One‐Pot Synthesis of 2‐Amino‐4‐aryl‐3‐carbalkoxy‐7,7‐dimethyl‐5,6,7,8‐tetrahydrobenzo[b]pyran Derivatives Catalyzed by KF/Basic Al2O3 Under Ultrasound Irradiation

Abstract

Synthesis of 2‐amino‐4‐aryl‐3‐carbalkoxy‐7,7‐dimethyl‐5‐oxo‐5,6,7,8‐tertrahydrobenzo[b]pyran derivatives was carried out in 81–98% yields by one‐pot condensation of aromatic aldehydes with cyanoacetic esters and 5,5‐dimethyl‐1,3‐cyclohexanedione catalyzed by KF/basic Al₂O₃ at room temperature under ultrasound irradiation.     

Flame retardant high density polyethylene optimized by on-line ultrasound extrusion

The effect of on-line ultrasound application by a special static mixer die which promotes extensional flow simultaneously during the single screw extrusion process was thoroughly studied. The proportion of aluminum trihydroxide (ATH) used as flame retardant on high density polyethylene (HDPE) was optimized. The morphological, thermal, flammability, combustion, mechanical and rheological properties of the materials were investigated. The morphological study pointed out that this process is able to strongly reduce the size of ATH particles and improve their dispersion and distribution within the polymer matrix. The addition of zinc borate (ZB) at low concentration (namely 3 phr) showed its well-known synergistic effect in the thermal, oxygen index and fire combustion behavior. According to the UL94 standard, the rating for all materials tested changed from HB to V2, with respect to materials prepared without ultrasound; furthermore a rating V0 was achieved only with the addition of 2 phr organo-clay. Rheological results under simple and small amplitude oscillatory shear flow confirmed the enhanced particle dispersion and finer particle morphology evidenced by larger values of the moduli and by deviations from the semicircular shape observed in the Cole–Cole diagram. Mechanical properties such as Izod impact resistance, tensile strength, strain at break and tenacity were also improved by the on-line ultrasound process. In this work, the appropriate on-line ultrasound extrusion conditions to use the lowest ATH content (30 phr or 21.5 in wt%) were found, rendering HDPE optimized flame retardant materials with improved processability and mechanical properties.     

Ultrasound-assisted addition of alcohols to N-acyliminium ions mediated by In(OTf)3 and synthesis of 1,2,3-triazoles

An easy and mild approach using ultrasound-assisted reaction addition of alcohols to N-acyliminium ion mediated by Lewis acid, In(OTf)₃, allowed the synthesis of ether pyrrolidinones; next, the products were converted to 1,2,3-triazoles using click chemistry reaction conditions. The products in both reactions were afforded in moderate to good yields.     

Solvent-free Brønsted acid-catalyzed Michael addition of nitrogen- and carbon-containing nucleophiles by ultrasound activation

A new method has been developed for the Michael addition of nitrogen- and carbon-containing nucleophiles to cyclic enones. Using this conjugate addition reaction, a variety of different nucleophiles can react with a range of cyclic enones in the presence of p-toluenesulfonic acid under solvent-free ultrasound irradiation conditions affording the corresponding C–N or C–C adducts in good to excellent yields. Comparatively, performing the reaction under ultrasound irradiation gives higher yields, is more efficient and environmentally benign than performing it at high pressure.     

Antioxidant capacity and antibacterial activity from Annona cherimola phytochemicals by ultrasound-assisted extraction and its comparison to conventional methods

In recent years, the food, pharmacy, and cosmetic industries have focused on the search of natural compounds with antimicrobial and antioxidant properties; commonly, these compounds are obtained from Kingdom plantae. The aim of the present work is comparing antibacterial and antioxidant capacity of Annona cherimola Mill leaves, using different extraction methods. The ultrasound assisted extraction technique (UAE) was compared with conventional techniques: Soxhlet and maceration. Water and ethanol were used as solvents for leaves extractions performed with these three methods. The main acetogenins reported in Annona cherimola Mill and Annona muricata L. species were simulated using the functional hybrid B3LYP and to confirm its presence, analysis of the compound composition was performed using FT-IR, UV–Vis and HPLC. Total phenolics (TP) and flavonoids (TF) were determined by spectroscopy techniques and novel Differential Pulse Voltammetry (DPV) electrochemical technique. Total Antioxidant Capacity (TAC) of the extracts was measured, using the DPPH, FRAP and CUPRAC techniques. The highest antioxidant content was found in the Soxhlet water extracts; even so, the UAE technique presented an attractive alternative due to considerable reduction in extraction time, which was greater than 99%, and possible selectivity in compounds extraction. Finally, antibacterial activity of the extracts was evaluated, obtaining the best results against gram-positive bacteria using UAE water extract. In this way, the UAE technique presents an excellent extraction option due to the considerable reduction in time and energy, as well as the increase in antibacterial activity.     

