A combination of ex situ and in situ characterization techniques was used to determine the mechanism of calcium carbonate (CaCO3) formation from calcium hydroxide (Ca(OH)2) dispersions in methanol/water (CH3OH/H2O) systems. Mid-infrared (mid-IR) analysis shows that in the absence of carbon dioxide (CO2) Ca(OH)2 establishes a reaction equilibrium with CH3OH, forming calcium hydroxide methoxide (Ca(OH)(OCH3)) and calcium methoxide (Ca(OCH3)2). Combined ex situ mid-IR, thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray absorption spectroscopy and scanning electron microscopy examination of the reaction product formed in the presence of CO2 reveals the formation of calcium dimethylcarbonate (Ca(OCOOCH3)2). This strongly suggests that carbonation takes place by reaction with the Ca(OCH3)2 formed from a Ca(OH)2 and CH3OH reaction. Time-resolved XRD indicates that in the presence of H2O the Ca(OCOOCH3)2 ester releases CH3OH and CO2, forming ACC, which subsequently transforms into vaterite and then calcite. TGA reveals that thermal decomposition of Ca(OCOOCH3)2 in the absence of H2O mainly leads to the reformation of Ca(OCH3)2, but this is accompanied by a significant parallel reaction that releases dimethylether (CH3OCH3) and CO2. CaCO3 is the final product in both decomposition pathways. For CH3OH/H2O mixtures containing more than 50 mol % H2O, direct formation of calcite from Ca(OH)2 becomes the dominant pathway, although the formation of some Ca(OCOOCH3)2 was still evident in the in situ mid-IR spectra of 20 and 40 mol % CH3OH systems. In the presence of ≤20 mol % H2O, hydrolysis of the ester led to the formation of an ACC sol–gel. In both the 90 and 100 mol % CH3OH systems, diffusion-limited ACC → vaterite → calcite transformations were observed. Traces of aragonite were also detected. We believe that this is the first time that these reaction pathways during the carbonation of Ca(OH)2 in a methanolic phase have been systematically and experimentally characterized.
Surface-functionalized noble metal nanoparticles with macrocyclic hosts have attracted enormous research interest owing to their applications in drug delivery, catalysis, bioimaging, etc. Stable p-sulfonatocalix[6]arene-functionalized gold nanoparticles (SCx6AuNPs) of the sizes ∼7.5 nm have been synthesized and characterized by using UV–vis absorption, transmission electron microscopy, and surface-enhanced Raman spectroscopy measurements. The efficient uptake and stimuli-responsive release of doxorubicin (Dox), an anticancer drug, by the SCx6AuNPs have been established for targeted drug delivery application. The decreased cytotoxicity of Dox loaded on SCx6AuNPs, especially toward normal cell lines, and its multistimuli responsive release validated in both cancerous (A549) and normal (W126) cell lines find promising for selectively targeted drug delivery applications toward cancer cells. At the cellular level, this study also establishes the efficient uptake of the SCx6AuNP nanoconjugates, and its validation has been done by bioimaging measurement by using thioflavin T (ThT) dye loaded on to SCx6AuNPs instead of Dox as the fluorescent tracking probe. The bright fluorescence microscopic image of ThT-SCx6AuNP-stained cancerous cell lines corroborates the uptake of SCx6AuNPs by the cell lines and its projected utility for drug delivery and bioimaging applications.
