Deuteriodifluoromethylation and gem‐Difluoroalkenylation of Aldehydes Using ClCF2H in Continuous Flow

The deuteriodifluoromethyl group (CF₂D) represents a challenging functional group due to difficult deuterium incorporation and unavailability of precursor reagents. Herein, we report the use of chlorodifluoromethane (ClCF₂H) gas in the continuous flow deuteriodifluoromethylation and gem‐difluoroalkenylation of aldehydes. Mechanistic studies revealed that the difluorinated oxaphosphetane (OPA) intermediate can proceed via alkaline hydrolysis in the presence of D₂O to provide α‐deuteriodifluoromethylated benzyl alcohols or undergo a retro [2+2] cycloaddition under thermal conditions to provide the gem‐difluoroalkenylated product.     

A Narrative Review on the Phytochemistry,Pharmacology and Therapeutic Potentials of Clinacanthus nutans (Burm. f.) Lindau Leaves as an Alternative Source of Future Medicine

The application of natural products and supplements has expanded tremendously over the past few decades. Clinacanthus nutans (C. nutans), which is affiliated to the Acanthaceae family, has recently caught the interest of researchers from the countries of subtropical Asia due to its medicinal uses in alternative treatment for skin infection conditions due to insect bites, microorganism infections and cancer, as well as for health well-being. A number of bioactive compounds from this plant’s extract, namely phenolic compounds, sulphur containing compounds, sulphur containing glycosides compounds, terpens-tripenoids, terpens-phytosterols and chlorophyll-related compounds possess high antioxidant activities. This literature search yielded about one hundred articles which were then further documented, including the valuable data and findings obtained from all accessible electronic searches and library databases. The promising pharmacological activities from C. nutans leaves extract, including antioxidant, anti-cancer, anti-viral, anti-bacterial, anti-fungal, anti-venom, analgesic and anti-nociceptive properties were meticulously dissected. Moreover, the authors also discuss a few of the pharmacological aspect of C. nutans leaves extracts against anti-hyperlipidemia, vasorelaxation and renoprotective activities, which are seldom available from the previously discussed review papers. From the aspect of toxicological studies, controversial findings have been reported in both in-vitro and in-vivo experiments. Thus, further investigations on their phytochemical compounds and their mode of action showing pharmacological activities are required to fully grasp both traditional usage and their suitability for future drugs development. Data related to therapeutic activity and the constituents of C. nutans leaves were searched by using the search engines Google scholar, PubMed, Scopus and Science Direct, and accepting literature reported between 2010 to present. On the whole, this review paper compiles all the available contemporary data from this subtropical herb on its phytochemistry and pharmacological activities with a view towards garnering further interest in exploring its use in cardiovascular and renal diseases.     

Wavelet-Based Method for Time-Domain Noise Analysis and Reduction in a Frequency-Scan Ion Trap Mass Spectrometer

We adopt an orthogonal wavelet packet decomposition (OWPD) filtering approach to cancel harmonic interference noises arising from an AC power source in time domain and remove the resulting rf voltage interference noise from the mass spectra acquired by using a charge detection frequency-scan quadrupole ion trap mass spectrometer. With the use of a phase lock resampling technique, the transform coefficients of the rf interference in signals become a constant, exhibiting a shift of the baseline in different rf phases. The rf interference is therefore removable by shifting the baselines back to zero in OWPD coefficients. The approach successfully reduces the time-domain background noise from 1367 electrons (rms) to 408 electrons (rms) (an improvement of 70?%) and removes the high frequency noise components in the charge detection ion trap mass spectrometry. Unlike other smoothing or averaging methods commonly used in the mass-to-charge (m/Ze) domain, our approach does not cause any distortion of original signals.     

Controlling Metallophilic Interactions in Chiral Gold(I) Double Salts towards Excitation Wavelength‐Tunable Circularly Polarized Luminescence

Materials exhibiting excitation wavelength‐dependent photoluminescence (Ex‐De PL) in the visible region have potential applications in bioimaging, optoelectronics and anti‐counterfeiting. Two multifunctional, chiral [Au(NHC)₂][Au(CN)₂] (NHC=(4R,5R)/(4S,5S)‐1,3‐dimethyl‐4,5‐diphenyl‐4,5‐dihydro‐imidazolin‐2‐ylidene) complex double salts display Ex‐De circularly polarized luminescence (CPL) in doped polymer films and in ground powder. Emission maxima can be dynamically tuned from 440 to 530 nm by changing the excitation wavelength. The continuously tunable photoluminescence is proposed to originate from multiple emissive excited states as a result of the existence of varied Au^I???Au^I distances in ground state. The steric properties of the NHC ligand are crucial to the tuning of Au^I???Au^I distances. An anti‐counterfeiting application using these two salts is demonstrated.     

Piceatannol Protects Brain Endothelial Cell Line (bEnd.3) against Lipopolysaccharide-Induced Inflammation and Oxidative Stress

Dysfunction of the blood–brain barrier (BBB) is involved in the pathogenesis of many cerebral diseases. Oxidative stress and inflammation are contributing factors for BBB injury. Piceatannol, a natural ingredient found in various plants, such as grapes, white tea, and passion fruit, plays an important role in antioxidant and anti-inflammatory responses. In this study, we examined the protective effects of piceatannol on lipopolysaccharide (LPS) insult in mouse brain endothelial cell line (bEnd.3) cells and the underlying mechanisms. The results showed that piceatannol mitigated the upregulated expression of adhesion molecules (ICAM-1 and VCAM-1) and iNOS in LPS-treated bEnd.3 cells. Moreover, piceatannol prevented the generation of reactive oxygen species in bEnd.3 cells stimulated with LPS. Mechanism investigations suggested that piceatannol inhibited NF-κB and MAPK activation. Taken together, these observations suggest that piceatannol reduces inflammation and oxidative stress through inactivating the NF-κB and MAPK signaling pathways on cerebral endothelial cells in vitro.     

Low molecular weight organogelators derived from threefold symmetric tricarbamates

A group of new low molecular weight organogelators based on threefold symmetric tricarbamate were synthesized and characterized. The tricarbamates with long alkyl chains were able to gelate a wide range of polar and nonpolar organic solvents such as acetonitrile and cyclohexane, generally at concentrations lower than 20 g/L. The best organogel formation was obtained using a threefold symmetric tricarbamate in n-dodecane, in which a sufficiently transparent gel was formed at the critical gelation concentration 1 g/L. Intermolecular hydrogen bonding by the tricarbamate in a nonpolar solvent benzene-d₆ was indicated by ¹H NMR spectra. Its maximum UV absorption was 11 nm higher in chloroform than in n-dodecane, and this red shift indicated increased conjugation between the benzene core and the carbamate substituents, which confirmed a change in its conformation from nonpolar to polar solvent. The self-assembling behavior of the tricarbamate in dilute solutions was investigated by TEM. Fiber-like networks were observed in a large range of solution concentrations.     

Highly enantioselective alkynylzinc addition to aromatic aldehydes catalyzed by self-assembled titanium catalysts

A highly enantioselective catalyst generated by a combination of BINOL and another ligand with Ti(OiPr)4 was found to be highly effective for the alkynylzinc addition to aromatic aldehydes with enantioselectivities as high as >99%.     

Catalytic hydrogenation of arenes with rhodium nanoparticles in a water-in-supercritical CO2 microemulsion

Rhodium nanoparticles dispersed by a CO2 microemulsion are effective catalysts for rapid hydrogenation of arenes in supercritical CO2.