum particles on the relationship between the surface and volume of the particles is not significant. From the obtained experimental results, it follows that the reaction does not proceed at the surface of the solid gypsum particles, but in the liquid phase between dissolved gypsum and ammonium carbonate. The diffusion of the dissolved gypsum through the liquid film formed at the surface of the solid gypsum particles is the rate-limiting step of the conversion reaction.     

The reaction of phenylpropylsilsesquioxane in the fiber spinning regime

A potential ceramic precursor, a phenylpropylsilsesquioxane co-oligomer from Petrarch Systems (Petpps), was studied under conditions where fiber spinning is performed. The reaction kinetics of residual silanols of Petpps are studied using Fourier transform infrared spectroscopy in the temperature range 100–150°C. The activation energy and the reaction order of the silanol condensation reaction in the molten Petpps are determined. A combination of gel permeation chromatography, liquid chromatography, and nuclear magnetic resonance spectroscopy is used to study the possibility of copolymerization between the phenyl and propyl silane moieties.     

Liquid Marble Photosensor

A liquid marble is a liquid droplet coated by a hydrophobic powder. The liquid marble does not wet adjacent surfaces and therefore can be manipulated as a dry soft body. A Belousov-Zhabotinsky (BZ) reaction is an oscillatory chemical reaction exhibiting waves of oxidation. We demonstrate how to make a photo-sensor from BZ medium liquid marbles. We insert electrodes into a liquid marble, prepared from BZ solution and coated with polyethylene powder. The electrodes record a potential difference which oscillates due to oxidation wave-fronts crossing the electrodes. When the BZ marble is illuminated by a light source, the oxidation wave-fronts are hindered and, thus, the electrical potential recorded ceases to oscillate. We characterise several types of responses of BZ marble photosensors to various stimuli, and provide explanations of the recorded activity. BZ liquid marble photosensors may find applications in the fields of liquid electronics, soft robotics and unconventional computing.     

Blue phase liquid crystals affected by graphene oxide modified with aminoazobenzol group

Liquid-crystalline blue phases (BPs) are stable only for very narrow temperature range between the isotropic and the chiral nematic phase that severely hinders their applicability. Herein, the aminoazobenzol group was chemically grafted onto epoxy group of graphene oxide (GO) via addition reaction. Successful grafting of aminoazobenzol group was confirmed using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), UV–vis absorption spectra and thermogravimetric analysis (TGA). The resultant aminoazobenzol group–modified GO sheets, which is reduced (RGO-Az), were easily redispersable in common organic solvents or liquid crystals (LCs). By doping different contents of RGO-Az, nanosheets could stabilise BP and increase the BP range. When doped with 0.5 wt% RGO-Az, the mixtures show the wider range with 5.9°C than the range with 3.6°C of BPLCs without RGO-Az. Meanwhile, the phase sequence and the range of the aforementioned phases are reproducible upon heating and cooling, which shows that the BPs doped with RGO-Az nanosheets are thermodynamically stable.     

Radiation-induced grafting of hexafluoroacetone to polyethylene

Although hexafluoroacetone is not polymerized by ionizing radiation, it is shown that γ-irradiation of hexafluoroacetone dissolved in polyethylene films produces a graft with a G value of 500 and, therefore, a kinetic chain length of 200. The effects of dose rate (0.021–3.55 Mrad/hr), temperature (21–53°C), and pressure (1.5–6.2 atm) on the graft rates have been measured. Also the effect of temperature (21–53°C) on the postirradiation grafting reaction and on the physical properties of the grafted films have been investigated. Together with solubility, diffusivity, infrared, and EPR data, the results lead to the following mechanism: The first step represents production of secondary alkyl radicals in the polyethylene by irradiation of the polymer–monomer system. The second step involves the linkage of the monomer to the radical site to form the alkoxy radical. Since it cannot add to another monomer unit, this radical abstracts a hydrogen atom from an adjacent polyethylene chain in the third step. Radical R· can then continue the kinetic chain. Radical combination and radical–impurity reactions terminate the chain. The graft may be unique in that it is the only one we have found in which a pendant group containing only one monomer unit is attached by a chain reaction. At dose rates up to 0.215 Mrad/hr, the grafting was linear with time and proportional to the 0.73 power of the dose rate at 21°C and to the 0.81 power at 53°C. The reaction is insensitive to increases in dose rate above 0.215 Mrad/hr where diffusivity measurements show the reaction to be diffusion-controlled. The rate of reaction increased 10% when the temperature was increased from 21 to 53°C. While there was significant postirradiation grafting reaction at 21°C, there was none at 53°C. The results do not fit the equations of reaction-controlled steady-state graft-polymerization kinetics. The deviations arise from an observed increase in monomer solubility in the film with increasing graft combined with low diffusivity of the monomer in polyethylene, and the presence of a radical-scavenging impurity which terminates the kinetic chain with the appearance of a relatively stable radical. EPR data suggests that the impurity is a trace of oxygen which may be produced radiolytically.     

