Physico-Chemical and Phytochemical Characterization of Moroccan Wild Jujube “Zizyphus lotus (L.)” Fruit Crude Extract and Fractions

Wild jujube “Ziziphus lotus (L.) Desf.” belongs to the Rhamnaceae family and is a traditionally herbaceous medicinal plant. It is very common in arid and semi-arid regions and is currently used for its antidiabetic, sedative, analgesic, anti-inflammatory and hypoglycemic activities. The aim of the present work was to characterize the physico-chemical properties and the phytochemical profile of wild jujube sample collected from the Guercif region, in order to determine the polyphenolic compounds and the antioxidant ability Analyses were carried out directly after the harvest for the determination of pH, refractive index, total soluble solid (°Brix), dry matter, sugar/acidity, total sugars, reducing sugars, as well as lipid and protein content. Results showed that the investigated fruit is acidic (pH 4.9 ± 0.23) and rich in sugars (80.2 g/100 g ± 3.81). The GC-MS analysis of the fruit revealed a number of volatile compounds, as many as 97, belonging to different chemical classes. The HPLC-DAD-ESI/MS analysis showed the presence of a total of 20 polyphenolic compounds in both EtOAc and MeOH-water extracts. Among them, p-Hydroxybenzoic acid was the most abundant in the EtOAc extract (185.68 µg/100 mg ± 0.5) whereas Quercetin 3-O-rhamnoside-7-O-glucoside was found in higher amounts in the MeOH-water extract (25.40 µg/100 mg ± 0.5). These components have medical interest, notably for human nutrition, as well as health benefits and therapeutic effects. Therefore, Moroccan jujube “Zizyphus lotus (L.)” fruit may have potential industrial applications for food formulations.     

“Texas-Sized” Molecular Boxes: From Chemistry to Applications

The design and synthesis of novel macrocyclic host molecules continues to attract attention because such species play important roles in supramolecular chemistry. However, the discovery of new classes of macrocycles presents a considerable challenge due to the need to embody by design effective molecular recognition features, as well as ideally the development of synthetic routes that permit further functionalization. In 2010, we reported a new class of macrocyclic hosts: a set of tetracationic imidazolium macrocycles, which we termed “Texas-sized” molecular boxes (TxSBs) in homage to Stoddart’s classic “blue box” (CBPQT⁴⁺). Compared with the rigid blue box, the first generation TxSB displayed considerably greater conformational flexibility and a relatively large central cavity, making it a good host for a variety of electron-rich guests. In this review, we provide a comprehensive summary of TxSB chemistry, detailing our recent progress in the area of anion-responsive supramolecular self-assembly and applications of the underlying chemistry to water purification, information storage, and controlled drug release. Our objective is to provide not only a review of the fundamental findings, but also to outline future research directions where TxSBs and their constructs may have a role to play.     

A Chewable Cure “Kanna”: Biological and Pharmaceutical Properties of Sceletium tortuosum

Sceletium tortuosum (L.) N.E.Br. (Mesembryanthemaceae), commonly known as kanna or kougoed, is an effective indigenous medicinal plant in South Africa, specifically to the native San and Khoikhoi tribes. Today, the plant has gained strong global attraction and reputation due to its capabilities to promote a sense of well-being by relieving stress with calming effects. Historically, the plant was used by native San hunter-gatherers and Khoi people to quench their thirst, fight fatigue and for healing, social, and spiritual purposes. Various studies have revealed that extracts of the plant have numerous biological properties and isolated alkaloids of Sceletium tortuosum are currently being used as dietary supplements for medicinal purposes and food. Furthermore, current research has focused on the commercialization of the plant because of its treatment in clinical anxiety and depression, psychological and psychiatric disorders, improving mood, promoting relaxation and happiness. In addition, several studies have focused on the isolation and characterization of various beneficial bioactive compounds including alkaloids from the Sceletium tortuosum plant. Sceletium was reviewed more than a decade ago and new evidence has been published since 2008, substantiating an update on this South African botanical asset. Thus, this review provides an extensive overview of the biological and pharmaceutical properties of Sceletium tortuosum as well as the bioactive compounds with an emphasis on antimicrobial, anti-inflammatory, anti-oxidant, antidepressant, anxiolytic, and other significant biological effects. There is a need to critically evaluate the bioactivities and responsible bioactive compounds, which might assist in reinforcing and confirming the significant role of kanna in the promotion of healthy well-being in these stressful times.     