Sonocatalytic injury of cancer cells attached on the surface of a nickel–titanium dioxide alloy plate

The present study demonstrates ultrasound-induced cell injury using a nickel–titanium dioxide (Ni–TiO₂) alloy plate as a sonocatalyst and a cell culture surface. Ultrasound irradiation of cell-free Ni–TiO₂ alloy plates with 1 MHz ultrasound at 0.5 W/cm² for 30 s led to an increased generation of hydroxyl (OH) radicals compared to nickel–titanium (Ni–Ti) control alloy plates with and without ultrasound irradiation. When human breast cancer cells (MCF-7 cells) cultured on the Ni–TiO₂ alloy plates were irradiated with 1 MHz ultrasound at 0.5 W/cm² for 30 s and then incubated for 48 h, cell density on the alloy plate was reduced to approximately 50% of the controls on the Ni–Ti alloy plates with and without ultrasound irradiation. These results indicate the injury of MCF-7 cells following sonocatalytic OH radical generation by Ni–TiO₂. Further experiments demonstrated cell shrinkage and chromatin condensation after ultrasound irradiation of MCF-7 cells attached on the Ni–TiO₂ alloy plates, indicating induction of apoptosis.     

An efficient and practical synthesis of methylene dioximes by combination of ultrasound and phase transfer catalyst

The reaction of oximes with dichloromethane was carried out in 71–98% yields at 20–30 °C for 2–3.5 h in the presence of sodium hydroxide by combination of benzyldimethyltetradecylammonium chloride and ultrasonication. The main advantage of the present procedure is that the reaction time is much shorter than classical methods.     

Ultrasound-assisted crystallization (sonocrystallization)

The positive influence of ultrasound (US) on crystallization processes is shown by the dramatic reduction of the induction period, supersaturation conditions and metastable zone width. Manipulation of this influence can be achieved by changing US-related variables such as frequency, intensity, power and even geometrical characteristics of the ultrasonic device (e.g. horn type size). The volume of the sonicated solution and irradiation time are also variables to be optimized in a case-by-case basis as the mechanisms of US action on crystallization remain to be established. Nevertheless, the results obtained so far make foreseeable that crystal size distribution, and even crystal shape, can be ‘tailored’ by appropriate selection of the sonication conditions.     

低功率超声增强碘帕醇氯氧化的效果和路径

研究了低功率超声(US, <38 W)对NaClO氧化非离子型碘代X射线造影剂—碘帕醇(IPM)的增强作用及机理, 考察了NaClO添加浓度和超声功率的影响, 分析并计算了体系中的主要活性物种及其贡献. 采用高效液相色谱/串联质谱(HPLC/MS/MS)对降解产物进行分析, 推测IPM的降解路径. 结果表明, 低功率US显著增强了NaClO对IPM的氧化效果, 在25 ℃, pH=5.8, NaClO浓度为0.12 mmol/L条件下, 10 mg/L IPM在60 min的降解率达到85.8%. 其中NaClO氧化、 HO·和活性氯自由基(RCSs)是US/NaClO增强IPM降解的主要原因, 自由基分析计算它们的贡献率分别为15.82%, 4.65%和79.53%. NaClO浓度在0~0.24 mmol/L范围内, IPM的降解率随NaClO浓度升高而增加, 60 min后降解率由4.75%增加到91.12%; 超声功率为28.5 W, 降解率达到最高. 在 15~45 ℃温度范围内, IPM的降解过程符合表观一级反应动力学, 反应活化能(E_a)为59.03 kJ/mol. HPLC/MS/MS共检测出5种中间产物, 结合密度泛函理论(DFT)计算结果, 初步推测了IPM在US/NaClO体系中的降解途径和机理.     

Washing off intensification of cotton and wool fabrics by ultrasounds

Wet textile washing processes were set up for wool and cotton fabrics to evaluate the potential of ultrasound transducers (US) in improving dirt removal. The samples were contaminated with an emulsion of carbon soot in vegetable oil and aged for three hours in fan oven. Before washing, the fabrics were soaked for 3 min in a standard detergent solution and subsequently washed in a water bath. The dirt removal was evaluated through colorimetric measurements. The total color differences ΔE of the samples were measured with respect to an uncontaminated fabric, before and after each washing cycle. The percentage of ΔE variation obtained was calculated and correlated to the dirt removal. The results showed that the US transducers enhanced the dirt removal and temperature was the parameter most influencing the US efficiency on the cleaning process. Better results were obtained at a lower process temperature.