Negative thermal expansion in NbF_3 and NbOF_2:A comparative theoretical study

Thermal expansion control is always an obstructive factor and challenging in high precision engineering field. Here,the negative thermal expansion of Nb F_3 and Nb OF_2 was predicted by first-principles calculation with density functional theory and the quasi-harmonic approximation(QHA). We studied the total charge density, thermal vibration, and lattice dynamic to investigate the thermal expansion mechanism. We found that the presence of O induced the relatively strong covalent bond in Nb OF_2, thus weakening the transverse vibration of F and O in Nb OF_2, compared with the case of Nb F_3.In this study, we proposed a way to tailor negative thermal expansion of metal fluorides by introducing the oxygen atoms.The present work not only predicts two NTE compounds, but also provides an insight on thermal expansion control by designing chemical bond type.     

Solution combustion synthesis,energy and environment: Best parameters for better materials

Solution combustion synthesis (SCS) is a worldwide used methodology for the preparation of inorganic ceramic and composite materials with controlled properties for a wide number of applications, from catalysis to photocatalysis and electrocatalysis, from heavy metal removal to sensoristics and electronics. The high versatility and efficiency of this technique have led to the introduction of many variants, which allowed important optimization to the prepared materials. Moreover, its ecofriendly nature encouraged further studies about the use of sustainable precursors for the preparation of nanomaterials for energy and environment, according to the concept of circular economy. On the other hand, the large variety of expressions to define SCS and the often-contradictory definitions of the SCS parameters witnessed a scarce consciousness of the potentiality of this methodology. In this review article, the most important findings about SCS and the selection criteria for its main parameters are critically reviewed, in order to give useful guidelines to those scientists who want to use this methodology for preparing materials with improved or new functional properties. This review aims as well (i) to bring more clarity in the SCS terminology (ii) to increase the awareness of the SCS as a convenient tool for the synthesis of materials and (iii) to propose a new perspective in the SCS, with special attention to the use of ecofriendly procedures. Part of the review is also dedicated to precautions and limitations of this powerful methodology.     

Nonionic Dendritic and Carbohydrate Based Amphiphiles: Self‐Assembly and Transport Behavior

Herein, a new series of non‐ionic dendritic and carbohydrate based amphiphiles is synthesized employing biocompatible starting materials and studied for supramolecular aggregate formation in aqueous solution. The dendritic amphiphiles 12 and 13 possessing poly(glycerol) [G2.0] as hydrophilic unit and C‐10 and C‐18 hydrophobic alkyl chains, respectively, exhibit low critical aggregation concentration (CAC) in the order of 10⁻⁵m and hydrodynamic diameters in the 8–10 nm range and supplemented by cryogenic transmission electron microscopy. Ultraviolet‐visible (UV‐Vis) and fluorescence spectroscopy suggests the effective solubilization of hydrophobic guests by the self‐assembled architectures, with the nanotransporters 12 and 13 possessing the highest encapsulation efficiency of 80.74 and 98.03% for curcumin. Efficient uptake of encapsulated curcumin in adenocarcinomic human alveolar basal epithelial (A549) cells is observed by confocal laser scanning microscopy. Amphiphiles 12 and 13 are non‐cytotoxic at the concentrations studied, however, curcumin encapsulated samples efficiently reduce the viability of A549 cells in vitro. Experimental studies indicate the ability of amphiphile 13 to encapsulate 1‐anilinonaphthalene‐8‐sulfonic acid (ANS) and curcumin with binding constant of 1.16 × 105⁵m ⁻¹ and 1.43 × 10⁶m ⁻¹, respectively. Overall, our findings demonstrate the potential of these dendritic amphiphiles for the development of prospective nanocarriers for the solubilization of hydrophobic drugs.     

Electronic and ligating properties of carbocyclic carbenes: A theoretical investigation

Carbocyclic carbenes (CCCs) are a class of nucleophilic carbenes which are very similar to N-heterocyclic carbenes (NHCs) in terms of their reactivity, but they do not contain a stabilizing heteroatom in their cyclic ring system. In this study, 17 representative known CCCs and 34 newly designed CCCs are evaluated using quantum chemical methods, and the results are compared in terms of their stability, nucleophilicity, and proton affinity (PA) parameters. The results are divided on the basis of ring size of the known and reported CCCs. The stability, nucleophilicity, PA, complexation energy, and bond strength–related parameters were estimated using M06/6-311++G(d,p) method. The results indicated that the CCCs known in the literature are strong σ-electron donating species and have considerable π-accepting properties. This study led to the design and identification of a few new CCCs with dimethylamine and diaminomethynyl substituents which can be singlet stable and are substantially nucleophilic. © 2018 Wiley Periodicals, Inc.     

Enhanced oral bioavailability through nanotechnology in Saudi Arabia: A meta-analysis

Oral administration represents the most suitable mean among different means of administering drugs because it ensures high compliance by patients. Nevertheless, the lacking aqueoussolubility, as well as, inadequate metabolic/enzymatic stability of medicines are leading obstacles to successful drug administration by oral route. Among different systems, drug administration systems based on nanotechnology have the potential to surmount the problems associated with oral drug administration. Drug delivery systems based on nanotechnology offer an alternative to deliver antihypertensive agents with enhanced therapeutic effect and bioavailability. In this study, meta-analysis was utilized in combining data relating to oral bioavailability (area under plasma concentration time curve, AUC) enhancement through nanotechnology from multiple studies. Twenty-one studies of the total 37articles included in this study were from the kingdom of Saudi Arabia and were included in a specific meta-analysis. From the analysis conducted, the overall enhancement power of the nanotechnology based formulations on drug bioavailability was found to be 7.94% (95 %CI [5.809, 10.064]). Haven utilized comprehensive and recent data of the confirmed the enhancement of bioavailability using nanotechnology which for this study was grouped into five: solid lipid nanoparticles; polymer based nanoparticles; SNEEDS/Nanoemulsion; liposomes/proliposomes and; nanostructured lipid carriers. Furthermore, the meta-analysis, provided evidence of insignificant differences between APG Bio-SNEDDS and its free drug suspension (Apeginin, APG), though with relative bioavailabiilty of 1.91. Notwithstanding most of the treatment showed a substantial relative bioavailability.     