High Yield Synthesis of Curcumin and Symmetric Curcuminoids: A “Click” and “Unclick” Chemistry Approach

The worldwide known and employed spice of Asian origin, turmeric, receives significant attention due to its numerous purported medicinal properties. Herein, we report an optimized synthesis of curcumin and symmetric curcuminoids of aromatic (bisdemethoxycurcumin) and heterocyclic type, with yields going from good to excellent using the cyclic difluoro-boronate derivative of acetylacetone prepared by reaction of 2,4-pentanedione with boron trifluoride in THF (ca. 95%). The subsequent cleavage of the BF₂ group is of significant importance for achieving a high overall yield in this two-step procedure. Such cleavage occurs by treatment with hydrated alumina (Al₂O₃) or silica (SiO₂) oxides, thus allowing the target heptanoids obtained in high yields as an amorphous powder to be filtered off directly from the reaction media. Furthermore, crystallization instead of chromatographic procedures provides a straightforward purification step. The ease and efficiency with which the present methodology can be applied to synthesizing the title compounds earns the terms “click” and “unclick” applied to describe particularly straightforward, efficient reactions. Furthermore, the methodology offers a simple, versatile, fast, and economical synthetic alternative for the obtention of curcumin (85% yield), bis-demethoxycurcumin (78% yield), and the symmetrical heterocyclic curcuminoids (80–92% yield), in pure form and excellent yields.     

Characterization of Phenolic Compounds,Vitamin E and Fatty Acids from Monovarietal Virgin Olive Oils of “Picholine marocaine” Cultivar

Olive oil is an important product in the Mediterranean diet, due to its health benefits and sensorial characteristics. Picholine marocaine is the most cultivated variety in Morocco. The present research aims to evaluate the phenolic compounds, vitamin E and fatty acids of commercial Picholine marocaine virgin olive oils (VOOs) from five different North Moroccan provinces (Chefchaouen, Taounate, Errachidia, Beni Mellal and Taza), using HPLC-photodiode array (PDA)/electrospray ionization (ESI)-MS, normal phase (NP)-HPLC/ fluorescence detector (FLD) and GC-flame ionization detector (FID)/MS, respectively. The obtained results showed an average content of 130.0 mg kg⁻¹ of secoiridoids (oleuropein aglycone, 10-hydroxy-oleuropein aglycone and ligstroside aglycone, oleocanthal and oleacein), 108.1 mg kg⁻¹ of phenolic alcohols (tyrosol and hydroxytyrosol), 34.7 mg kg⁻¹ of phenolic acids (caffeic acid, ferulic acid and elenolic acid), and 8.24 mg kg⁻¹ of flavonoids (luteolin, luteolin glucoside, apigenin). With regard to vitamin E, α-tocopherol was the most abundant vitamin E (57.9 mg kg⁻¹), followed by α-tocotrienol (2.5 mg kg⁻¹), γ-tocopherol (4.5 mg kg⁻¹) and β-tocopherol (1.9 mg kg⁻¹), while δ-tocopherol was not detected. Moreover, 14 fatty acids were found and, among them, oleic acid (76.1%), linoleic acid (8.1%) palmitic acid (8.7%) and stearic acid (2.5%) were the major fatty acids detected. Finally, heat map and principal component analysis allowed us to classify the studied provinces in terms of VOO chemical composition: Chefchaouen (tyrosol and hydroxytyrosol), Taounate (oleuropein aglycone), Errachidia (ferulic acid, w-3 and w-6), Beni Mellal (oleocanthal) and Taza (luteolin and oleic acid).     

金属组学方法识别水中络合态重金属形态及其吸附净化技术研究进展

Cu²⁺、Pb²⁺和Ni²⁺等重金属离子可与水中乙二胺四乙酸、柠檬酸、酒石酸等有机分子形成络合态重金属。相比于游离态离子,络合态重金属具有更高的水溶性和环境毒性,在广泛的pH值范围内稳定存在且形态复杂,难以通过化学沉淀等常规方法高效去除。对近年来基于金属组学方法的水中络合态重金属复杂形态分析方法进行总结,对吸附净化技术在络合态重金属废水处理中的研究进展进行综述,并对上述领域需要解决的问题进行了探讨和展望。     

Click Chemistry of Melamine Dendrimers: Comparison of “Click-and-Grow” and “Grow-Then-Click” Strategies Using a Divergent Route to Diversity

