Bifunctional thiosquaramide catalyzed asymmetric reduction of dihydro-β-carbolines and enantioselective synthesis of (−)-coerulescine and (−)-horsfiline by oxidative rearrangement

Tetrahydro-β-carboline (THBC) is a tricyclic ring system that can be found in a large number of bioactive alkaloids. Herein, we report a simple and efficient method for the synthesis of enantiopure THBCs through a chiral thiosquaramide (11b) catalyzed imine reduction of dihydro-β-carbolines (17a–f). The in situ generated Pd–H employed as hydride source in the reaction of differently substituted chiral THBCs (18a–f) afforded high selectivities (R isomers, up to 96% ee) and good isolated yields (up to 88%). Moreover, the chiral thiosquaramide used also afforded exceptional catalyst activity in the syntheses of (−)-coerulescine (5) and (−)-horsfiline (6) with excellent enantioselectivities up to 98% and 93% ee, respectively, via an enantioselective oxidative rearrangement approach.

A simple and efficient asymmetric synthesis of THBCs through a chiral thiosquaramide 11b catalyzed imine reduction of dihydro-β-carbolines (17a−f) and syntheses of (−)-coerulescine and (–)-horsfiline via enantioselective oxidative rearrangement.     

Cu(ii)-thiophene-2,5-bis(amino-alcohol) mediated asymmetric Aldol reaction and Domino Knoevenagel Michael cyclization: a new highly efficient Lewis acid catalyst

The highly efficient Lewis acid-catalytic system Cu(ii)-thiophene-2,5-bis(amino-alcohol) has been developed for enantioselective Aldol reaction of isatin derivatives with ketones. The new catalytic system also proved to be highly enantioselective for the one pot three-component Domino Knoevenagel Michael cyclization reaction of substituted isatin with malononitrile and ethylacetoacetate. The chiral ligand (2S,2′S)-2,2′-((thiophene-2,5-diylbis(methylene))bis(azanediyl))bis(3-phenylpropan-1-ol) (L1) in combination with Cu(OAc)₂·H₂O employed as a new Lewis acid catalyst, furnished 3-substituted-3-hydroxyindolin-2-ones derivatives (3a–s) in good to excellent yields (81–99%) with high enantioselectivities (up to 96% ee) and spiro[4H-pyran-3,3-oxindole] derivatives (6a–l) in excellent yields (89–99%) with high ee (up to 95%). These aldol products and spiro-oxindoles constitute a core structural motif in a large number of pharmaceutically active molecules and natural products.

The highly efficient Lewis acid-catalytic system Cu(ii)-thiophene-2,5-bis(amino-alcohol) has been developed for enantioselective Aldol reaction of isatin derivatives with ketones.     

A convenient approach to difluoromethylated all-carbon quaternary centers via Ni(ii)-catalyzed enantioselective Michael addition

A Ni(ii)-catalyzed enantioselective Michael addition of 2-acetyl azarenes with β-difluoromethyl substituted nitroalkenes was successfully realized, which afforded chiral CF₂H-containing compounds in good enantioselectivities (up to 93% ee). This protocol provides a new convenient approach to all-carbon quaternary stereogenic centers featuring a CF₂H group.

Ni(ii)-catalyzed enantioselective Michael addition afforded compounds with all-carbon quaternary stereogenic centers featuring a CF₂H group in good enantioselectivities.     

Antiproliferative activity of new pentacyclic triterpene and a saponin from Gladiolus segetum Ker-Gawl corms supported by molecular docking study

