Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

Hydrodynamics of a flexible cylinder under modulated vortex-induced vibrations

Both amplitude modulation and frequency modulation of Vortex-induced Vibration (VIV) are observed in a recent model test of a flexible cylinder under oscillatory flow, but its hydrodynamics has not yet been broached in detail. This paper employs the Forgetting Factor Least Squares (FF-LS) method for identification of time-varying hydrodynamics of a flexible cylinder under modulated VIV. The FF-LS method’s applicability to accurately identify time-varying hydrodynamic coefficients is demonstrated through an elastically mounted rigid cylinder under flow with a given modulated motion. Furthermore, we propose a framework to predict instantaneous amplitude (envelope) and frequency using time-varying hydrodynamic coefficients to establish their analytical relationship. This prediction method is further extended to a highly tensioned flexible cylinder through Fourier series expansion in the spatial domain. By performing the identification procedure for all sampled data of a flexible cylinder undergoing oscillatory flow, we obtain the corresponding time-varying hydrodynamics in the cross-flow direction considering the amplitude and frequency modulation. The results show that, under modulated VIV, hydrodynamic coefficients of the flexible cylinder also show time-varying characteristics. We further investigate differences between identified hydrodynamic coefficients and those obtained from the database of a cylinder with modulated motion under flow. Prediction results using these identified time-varying coefficients reveal that the time-varying excitation coefficients mainly influence the amplitude modulation, and the time-varying added-mass coefficients contain the major information of frequency modulation. These results further suggest including the temporal derivative of the instantaneous amplitude as one determining parameter in building databases to improve the prediction of modulated VIV.     

UPLC-Q/TOF-MS coupled with multivariate analysis for comparative analysis of metabolomic in Dendrobium nobile from different growth altitudes

Dendrobium nobile alkaloids (DNLA) and glycosides are the main active components extracted from Dendrobium nobile Lindl. (D. nobile) used for thousands of years in China. The pharmacological effects of the above chemical components are significantly different. D. nobile is mainly grown at an altitude ranging from 230 to 800 m in Chishui City, Northwest Guizhou Province. However, it is unclear whether the metabolite in D. nobile is influenced by the planting altitude. Hence, to reveal the different metabolite in D. nobile cultivated at the altitude of 336 m, 528 m, and 692 m, ultra-high performance liquid chromatography with Q/TOF-MS couple with multivariate analysis were developed. Using the orthogonal partial least squares-discriminant analysis, 19 different metabolites were discovered and then tentatively assigned their structures as alkaloids and glycosides by comparing mass spectrometry data with in-house database and literature. Moreover, the result of semiquantitative analysis showed the content of dendrobine that was belonged to alkaloids significantly increased at the altitude of 692 m, whereas the content of glycosides demonstrated an accumulation trend at the altitude of 528 m. The results could provide valuable information for the optimal clinical drug therapeutics and provide a reference for quality control.     

Amperometric Detection of Ethanol Vapors by Screen Printed Electrodes Modified by Paper Crowns Soaked with Room Temperature Ionic Liquids

A convenient assembly recently proposed for screen printed gold electrodes (SPEs) suitable for measurements in gaseous samples is here tested for the analysis of the ethanol content in alcoholic drinks. This assembly involves the use of a circular crown of filter paper, soaked in the room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium hydrogen sulfate, which is simply placed upon a disposable screen printed cell, so as to contact the outer edge of the gold disc working electrode, as well as peripheral counter and reference electrodes. The electrical contact between the paper crown soaked in RTIL and the SPE electrode is assured by a gasket and all components are installed in a polylactic acid holder. This assembly provides a portable and disposable electrochemical platform, assembled by the easy immobilization onto a porous and inexpensive supporting material such as paper of a RTIL characterized by profitable electrical conductivity and negligible vapor pressure. The electroanalytical performance of this device was assayed for the flow injection analysis of the ethanol concentration in some real samples of wine and beer and the results obtained are compared with the alcoholic degree reported in the relevant bottle-labels, thus highlighting a substantially satisfactory agreement. Repeatable sharp peaks (RSD=6–8 %) were detected for ethanol over a wide linear range (1–20 % v/v in water) and a detection and quantitation limit of 0.55 % v/v and 1.60 % v/v were inferred for a signal-to-noise ratio of 3 and 10, respectively.     

Single Atom Ring Contraction of Peptide Macrocycles Using Cornforth Rearrangement

Site-selective transformations of densely functionalized scaffolds have been a topic of intense interest in chemical synthesis. Herein we have repurposed the rarely used Cornforth rearrangement as a tool to effect a single-atom ring contraction in cyclic peptide backbones. Investigations into the kinetics of the rearrangement were carried out to understand the impact of electronic factors, ring size, and linker type on the reaction efficiency. Conformational analysis was undertaken and showed how subtle differences in the peptide backbone result in substrate-dependent reaction profiles. This methodology can now be used to perform conformation-activity studies. The chemistry also offers an opportunity to install building blocks that are not compatible with traditional C-to-N iterative synthesis of macrocycle precursors.     

