An efficient and novel method for the synthesis of cardiolipin and its analogs

A novel synthetic method has been developed for cardiolipin and its analog via a chlorophosphoramidite coupling reaction followed by oxidation. The reagent, N,N-diisopropylmethylphosphoramidic chloride, couples effectively with 1,2-O-dimyristoyl-sn-glycerol in the presence of an amidite activator to form a phosphoamidite intermediate, which then reacts with 2-O-benzylglycerol in the presence of a basic catalyst followed by in situ oxidation to give the corresponding protected cardiolipin. Deprotection of the protecting groups provides tetramyristoyl cardiolipin in good overall yield of 60%. The synthetic method is applicable to large-scale synthesis of cardiolipin and various analogs with or without unsaturation for liposomal drug delivery. Presented at the 94th AOCS Annual Meeting & Expo, Kansas City, Missouri, May 4–7, 2003.     

A short,concise route to diphosphatidylglycerol (Cardiolipin) and its variants

A new approach is described for the synthesis of the cardiolipin family of phospholipids that uses phosphonium salt methodology. The method involves the reaction of 2-O-protected glycerol with a trialkyl phosphite derived from 1,2-diacyl-sn-glycerol in the presence of pyridinium bromide perbromide and triethylamine to afford the phosphoric triesters. The synthesis involves three steps and allows the preparation of a wide range of cardiolipins with different substitution patterns and chain lengths, including unsaturated derivatives. The use of inexpensive protecting groups and the ease of purification facilitate this synthetic route and allow its scale-up in a higher overall yield (72%) than the literature methods.     

Low‐Cost and Highly Efficient Carbon‐Based Perovskite Solar Cells Exhibiting Excellent Long‐Term Operational and UV Stability

Today's perovskite solar cells (PSCs) mostly use components, such as organic hole conductors or noble metal back contacts, that are very expensive or cause degradation of their photovoltaic performance. For future large‐scale deployment of PSCs, these components need to be replaced with cost‐effective and robust ones that maintain high efficiency while ascertaining long‐term operational stability. Here, a simple and low‐cost PSC architecture employing dopant‐free TiO₂ and CuSCN as the electron and hole conductor, respectively, is introduced while a graphitic carbon layer deposited at room temperature serves as the back electrical contact. The resulting PSCs show efficiencies exceeding 18% under standard AM 1.5 solar illumination and retain ≈95% of their initial efficiencies for >2000 h at the maximum power point under full‐sun illumination at 60 °C. In addition, the CuSCN/carbon‐based PSCs exhibit remarkable stability under ultraviolet irradiance for >1000 h while under similar conditions, the standard spiro‐MeOTAD/Au based devices degrade severely.     

Large‐Grain Tin‐Rich Perovskite Films for Efficient Solar Cells via Metal Alloying Technique

Fast research progress on lead halide perovskite solar cells has been achieved in the past a few years. However, the presence of lead (Pb) in perovskite composition as a toxic element still remains a major issue for large‐scale deployment. In this work, a novel and facile technique is presented to fabricate tin (Sn)‐rich perovskite film using metal precursors and an alloying technique. Herein, the perovskite films are formed as a result of the reaction between Sn/Pb binary alloy metal precursors and methylammonium iodide (MAI) vapor in a chemical vapor deposition process carried out at 185 °C. It is found that in this approach the Pb/Sn precursors are first converted to (Pb/Sn)I₂ and further reaction with MAI vapor leads to the formation of perovskite films. By using Pb–Sn eutectic alloy, perovskite films with large grain sizes up to 5 µm can be grown directly from liquid phase metal. Consequently, using an alloying technique and this unique growth mechanism, a less‐toxic and efficient perovskite solar cell with a power conversion efficiency (PCE) of 14.04% is demonstrated, while pure Sn and Pb perovskite solar cells prepared in this manner yield PCEs of 4.62% and 14.21%, respectively. It is found that this alloying technique can open up a new direction to further explore different alloy systems (binary or ternary alloys) with even lower melting point.     

Sustainable Synthesis of Co@NC Core Shell Nanostructures from Metal Organic Frameworks via Mechanochemical Coordination Self‐Assembly: An Efficient Electrocatalyst for Oxygen Reduction Reaction

Herein, a new type of cobalt encapsulated nitrogen‐doped carbon (Co@NC) nanostructure employing Zn_xCo_1?x(C₃H₄N₂) metal–organic framework (MOF) as precursor is developed, by a simple, ecofriendly, solvent‐free approach that utilizes a mechanochemical coordination self‐assembly strategy. Possible evolution of Zn_xCo_1?x(C₃H₄N₂) MOF structures and their conversion to Co@NC nanostructures is established from an X‐ray diffraction technique and transmission electron microscopy analysis, which reveal that MOF‐derived Co@NC core–shell nanostructures are well ordered and highly crystalline in nature. Co@NC–MOF core–shell nanostructures show excellent catalytic activity for the oxygen reduction reaction (ORR), with onset potential of 0.97 V and half‐wave potential of 0.88 V versus relative hydrogen electrode in alkaline electrolyte, and excellent durability with zero degradation after 5000 potential cycles; whereas under similar experimental conditions, the commonly utilized Pt/C electrocatalyst degrades. The Co@NC–MOF electrocatalyst also shows excellent tolerance to methanol, unlike the Pt/C electrocatalyst. X‐ray photoelectron spectroscopy (XPS) analysis shows the presence of ORR active pyridinic‐N and graphitic‐N species, along with CoN_x? C_y and Co? N_x ORR active (M–N–C) sites. Enhanced electron transfer kinetics from nitrogen‐doped carbon shell to core Co nanoparticles, the existence of M–N–C active sites, and protective NC shells are responsible for high ORR activity and durability of the Co@NC–MOF electrocatalyst.     