A new triterpenoidal saponin identified as 3-O-[β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 4)-β-d-xylopyranosyl]-2β,3β,16α-trihydroxyolean-12-en-23,28-dioic acid-28-O-α-l-rhamnopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 2)-α-l-arabinopyranoside 1 together with a new oleanane triterpene identified as 2β,3β,13α,22α-tetrahydroxy olean-23,28-dioic acid 2 and 6 known compounds (3–8) have been isolated from Gladiolus segetum Ker-Gawl corms. The structural elucidation of the isolated compounds was confirmed using different chemical and spectroscopic methods, including 1D and 2D NMR experiments as well as HR-ESI-MS. Moreover, the in vitro cytotoxic activity of the fractions and that of the isolated compounds 1–8 were investigated against five human cancer cell lines (PC-3, A-549, HePG-2, MCF-7 and HCT-116) using doxorubicin as a reference drug. The results showed that the saponin fraction exhibited potent in vitro cytotoxic activity against the five human cancer cell lines, whereas the maximum activity was exhibited against the PC-3 and A-549 cell lines with the IC₅₀ values of 1.13 and 1.98 μg mL⁻¹, respectively. In addition, compound 1 exhibited potent activity against A-549 and PC-3 with the IC₅₀ values of 2.41 μg mL⁻¹ and 3.45 μg mL⁻¹, respectively. Interestingly, compound 2 showed the maximum activity against PC-3 with an IC₅₀ of 2.01 μg mL⁻¹. These biological results were in harmony with that of the molecular modeling study, which showed that the cytotoxic activity of compound 2 might occur through the inhibition of the HER-2 enzyme.

A new triterpenoidal saponin 1, a new oleanane triterpene 2, and 6 known compounds (3–8) have been isolated from Gladiolus segetum Ker-Gawl corms.     

Copolyesters of ε-caprolactone and l-lactide catalyzed by a tetrabutylammonium phthalimide-N-oxyl organocatalyst

Aliphatic polyesters are biocompatible materials that can be used in biomedical applications. We report here the use of tetrabutylammonium phthalimide-N-oxyl catalyst (TBAPINO), as a thermally stable organocatalyst for the ring-opening polymerization (ROP) of cyclic esters under mild conditions. In the solution ROP of ε-caprolactone (ε-CL), quantitative conversion and M_n of ∼20 000 g mol⁻¹ are achieved in a wide temperature range from −15 to 60 °C. Under bulk condition, the conversion of ε-CL reaches over 85% at 120 °C within 2 h. The living ROP character of l-lactide (l-LA) catalyzed over TBAPINO is proved by multiple additions of monomer in the bulk polymerization. The catalyst shows comparable selectivity towards the ring-opening polymerization of l-LA and ε-CL. Their copolymerization over TBAPINO is carried out in one-pot bulk condition in terms of the reaction time, monomer feed ratio, and sequence of addition. The colorless poly(ε-caprolactone-co-lactide) (PCLA) is obtained with considerable conversion of both monomers with the M_n over 22 000 g mol⁻¹.

By utilizing tetrabutylammonium phthalimide-N-oxyl organocatalyst, copolymer PCLA with M_n over 20 000 g mol⁻¹ was synthesized by sequential ring-opening polymerization of ε-caprolactone and l-lactide under bulk conditions.     

Structure characterization and anticoagulant activity of a novel polysaccharide from Leonurus artemisia (Laur.) S. Y. Hu F

An acidic polysaccharide, named LAP-1, was extracted and isolated from Leonurus artemisia (Laur.), and was further purified with ion exchange chromatography and gel chromatography. The extraction conditions of the crude polysaccharides were optimized by single-factor experiments and response surface methodology. The primary structure of the purified polysaccharide was measured by FT-IR, GC-MS, and NMR. The results showed that LAP-1 was mainly composed of galacturonic acid (GalA), mannose (Man), xylose (Xyl), rhamnose (Rha), arabinose (Ara), glucose (Glc), galactose (Gal), fucose (Fuc), ribose (Rib), and glucuronic acid (GlcA) in the molar ratio of 8.74 : 3.45 : 1.02 : 1 : 2.11 : 5.60 : 4.73 : 1.08 : 1.09 : 1.47. Primary structure analysis results indicated that LAP-1 contained characteristic glycosyl linkages such as →1)-α-d-Manp, →1)-α-d-Glcp, →1)-α-d-Arap-(2→, →1)-β-d-Galp-(3→, →1)-β-d-Manp-(4→, →1)-β-d-Galp-(4→, →1)-β-d-Glcp-(4→, →1)-β-d-GalAp-(4→, →1)-β-d-GlcAp-(4→, →1)-β-d-Manp-(4,6→, →1)-β-d-Manp-(3,4→. The M_w/M_n (PDI), M_n, M_z and M_w of LAP-1 were determined to be 1.423, 6.979 × 10³ g mol⁻¹, 1.409 × 10⁴ g mol⁻¹, and 9.930 × 10³ g mol⁻¹ by HPSEC-MALLS-RID and DLS. SEM, TEM and AFM results indicated that LAP-1 was a highly branched structure. LAP-1 showed mild anticoagulant activity, low toxicity, and less spontaneous bleeding compared with heparin sodium. These results demonstrated the effective coagulation activity of Leonurus artemisia polysaccharides. Thus, the purified LAP-1 could be explored as a promising anticoagulant agent for the treatment of coagulation disorders.