Deciphering Internal and External π-Conjugation in C3-Symmetric Multiple Azobenzene Connected Systems in Self-Assembly

Two tripodal C₃-symmetric photoswitchable molecular systems T1 and T2 are reported that have extended conjugation at external and internal positions using an acryl group. The influence of the extended π-bonds in their absorption properties, thermal relaxation of the photoisomers and their propensities in forming supramolecular self-assemblies have been explored through spectroscopy, and microscopic studies. In particular, the investigations on the self-assembly have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM), polarized optical microscopy (POM), X-ray diffraction studies (XRD) and atomic force microscopy (AFM). Remarkably, the position of the acryl group influences the behaviour of the two target molecules in supramolecular assembly, and also in the formation of photoresponsive organic hydrogels or microcrystals.     

Reduction and pH dual‐responsive block copolymers containing pendent p‐nitrobenzyl carbamate functionalities: Synthesis and self‐assembly behavior

We report on the preparation of reduction‐responsive amphiphilic block copolymers containing pendent p‐nitrobenzyl carbamate (pNBC)‐caged primary amine moieties by reversible addition–fragmentation chain transfer (RAFT) radical polymerization using a poly(ethylene glycol)‐based macro‐RAFT agent. The block copolymers self‐assembled to form micelles or vesicles in water, depending on the length of hydrophobic block. Triggered by a chemical reductant, sodium dithionite, the pNBC moieties decomposed through a cascade 1,6‐elimination and decarboxylation reactions to liberate primary amine groups of the linkages, resulting in the disruption of the assemblies. The reduction sensitivity of assemblies was affected by the length of hydrophobic block and the structure of amino acid‐derived linkers. Using hydrophobic dye Nile red (NR) as a model drug, the polymeric assemblies were used as nanocarriers to evaluate the potential for drug delivery. The NR‐loaded nanoparticles demonstrated a reduction‐triggered release profile. Moreover, the liberation of amine groups converted the reduction‐responsive polymer into a pH‐sensitive polymer with which an accelerated release of NR was observed by simultaneous application of reduction and pH triggers. It is expected that these reduction‐responsive block copolymers can offer a new platform for intracellular drug delivery. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1333–1343     

Self‐assembled polyurea macromer nanodispersion and resulting hybrid polyurea‐acrylic emulsions and films

A polyurea macromer (PUM) was synthesized and dispersed in basic conditions to form self‐assembled nanoparticles (<20 nm dispersions, up to 30 wt % aq. soln.). These nanoparticles enabled surfactant‐free emulsion polymerization to form hybrid polyurea‐acrylic particles despite the absence of a measureable water‐soluble fraction. The T_g of the starting PUM material was a strong function of the PUM's extent of neutralization and hydration (varying between 100 °C and >175 °C) due to changes in hydrogen and ionic bonding. Two separate hybrid polyurea‐acrylic emulsion systems were prepared: one by direct polymerization of (meth)acrylic monomers in the presence of the nanodispersion and a second by a physical blend of PUM nanodispersion with an acrylic latex control. The direct polymerization method resulted in a hybrid emulsion particle size that developed by a mechanism resembling conventional emulsion polymerization and was unlike that described for seeded polyurethane dispersion systems. Film hardness was shown to increase with increasing coating thickness for the hybrid film prepared by direct polymerization. The resulting mechanical properties could be explained by applying mechanical models for a composite foam structure. These results were unprecedented for normal elastomer films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1373–1388     

油-气-水三相流超声传感器持气率测量*

为探索油-气-水三相流持气率测量难题,该文开展了脉冲透射式超声传感器持气率测量动态实验研究。首先,利用超声传感器与光纤传感器组合,测取了油-气-水三相流中段塞流、混状流、泡状流的响应信号;其次,提取了超声脉冲信号的最大值序列来反映不同流型时超声传感器响应特性,同时,借助双头光纤传感器与相关测速法,计算得到了流体中气泡弦长序列;最后,结合流型与泡径信息,利用超声传感器测量了不同流型下持气率,并分析了不同流型持气率预测的误差来源,为其他油-气-水三相流持气率测量传感器设计提供了借鉴。     

基于CARS技术的超燃冲压发动机点火过程温度测量

相干anti-Stokes Raman散射（coherent anti-Stokes Raman scattering，CARS）技术作为一种非接触测量手段，已广泛应用于多种发动机模型燃烧室温度测量及地面试验.然而，目前的工作主要集中在稳态燃烧场温度的测量，缺乏用高分辨率的单脉冲来测量瞬变的燃烧火焰温度及组分浓度的研究.基于CARS理论，结合多参数拟合算法，开发了基于MATLAB的CARS光谱计算和拟合程序CARSCF；利用McKenna平面火焰炉在不同工况下进行了温度测量，并与DLR测量结果进行对比，结果显示开发的CARSCF具有较高的测量重复性和准确性；最后将CARS技术应用于测量超燃冲压发动机点火过程中的温度测量，获取了点火过程中的温度.结果显示，在来流Mach数为3的条件下，H₂/air点火过程中温度呈现急剧上升然后缓慢下降，而CARS信号则呈现急剧上升然后急剧下降随后又缓慢上升的趋势，并且在点火过程中最高温度为1 511 K.