Modeling of fluid flow in a tube with a moving indentation

The time-dependent flow in a tube with a moving indentation is numerically simulated using a dynamic mesh model. The model was used to simulate the flow in a tube with an indentation moving at different frequencies. The model was validated for a two-dimensional channel with a moving indentation. The results exhibited good agreement with the available experimental results. The results show that a single vortex was formed at a wall frequency of 0.1 Hz and was swept out of the tube at the end of the period. At a higher frequency of 1 Hz, vortex doubling occurred with reverse flow dominating downstream of the indentation. The results also show that the wall shear stress was larger for the higher frequency case of the moving indentation.     

Synthesis and characterization of APTMS/melamine cured hyperbranched polyester-epoxy hybrid coatings

An epoxy-terminated hyperbranched polyester (EPHBP) was prepared by the reaction of hyperbranched polyester (HBP) and epichlorohydrin (EPH). Herein, we have synthesized a new kind of highly epoxy ended branched polyester to enhance the chemical bonding at the interfaces and to reduce the melt viscosity. The structural investigation of the hyperbranched polyesters was carried by spectroscopic techniques such as nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR) while molar masses were determined using gel permeation chromatography (GPC). The effect of the content of hexamethoxy methyl melamine (HMMA) and 3-amino propyltrimethoxysilane (APTMS) mixture on the thermal, mechanical and interfacial properties of EPHBP resins were also studied. The thermal, dynamic mechanical and mechanical properties of the heat cured coating films were also investigated. The combined analysis of the results indicate that the introduction of APTMS results in the enhancement of the thermal stability, glass-transition temperature (T_g), storage modulus, tensile strength and contact angle of the cured films. The improvement in properties depends on the APTMS content of the cured films. The cured films have also shown higher elongation at break due to the use of HMMA and presence of unmodified epoxide groups which indicates good flexibility and toughness of the coating films.     

Numerical computation of nonlinear oscillatory two‐immiscible magnetohydrodynamic flow in dual porous media system: FTCS and FEM study

The transient Hartmann magnetohydrodynamic flow of two immiscible fluids flowing through a horizontal channel containing two porous media with oscillating lateral wall mass flux is studied. A two‐dimensional spatial model is developed for two fluids, one of which is electrically conducting and the other is electrically insulating. Both the fluid regimes are driven by a common pressure gradient. A Darcy‐Forchheimer drag force model is used to simulate the porous media effects on the flow in both the fluid regimes. Special boundary conditions are imposed at the interface. The governing second‐order nonlinear partial differential dimensionless equations are obtained for each region using a set of transformations. The resulting transport equations are controlled by the Hartmann hydromagnetic parameter (Ha), viscosity ratio parameter (α), two Darcy numbers (Da ₁ and Da ₂), two Forchheimer numbers (Fs ₁ and Fs ₂), two Reynolds numbers (Re ₁ and Re ₂), frequency parameter ( εA) associated with the transpiration (lateral wall flux) velocity and a periodic frequency parameter ( ω*t*). Numerical forward time/central space finite‐difference solutions are obtained for a wide range of the governing parameters. Bench marking is performed with a Galerkin finite‐element method (MAGNETO‐FEM), and the results are found to be in excellent agreement. Applications of the model include magnetic cleanup operations in coastal/ocean seabed oil spills and electromagnetic purification of petroleum reservoir fluids.     

Effect of reinforcement of sustainable β‐CaSiO3 nanoparticles in bio‐based epoxy resin system

The β‐CaSiO₃ nanoparticles (NPs) were prepared using calcium carbonate from egg shells and silica as precursors. These NPs were incorporated (1–4 wt %) into bio‐based epoxy resin to fabricate nanocomposites. Thermal and mechanical tests were carried out on these composites. The results of dynamic mechanical analysis showed significant improvement in the storage modulus of 1 and 2 wt % composites. The thermomechanical analysis data revealed ～19 and 20% of reduction in coefficient of thermal expansion for 1 wt % of CaSiO₃ before and after glass transition as compared to the neat epoxy system. Thermogravimetric analysis results also showed delayed thermal degradation of the composites by significant amounts (17–35°C) for 5% of decomposition, a proportional increase in residues corresponding to the loading concentrations. The flexure tests showed significant improvements in strength (17–36%), modulus (5–33%), and toughness for 1–4 wt % of reinforcement of β‐CaSiO₃ NPs. Theoretical calculations of the reinforcement effect on the flexure modulus of the composites agree well with the experimental values. The scanning electron micrograph of the fractured surfaces revealed better interfacial interactions in the composites and enhancements in crack path deflections over the neat specimen. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40867.