An acidic polysaccharide, denoted LAP-1 was extracted, isolated and purified from Leonurus artemisia (Laur.), in addition to its structure and anticoagulant activity were explored.     

Phosphorus pentoxide as a cost-effective,metal-free catalyst for ring opening polymerization of ε-caprolactone

The ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) using phosphorus pentoxide (P₂O₅) as a metal-free catalyst and isopropanol (iPrOH) as initiator resulted in the preparation of poly(ε-caprolactone) with narrow weight distribution. NMR spectroscopy analyses of the prepared PCL indicated the presence of the initiator residue at the end of the polymer chain, implying the occurrence of the ε-CL-catalysis ROP through a monomer activation mechanism. Kinetic experiments confirmed the controlled/living nature of ε-CL ring-opening catalyzed by phosphorus pentoxide. The commercial availability of phosphorus pentoxide and its easy-handling provide additional opportunities for polymer synthesis and nanocomposite manufacturing.

The ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) using phosphorus pentoxide (P₂O₅) as a metal-free catalyst and isopropanol (iPrOH) as initiator resulted in the preparation of poly(ε-caprolactone) with narrow weight distribution.     

Enantioselective Michael addition of malonates to α,β-unsaturated ketones catalyzed by 1,2-diphenylethanediamine

A general and highly enantioselective Michael addition of malonates to cinnamones and chalcones has been developed. The commercially available 1,2-diphenylethanediamine could be directly utilized as the organocatalyst to furnish the desired adducts in satisfactory yield (61–99%) and moderate to excellent enantiopurity (65 to >99% ee). β-Ketoester was also a competent donor and was employed to construct densely functionalized cyclohexenones via a tandem Michael-aldol condensation process.

1,2-Diphenylethanediamine could be directly utilized to promote the Michael addition of malonates and β-ketoesters to various α,β-unsaturated ketones.     

Structure-based approach: molecular insight of pyranocumarins against α-glucosidase through computational studies

α-glucosidase is an enzyme that catalyzes the release of α-glucose molecules through hydrolysis reactions. Regulation of this enzyme can increase sugar levels in type-2 diabetes mellitus (DM) patients. Pyranocoumarin derivatives have been identified as α-glucosidase inhibitors. Through an in silico approach, this work studied the inhibition of three pyranocoumarin compounds against the α-glucosidase at the molecular level. Molecular docking and molecular dynamics simulation were performed to understand the dynamics behavior of pyranocoumarin derivatives against α-glucosidase. The prediction of free binding energy (ΔG_bind) using the Quantum Mechanics/Molecular Mechanics-Generalized Born (QM/MM-GBSA) approach for each system had the following results, PC1-α-Glu: −13.97 kcal mol⁻¹, PC2-α-Glu: −3.69 kcal mol⁻¹, and PC3-α-Glu: −13.68 kcal mol⁻¹. The interaction energy of each system shows that the grid score, ΔG_bind, and ΔG_exp values had a similar correlation, that was PC1-α-Glu > PC3-α-Glu > PC2-α-Glu. Additionally, the decomposition energy analysis (ΔG^residue_bind) was carried out to find out the contribution of the key binding residue. The results showed that there were 15 key binding residues responsible for stabilizing pyranocumarin binding with criteria of ΔG^residue_bind < −1.00 kcal mol⁻¹. The evaluation presented in this work could provide information on the molecular level about the inhibitory efficiency of pyranocoumarin derivatives against a-glucosidase enzyme based on computational studies.

We presented the structure-based approach (molecular docking and MD simulation) to understand the dynamics behavior and inhibitory efficiency of pyranocoumarin derivatives against α-glucosidase at the molecular level.     