Dendrimers are attractive macromolecules for a broad range of applications owing to their well-defined shapes and dimensions, highly branched and globular architectures, and opportunities for exploiting multivalency. Triazine dendrimers in particular offer advantages such as ease of synthesis, stability, well-defined spherical structure, multivalency, potential to achieve acceptable drug loadings, and low polydispersity. In this study, the potential utility of alkyne-azide “click” cycloadditions of first-, second-, and third-generation triazine dendrimers containing three or six alkynyl groups with benzyl azide was examined using copper catalysts. “Click-and-grow” and “grow-then-click” strategies were employed. For the first- and second- generation dendrimers, the desired triazole derivatives were obtained in high yields and purified by simple reprecipitation without column chromatography; however, some difficulties were observed in the preparation of third-generation dendrimers. The desired reaction proceeded under microwave irradiation as well as with simple heating. This click chemistry can be utilized for various melamine dendrimers that are fabricated with other amine linkers.     

Temperature Responsive Polymer Conjugate Prepared by “Grafting from” Proteins toward the Adsorption and Removal of Uremic Toxin

In this study, temperature-responsive polymer-protein conjugate was synthesized using a “grafting from” concept by introducing a chain transfer agent (CTA) into bovine serum albumin (BSA). The BSA-CTA was used as a starting point for poly(N-isopropylacrylamide) (PNIPAAm) through reversible addition-fragmentation chain transfer polymerization. The research investigations suggest that the thermally responsive behavior of PNIPAAm was controlled by the monomer ratio to CTA, as well as the amount of CTA introduced to BSA. The study further synthesized the human serum albumin (HSA)-PNIPAAm conjugate, taking the advantage that HSA can specifically adsorb indoxyl sulfate (IS) as a uremic toxin. The HSA-PNIPAAm conjugate could capture IS and decreased the concentration by about 40% by thermal precipitation. It was also revealed that the protein activity was not impaired by the conjugation with PNIPAAm. The proposed strategy is promising in not only removal of uremic toxins but also enrichment of biomarkers for early diagnostic applications.     

Simulated Gastric and Intestinal Fluid Electrolyte Solutions as an Environment for the Adsorption of Apple Polyphenols onto β-Glucan

Interactions with dietary fibers in the gastrointestinal tract might affect the potential bioactivities of phenolic compounds. In this study, the interactions between apple phenolic compounds and β-glucan (a dietary fiber) were studied by studying the adsorption process in simulated gastric and intestinal fluid electrolyte solutions. Phenolic compounds were extracted from apples, adsorbed onto β-glucan (2 h, 37 °C, in gastric or intestinal fluid electrolyte solutions), and determined using high performance liquid chromatography. Phenolic compounds (flavan-3-ols, flavonols, phenolic acids, and dihydrochalcone) were stable in the gastric fluid (pH 3). In the intestinal fluid (pH 7), flavan-3-ols were not found and chlorogenic acid isomerized. Polyphenols from the apple peel (up to 182 and 897 mg g⁻¹) and flesh (up to 28 and 7 mg g⁻¹) were adsorbed onto β-glucan in the gastric and intestinal fluids, respectively. The adsorption was affected by the initial concentration of the polyphenols and β-glucan and by the environment (either gastric or intestinal fluid electrolyte solution). By increasing the initial polyphenol amount, the quantity of adsorbed polyphenols increased. Increasing the amount of β-glucan decreased the amount adsorbed. The results can be helpful in explaining the fate of phenolic compounds in the gastrointestinal tract.     

Electrochemical Determination of the “Furanic Index” in Honey

5-(hydroxymethyl)furan-2-carbaldehyde, better known as hydroxymethylfurfural (HMF), is a well-known freshness parameter of honey: although mostly absent in fresh samples, its concentration tends to increase naturally with aging. However, high quantities of HMF are also found in fresh but adulterated samples or honey subjected to thermal or photochemical stresses. In addition, HMF deserves further consideration due to its potential toxic effects on human health. The processes at the origin of HMF formation in honey and in other foods, containing saccharides and proteins—mainly non-enzymatic browning reactions—can also produce other furanic compounds. Among others, 2-furaldehyde (2F) and 2-furoic acid (2FA) are the most abundant in honey, but also their isomers (i.e., 3-furaldehyde, 3F, and 3-furoic acid, 3FA) have been found in it, although in small quantities. A preliminary characterization of HMF, 2F, 2FA, 3F, and 3FA by cyclic voltammetry (CV) led to hypothesizing the possibility of a comprehensive quantitative determination of all these compounds using a simple and accurate square wave voltammetry (SWV) method. Therefore, a new parameter able to provide indications on quality of honey, named “Furanic Index” (FI), was proposed in this contribution, which is based on the simultaneous reduction of all analytes on an Hg electrode to ca. −1.50 V vs. Saturated Calomel Electrode (SCE). The proposed method, validated, and tested on 10 samples of honeys of different botanical origin and age, is fast and accurate, and, in the case of strawberry tree honey (Arbutus unedo), it highlighted the contribution to the FI of the homogentisic acid (HA), i.e., the chemical marker of the floral origin of this honey, which was quantitatively reduced in the working conditions. Excellent agreement between the SWV and Reverse-Phase High-Performance Liquid Chromatography (RP-HPLC) data was observed in all samples considered.     