Kinetics of thiophene hydrodesulfurization over a supported Mo–Co–Ni catalyst

In this study, the kinetics of thiophene (TH) hydrodesulfurization (HDS) over the Mo–Co–Ni-supported catalyst was investigated. Trimetallic catalyst was synthesized by pore volume impregnation and the metal loadings were 11.5 wt % Mo, 2 wt % Co, and 2 wt % Ni. A large surface area of 243 m²/g and a relatively large pore volume of 0.34 cm³/g for the fresh Mo–Co–Ni-supported catalyst indicate a good accessibility to the catalytic centers for the HDS reaction. The acid strength distribution of the fresh and spent catalysts, as well as for the support, was determined by thermal desorption of diethylamine (DEA) with increase in temperature from 20 to 600 °C. The weak acid centers are obtained within a temperature range between 160 and 300 °C, followed by medium acid sites up to 440 °C. The strong acid centers are revealed above 440 °C. We found a higher content of weak acid centers for fresh and spent catalysts as well as alumina as compared to medium and strong acid sites. The catalyst stability in terms of conversion as a function of time on stream in a fixed bed flow reactor was examined and almost no loss in the catalyst activity was observed. Consequently, this fact demonstrated superior activity of the Mo–Co–Ni-based catalyst for TH HDS. The activity tests by varying the temperature from 200 to 275 °C and pressure from 30 to 60 bar with various space velocities of 1–4 h^?1 were investigated. A Langmuir–Hinshelwood model was used to analyze the kinetic data and to derive activation energy and adsorption parameters for TH HDS. The effect of temperature, pressure, and liquid hourly space velocity on the TH HDS activity was studied.     

Kinetics of the <Emphasis Type="Italic">n</Emphasis>-Decanol Oxyethylation Reaction with Allowance for Association

The kinetics of n-decanol oxyethylation in the temperature range of 60–150°C at a pressure of 1.4MPa is investigated under conditions of base catalysis and an excess of alcohol in the initial step of the reaction (initial concentration of ethylene oxide in the reaction mixture, approximately 1 mol/L; that of the catalyst, 10^?1 to 10^?3 mol/L). The experimental results are satisfactorily described by a kinetic equation that allows for the association of alcohol molecules and is first order with respect to the concentration of alcohol associates. Based on kinetic studies and thermogravimetry, it is concluded that the structural rearrangement of liquid decanol occurs at a temperature of around 87.5°C.     

Freezing of a liquid marble

In this study, we present for the first time the observations of a freezing liquid marble. In the experiment, liquid marbles are gently placed on the cold side of a thermo-electric cooler (TEC), and the morphological changes are recorded and characterized thereafter. These liquid marbles are noticed to undergo a shape transition from a spherical to a flying-saucer-shaped morphology. The freezing dynamics of liquid marbles is observed to be very different from that of a freezing water droplet on a superhydrophobic surface. For example, the pointy tip appearing on a frozen water drop could not be observed for a frozen liquid marble. In the end, we highlight a possible explanation of the observed morphology.     

Investigation of clorine trifluoride absorption by crystalline calcium carbonate

The effect of temperature factor on the efficiency of absorption of fluorine- and chlorine gas by a chemical absorbent, marble chips of a grade CA-MC, was researched. The degree of absorption of fluoride compounds at room temperature was 91%. The degree of recovery of total chlorine was 47.3%, that is because the low reactivity of the absorbent and an increase in an amount of Cl₂ in gases due to displacement of it by the fluorides from formed CaCl₂. Calculation of thermodynamic characteristics of the processes showed that the equilibrium constant for the reaction of chlorine with CaCO₃ increased with a temperature growth, which proved larger intensity of the chlorine absorption by the hot absorbent. According to the suggested method, the gases containing chlorine fluorides successively passed through three distinct temperature zone of calcium carbonate: 230–600°C, 25–35°C and 300–600°C. In this case, the degree of recovery of fluorine compounds was 99%, and 98% of elemental chlorine was absorbed.     

Palladium nanoparticles deposited on a graphene–benzimidazole support as an efficient and recyclable catalyst for aqueous‐phase Suzuki–Miyaura coupling reaction

Graphene oxide was functionalized with benzimidazole for palladium immobilization. The resultant graphene–benzimidazole‐supported palladium composite (G‐BI‐Pd) was characterized using infrared and Raman spectroscopies, transmission electron microscopy and energy‐dispersive X‐ray spectroscopy. G‐BI‐Pd showed excellent catalytic activity and fast reaction kinetics in the aqueous‐phase Suzuki–Miyaura reaction of aryl iodides and bromides with phenylboronic acid under relatively mild conditions (5–25 min, 80 °C). The catalyst can be used several times without any significant loss of its catalytic activity.     