The versatility of environmentally benign and inexpensive deep eutectic solvents (DESs) lies in their widely varying physicochemical properties. Depending on its constituents, a DES may be highly polar or nonpolar in nature. This offers an enticing possibility of formation of novel nonaqueous microemulsions (MEs). Evidence of the presence of polar DES-in-nonpolar DES MEs is presented with reline (formed by mixing choline chloride and urea in 1 : 2 mol ratio) as the polar DES forming the ME pools, Thy : DA [formed by mixing thymol (Thy) and n-decanoic acid (DA) in 1 : 1 mol ratio] nonpolar DES as the bulk oil phase and nonionic surfactant Brij-35 as the emulsifying agent. While only sparingly miscible in Thy : DA, as high as 2.5 M reline can be solubilized in this DES in the presence of 100 mM Brij-35; reline loading (wRel = [reline]/[Brij-35]) as high as 25 can be achieved. The ternary phase diagram of the Thy : DA/Brij-35/reline system reveals a clear and transparent single-phase region where MEs may be forming. Dynamic light scattering confirms the presence of MEs of 2–10 nm size. Even as up to 2.5 M (ca. 0.35 mole fraction) reline, whose dynamic viscosity (η) and electrical conductivity (κ) are very high, is added to 100 mM Brij-35 solution of Thy : DA, the η and κ values of the solution increase insignificantly, thus conforming to the formation of MEs in the solution. Fourier transform infrared (FTIR) absorbance spectra and fluorescence probe responses further indicate that reline is not dispersed in the medium but rather forms polar pools of the MEs. These novel nonaqueous polar DES-in-nonpolar DES MEs will not only expand the application potential of DESs but also offer a new class of organized media with widespread potential.
Understanding the dissolution process of surfactant solutions is important in formulating product design processes. The main goal of this study is to gain further insights into how additives and mixtures affect surfactant dissolution processes. To achieve this goal, dissipative particle dynamic simulations were used. Lamellar phases at 80% volume of surfactant were initially equilibrated with water. After reaching an equilibrium state, the dissolution simulations were carried out for different surfactant mixtures. To track the dissolution process, different metrics were used, including visual analysis, local concentration analysis, diffusion, and cluster size calculations. Results show that by having a mixture of surfactants, the diffusion of the micelles is not affected only by the size of the micelles as in pure surfactant systems, but there is also an effect due to the composition of the micelles. When oil is added to a surfactant system, the system acts like a longer chain surfactant system, but only when the chain of oil becomes sufficiently long.
In the rapidly evolving Internet of Things (IoT) society, the demand for microbatteries with high areal energy density is surging. As a promising strategy to enhance areal energy density, three-dimensional (3D) batteries have attracted attention. The feature of 3D batteries is the decoupling of the electrode thickness from the ion-transport distance through the modification of the spatial arrangement of the positive and negative electrodes beyond the conventional parallel plates configuration. This allows for the accommodation of a larger amount of active materials without increasing internal resistance. However, identifying the optimal 3D geometry is a complex task, as it depends on printable materials, the resolution of the fabrication equipment, as well as battery usage, which constitutes a multiobjective optimization problem. To overcome this challenge, we propose a novel approach to determine the optimal 3D microbattery geometry. Our innovative method involves a 3D battery optimization system, which integrates an automatic geometry generator with a quick and accurate performance simulator. This approach allows, for the first time, the discovery of material- and discharge-current-dependent optimal geometries. We successfully apply this optimization scheme to two standard electrode pairs (LiFePO4/Li4Ti5O12 and LiNi0.5Mn0.3Co0.2O2/graphite), demonstrating a significant increase in energy density (30%–40% greater than the current state-of-the-art geometry), particularly under high current conditions. These findings underscore the importance of tailor-made batteries for diverse IoT applications and showcase the potential of our approach in realizing such designs.
Investigating chemosensors that are capable of quantifying pressure in solution, particularly hydrostatic pressure, which is one of the mechanical forces, is an attractive challenge in chemistry from the viewpoint of “mechano”-science. Herein, we report the investigation of chiral porphyrin tweezers, Por-Cy and Por-DPhEt, comprising different flexible linkers; Por-Cy and Por-DPhEt displayed distinct ratiometric signaling by using the higher excited S2 state with a standard excited S1 level. A novel operative mechanism using the S1/S2 fluorescence ratio was revealed using hydrostatic pressure-ultraviolet/visible (UV/vis), fluorescence/excitation, circular dichroism spectroscopy, and lifetime measurements, which can be further controlled by the open-closed conformational change inherent in the tweezer skeleton. Furthermore, the fluorescent chiral tweezers exhibited a promising |glum| of 2.9 × 10–3, indicating that they are potential candidates for sensory applications in chiral environments. This study provides opportunities for the development of smart pressure-responsive chemosensors.
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：