膨润土对干电池溶液中重金属离子的吸附作用

膨润土对干电池溶液中重金属离子的吸附作用蒋引珊，董振亮，张雨力（长春地质学院应用化学系长春１３００２６）关键词膨润土，蒙脱石，电池溶液，重金属离子，吸附由于膨润土中主要矿物蒙脱石特殊的层状结构和离子导电性、凝胶性，充当电池糊层材料既节省粮食又降低成本...     

Biomimetic Approaches to “Transparent” Photovoltaics: Current and Future Applications

There has been a surge in the interest for (semi)transparent photovoltaics (sTPVs) in recent years, since the more traditional, opaque, devices are not ideally suited for a variety of innovative applications spanning from smart and self-powered windows for buildings to those for vehicle integration. Additional requirements for these photovoltaic applications are a high conversion efficiency (despite the necessary compromise to achieve a degree of transparency) and an aesthetically pleasing design. One potential realm to explore in the attempt to meet such challenges is the biological world, where evolution has led to highly efficient and fascinating light-management structures. In this mini-review, we explore some of the biomimetic approaches that can be used to improve both transparent and semi-transparent photovoltaic cells, such as moth-eye inspired structures for improved performance and stability or tunable, coloured, and semi-transparent devices inspired by beetles’ cuticles. Lastly, we briefly discuss possible future developments for bio-inspired and potentially bio-compatible sTPVs.     

Metabolite Profiling of “Green” Extracts of Cynara cardunculus subsp. scolymus,Cultivar “Carciofo di Paestum” PGI by 1H NMR and HRMS-Based Metabolomics

Globe artichoke (Cynara cardunculus L. var. scolymus L.), is a perennial plant widely cultivated in the Mediterranean area, known for its edible part named capitula or heads. Its functional properties are related to its high levels of polyphenolic compounds and inulin. “Carciofo di Paestum”, an Italian traditional cultivar, is a labeled PGI (Protected Geographical Indication) product of the Campania region, representing an important economic resource. So far, a few chemical investigations were performed on this cultivar, mainly focused on the analysis of methanol extracts. Due to the increasing use of food supplements, in this study, a comprehensive analysis of green extracts of “Carciofo di Paestum” PGI heads was performed. EtOH, EtOH: H₂O (80:20, 70:30, 60:40) extracts, as well as infusions and decoctions prepared according to Pharmacopeia XII were analyzed by LC-ESI/QExactive/MS/MS. A total of 17 compounds corresponding to caffeoylquinic acid derivatives, phenolics, flavonoids, and terpenoids were identified. The extracts were further submitted to NMR analysis to highlight the occurrence of primary metabolites. Both LCMS and NMR data were analyzed by Principal Component Analysis (PCA), showing significant differences among the extraction methods. Moreover, 5-caffeoylquinic acid and 1,5-dicaffeoylquinic acid were quantified in the extracts by LC-ESI/QTrap/MS/MS using the Multiple Reaction Monitoring (MRM) method. Furthermore, the phenolic content, antioxidant activity, and α-glucosidase inhibitory activity of C. cardunculus var. scolymus “Carciofo di Paestum” extracts were evaluated.     