Thermal degradation kinetics study and thermal cracking of waste cooking oil for biofuel production

Thermal cracking of waste cooking oil (WCO) for production of liquid fuel has gained special interest due to the growing demand of renewable fuel, depleting fossil fuel reserves and environmental issues. In the present work, thermal cracking of WCO to produce liquid hydrocarbon fuels without any preprocessing has been studied. Moreover, non-isothermal kinetics of WCO using thermogravimetric analysis (TGA) has been studied under an inert atmosphere at various heating rates. According to TGA result, active thermal decomposition of WCO was found to be between 318 and 500 °C. Furthermore, the temperature at which the maximum mass loss rate attained was shifted to higher values as the heating rates increased from 10 to 50 °C min^?1 and the values were found to be approximately similar to that of R ₅₀. Besides, model-free iso-conversion kinetic methods such as Friedman (FM), Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) were used to determine the activation energies of WCO degradation. The average activation energy for the thermal degradation of WCO was found to be 243.7, 211.23 and 222 kJ mol^?1 for FM, KAS and FWO kinetic methods, respectively. Additionally, the cracking of WCO was studied in a semi-batch reactor under an inert atmosphere and the influences of cracking temperature, time and heating rates on product distribution were investigated. From the reaction, an optimum yield of 72 mass% was obtained at a temperature of 475 °C, time of 180 min and a heating rate of 10 °C min^?1. The physicochemical properties studied were in accordance with ASTM standards.     

Kinetics of anhydride formation in poly(acrylic acid) and its effect on the properties of a PAA-alumina composite

The kinetics of anhydride formation of poly(acrylic acid) (PAA) in porous PAA–alumina composites have been investigated by using a thermogravimetric technique (TGA). Three distinct reaction peaks at 200°C (I), 250°C (II), and 390°C (III) were identified in the dynamic TGA thermogram. These peaks were attributed to bound water removal (I), anhydride formation (II), and polymer degradation (III). The kinetics of the anhydride reaction were studied in a temperature range of 220–240°C and found to follow a second-order mechanism with an activation energy of approximately 38 kcal/mole. In addition, the bound water was found to inhibit the onset of anhydride formation. The degree of conversion to anhydride was correlated with the equilibrium swelling level attained by the composite in water.     

Kinetics of bulk polymerization of trimeric phosphonitrilic chloride

The kinetics of the pure bulk polymerization of trimeric phosphonitrilic chloride were investigated in the temperature range 240–255°C. The reaction was found to be secondorder with an activation energy of 57 kcal./mole. Polymerization catalyzed by benzoic acid was first-order, and the reactivities of benzoic acid and sodium benzoate at 235°C. were found to be about similar. The volatile decomposition products for the benzoic acid reaction were identified. Mechanisms are postulated for the catalyzed and uncatalyzed reactions.     

Evaluation of kinetic parameters for oxidation of thioacids by benzimidazolium dichromate: A mechanistic study

In a non-aqueous medium, oxidation kinetics of thioglycolic, thiolactic and thiomalic acids by benzimidazolium dichromate have been studied. In the temperature range of 20°C–50°C, oxidation kinetics were examined by spectrophotometry. In terms of oxidant, the reaction is dependent on the unitary order. In the case of thioacids, we find the Michaelis-Menten type kinetics. Hydrogen-ions act as catalyst in this process. The reaction rate slows down as the Mn²⁺ ion concentration increases. The reaction does not cause acrylonitrile to polymerize. The formation of a thioester into the pre-equilibrium followed by its progressive degradation was postulated as a mechanism.     

Solution-based fabrication of a graphene–ZnO nanocomposite

Graphene-based composites represent a new class of materials with potential for many applications. Graphene can be attached to a metal, a semiconductor, or any polymer. In this work, our approach was to attach graphene to a well-known semiconductor, ZnO. We synthesized graphene–ZnO composites by a simple, low-cost, environmentally friendly solvothermal method, carrying out the reaction in different conditions in order to discover the optimum condition, and also to obtain a high-quality product. Our research demonstrated that the optimum temperature to obtain a high-quality product is 180 °C for 20 h. All obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy, electron dispersion spectrometry, X-ray photoelectron spectrometry, Raman spectroscopy, Fourier transform infrared spectrometry, UV–visible spectrophotometry, and thermogravimetric analysis. The XRD confirmed that the crystal structure of the ZnO in the nanocomposite was wurtzite type. The prepared composite was stable to 800 °C with its 80 % weight.     

La cristallisation du polydioxolanne

Crystallization kinetics have been studied for two samples of polydioxolan (molecular weights 10.000 and 30.000). The crystallization was followed at temperatures between 0 and 21°C in a DSC calorimeter. The results obey Avrami's equation. The Avrami exponent was found to be two indicating a spontaneous and probably heterogeneous mode of nucleation. Over the temperature range studied, the crystallization lead to the growth of two-dimensional spherulites.The morphology of polydioxolan samples was studied by optical microscopy and small-angle light scattering. Samples crystallized in liquid nitrogen are made of small spherulites of the order of 5 μm. Samples crystallized between 0 and 21°C are made of large spherulites, of the order of 1 mm. Samples crystallized at 25 and 35°C show large and “abnormal” spherulites, made of two optical phases corresponding to the centre and the perimeter.No difference was seen between the morphologies of the two samples studied. In both cases, the time of half-crystallization was the same when plotted as a function of the degree of supercooling. Equilibrium melting points of 79 and 85°C were found for the low and high molecular weight samples, respectively.