The Crucial Role of Sb2F10 in the Chemical Synthesis of F2

The purely chemical synthesis of fluorine is a spectacular reaction which for more than a century had been believed to be impossible. In 1986, it was finally experimentally achieved, but since then this important reaction has not been further studied and its detailed mechanism had been a mystery. The known thermal stability of MnF₄ casts serious doubts on the originally proposed hypothesis that MnF₄ is thermodynamically unstable and decomposes spontaneously to a lower manganese fluoride and F₂. This apparent discrepancy has now been resolved experimentally and by electronic structure calculations. It is shown that the reductive elimination of F₂ requires a large excess of SbF₅ and occurs in the last reaction step when in the intermediate [SbF₆][MnF₂][Sb₂F₁₁] the addition of one more SbF₅ molecule to the [SbF₆]⁻ anion generates a second tridentate [Sb₂F₁₁]⁻ anion. The two tridentate [Sb₂F₁₁]⁻ anions then provide six fluorine bridges to the Mn atom thereby facilitating the reductive elimination of the two fluorine ligands as F₂.     

An In Situ Investigation of the Protein Corona Formation Kinetics of Single Nanomedicine Carriers by Self-Regulated Electrochemiluminescence Microscopy

Protein coronas are present extensively at the bio-nano interface due to the natural adsorption of proteins onto nanomaterials in biological fluids. Aside from the robust property of nanoparticles, the dynamics of the protein corona shell largely define their chemical identity by altering interface properties. However, the soft coronas are normally complex and rapidly changing. To real-time monitor the entire formation, we report here a self-regulated electrochemiluminescence (ECL) microscopy based on the interaction of the Ru(bpy)₃³⁺ with the nanoparticle surface. Thus, the heterogeneity of the protein corona is in situ observed in single nanoparticle “cores” before and after loading drugs in nanomedicine carriers. The label-free, optical stable and dynamic ECL microscopy minimize misinterpretations caused by the variation of nanoparticle size and polydispersity. Accordingly, the synergetic actions of proteins and nanoparticles properties are uncovered by chemically engineered protein corona. After comparing the protein corona formation kinetics in different complex systems and different nanomedicine carriers, the universality and accuracy of this technique were well demonstrated via the protein corona formation kinetics curves regulated by competitive adsorption of Ru(bpy)₃³⁺ and multiple proteins on surface of various carriers. The work is of great significance for studying bio-nano interface in drug delivery and targeted cancer treatment.     

Promoter-Controlled Synthesis and Conformational Analysis of Cyclic Mannosides up to a 32-mer

Cyclodextrins are widely used as carriers of small molecules for drug delivery owing to their remarkable host properties and excellent biocompatibility. However, cyclic oligosaccharides with different sizes and shapes are limited. Cycloglycosylation of ultra-large bifunctional saccharide precursors is challenging due to the constrained conformational spaces. Herein we report a promoter-controlled cycloglycosylation approach for the synthesis of cyclic α-(1→6)-linked mannosides up to a 32-mer. Cycloglycosylation of the bifunctional thioglycosides and (Z)-ynenoates was found to be highly dependent on the promoters. In particular, a sufficient amount of a gold(I) complex played a key role in the proper preorganization of the ultra-large cyclic transition state, providing a cyclic 32-mer polymannoside, which represents the largest synthetic cyclic polysaccharide to date. NMR experiments and a computational study revealed that the cyclic 2-mer, 4-mer, 8-mer, 16-mer, and 32-mer mannosides adopted different conformational states and shapes.     

Expanding the Range of Bioorthogonal Tags for Multiplex Stimulated Raman Scattering Microscopy

Multiplex optical detection in live cells is challenging due to overlapping signals and poor signal-to-noise associated with some chemical reporters. To address this, the application of spectral phasor analysis to stimulated Raman scattering (SRS) microscopy for unmixing three bioorthogonal Raman probes within cells is reported. Triplex detection of a metallacarborane using the B−H stretch at 2480–2650 cm⁻¹, together with a bis-alkyne and deuterated fatty acid can be achieved within the cell-silent region of the Raman spectrum. When coupled to imaging in the high-wavenumber region of the cellular Raman spectrum, nine discrete regions of interest can be spectrally unmixed from the hyperspectral SRS dataset, demonstrating a new capability in the toolkit of multiplexed Raman imaging of live cells.