桥连对嵌段共聚物自组装的调控

通过嵌段共聚物自组装形成"桥连"是制备具有优异力学性能的网络结构的有效途经,具有重要的应用价值.但是,过去的研究工作很少讨论"桥连"对嵌段共聚物自组装行为本身的影响.该研究评论主要总结了最近几年利用"桥连"对嵌段自组装行为进行调控的工作进展.作者设计了BABCB三组分线性多嵌段共聚物,当其自组装形成二元"介观晶体"(球、柱)结构时,中间B嵌段连接A和C相区(嵌段聚集成的"大原子"),自然地形成桥连;减小中间桥连B嵌段的相对长度,就可以增加其拉伸程度,从而降低介观晶体的配位数;另外,两个末端B嵌段的相对长度可以直接调控A和C"大原子"之间的相对配位数.基于这两个机理,自洽场理论计算预测了各种配位数相等和不相等的二元介观晶体结构.进一步,将"拉伸桥连"概念拓展到AB型嵌段共聚物体系中,并且通过多臂星型嵌段共聚物分子结构中的"组合构型熵效应"在AB型嵌段共聚物中形成高比率的桥连构型,使传统的六角柱状结构转变为了四配位的四方柱状和三配位的石墨烯类柱状结构.未来,在ABC三组分嵌段共聚物体系的设计中引入拓扑结构以及使用共混等方法,有望在介观尺度重铸大多数已知的原子/离子二元晶体结构,甚至超越原子...     

Characterization of Effects of Different Tea Harvesting Seasons on Quality Components,Color and Sensory Quality of “Yinghong 9” and “Huangyu” Large-Leaf-Variety Black Tea

Harvesting seasons are crucial for the physicochemical qualities of large-leaf-variety black tea. To investigate the effect of harvesting seasons on physicochemical qualities, the color and sensory characteristics of black tea produced from “Yinghong 9” (Yh) and its mutant “Huangyu” (Hy) leaves were analyzed. The results demonstrated that Hy had better chemical qualities and sensory characteristics, on average, such as a higher content of tea polyphenols, free amino acids, caffeine, galloylated catechins (GaCs) and non-galloylated catechins (NGaCs), while the hue of the tea brew (ΔE*ab and Δb*) increased, which meant that the tea brew was yellower and redder. Moreover, the data showed that the physicochemical qualities of SpHy (Hy processed in spring) were superior to those of SuHy (Hy processed in summer) and AuHy (Hy processed in autumn), and 92.6% of the total variance in PCA score plots effectively explained the separation of the physicochemical qualities of Yh and Hy processed in different harvesting seasons. In summary, Hy processed in spring was superior in its physicochemical qualities. The current results will provide scientific guidance for the production of high-quality large-leaf-variety black tea in South China.     

Synthesis and Structure of Nido-Carboranyl Azide and Its “Click” Reactions

Novel zwitter-ionic nido-carboranyl azide 9-N₃(CH₂)₃Me₂N-nido-7,8-C₂B₉H₁₁ was prepared by the reaction of 9-Cl(CH₂)₃Me₂N-nido-7,8-C₂B₉H₁₁ with NaN₃. The solid-state molecular structure of nido-carboranyl azide was determined by single-crystal X-ray diffraction. 9-N₃(CH₂)₃Me₂N-nido-7,8-C₂B₉H₁₁ was used for the copper(I)-catalyzed azide-alkyne cycloaddition with phenylacetylene, alkynyl-3β-cholesterol and cobalt/iron bis(dicarbollide) terminal alkynes to form the target 1,2,3-triazoles. The nido-carborane-cholesterol conjugate 9-3β-Chol-O(CH₂)C-CH-N₃(CH₂)₃Me₂N-nido-7,8-C₂B₉H₁₁ with charge-compensated group in a linker can be used as a precursor for preparation of liposomes for Boron Neutron Capture Therapy (BNCT). A series of novel zwitter-ionic boron-enriched cluster compounds bearing a 1,2,3-triazol-metallacarborane-carborane conjugated system was synthesized. Prepared conjugates contain a large amount of boron atom in the biomolecule and potentially can be used for BNCT.     

Triterpenoid Saponins from the Cultivar “Green Elf” of Pittosporum tenuifolium

Four oleanane-type glycosides were isolated from a horticultural cultivar “Green Elf” of the endemic Pittosporum tenuifolium (Pittosporaceae) from New Zealand: three acylated barringtogenol C glycosides from the leaves, with two previously undescribed 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, 3-O-β-d-galactopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, and the known 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C (Eryngioside L). From the roots, the known 3-O-β-d-glucopyranosyl-(1→2)-β-d-galactopyranosyl-(1→2)-β-d-glucuronopyranosyloleanolic acid (Sandrosaponin X) was identified. Their structures were elucidated by spectroscopic methods including 1D- and 2D-NMR experiments and mass spectrometry (ESI-MS). According to their structural similarities with gymnemic acids, the inhibitory activities on the sweet taste TAS1R2/TAS1R3 receptor of an aqueous ethanolic extract of the leaves and roots, a crude saponin mixture, 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, and Eryngioside L were evaluated.