Asymmetric ring-opening reaction of meso-epoxides with aromatic amines using homochiral metal–organic frameworks as recyclable heterogeneous catalysts

An efficient asymmetric ring-opening (ARO) reaction of meso-epoxides with aromatic amines catalysed by a series of homochiral metal–organic frameworks (MOFs) was carried out. Excellent results (up to 95% ee) for the ARO of cyclohexene oxide with several aromatic amines were achieved with a homochiral MOF derived from the ligand (R)-2,2′-dihydroxyl-1,1′-binaphthalene-5,5′-dicarboxylic acid. Furthermore, homochiral MOFs based on (R)-2,2′-dihydroxy-1,1′-binaphthyl-4,4′-di(4-benzoic acid) and (R)-2,2′-diethoxy-1,1′-binaphthyl-4,4′-di(5-isophthalic acid) catalysed ARO reactions of cis-stilbene oxide with 1-naphthylamine in high yield (up to 95%) and excellent enantioselectivity (up to 97%) of the β-amino alcohol. The MOF catalysts were recoverable and recyclable with retention of their performance.

Asymmetric ring-opening reactions of meso-epoxides by aromatic amines were achieved by using some chiral metal–organic frameworks. The corresponding β-amino alcohols were obtained with good yields and enantioselectivities (up to 97% ee).     

Photo-responsive polymeric micelles and prodrugs: synthesis and characterization

Bio-recognizable and photocleavable amphiphilic glycopolymers and prodrugs containing photodegradable linkers (i.e. 5-hydroxy-2-nitrobenzyl alcohol) as junction points between bio-recognizable hydrophilic glucose (or maltose) and hydrophobic poly(α-azo-ε-caprolactone)-grafted alkyne or drug chains were synthesized by combining ring-opening polymerization, nucleophilic substitution, and “click” post-functionalization with alkynyl-pyrene and 2-nitrobenzyl-functionalized indomethacin (IMC). The block-grafted glycocopolymers could self-assemble into spherical photoresponsive micelles with hydrodynamic sizes of <200 nm. Fluorescence emission measurements indicated the release of Nile red, a hydrophobic dye, encapsulated by the Glyco-ONB-P(αN₃CL-g-alkyne)_n micelles, in response to irradiation caused by micelle disruption. Light-triggered bursts were observed for IMC-loaded or -conjugated micelles during the first 5 h. Following light irradiation, the drug release rate of IMC-conjugated micelles was faster than that of IMC-loaded micelles. Selective lectin binding experiments confirmed that glycosylated Glyco-ONB-P(αN₃CL-g-alkyne)_n could be used in bio-recognition applications. The nano-prodrug with and without UV irradiation was associated with negligible levels of toxicity at concentrations of less than 30 μg mL⁻¹. The confocal microscopy and flow cytometry results indicated that the uptake of doxorubicin (DOX)-loaded micelles with UV irradiation by HeLa cells was faster than without UV irradiation. The DOX-loaded Gluco-ONB-P(αN₃CL-g-PONBIMC)₁₀ micelles effectively inhibited HeLa cells'' proliferation with a half-maximal inhibitory concentration of 8.8 μg mL⁻¹.

Bio-recognizable and photocleavable amphiphilic glycopolymers and prodrugs containing photodegradable linkers as junction points between hydrophilic glycose and hydrophobic poly(α-azo-ε-caprolactone)-grafted alkyne or drug chains were synthesized.     

cis-1 Isomers of tethered bismethano[70]fullerene as electron acceptors in organic photovoltaics

Isomer-controlled [70]fullerene bis-adducts can achieve high performance as electron-acceptors in organic photovoltaics (OPVs) because of their stronger absorption intensities than [60]fullerene derivatives, higher LUMO energy levels than mono-adducts, and less structural and energetic disorder than random isomer mixtures. Especially, attractive are cis-1 isomers that have the closest proximity of addends owing to their plausible more regular close packed structure. In this study, propylene-tethered cis-1 bismethano[70]fullerene with two methyl, ethyl, phenyl, or thienyl groups were rationally designed and prepared for the first time to investigate the OPV performances with an amorphous conjugated polymer donor (PCDTBT). The cis-1 products were found to be a mixture of two regioisomers, α-1-α and α-1-β as major and minor components, respectively. Among them, the cis-1 product with two ethyl groups (Et₂-cis-1-[70]PBC) showed the highest OPV performance, encouraging us to isolate its α-1-α isomer (Et₂-α-1-α-[70]PBC) by high-performance liquid chromatography. OPV devices based on Et₂-cis-1-[70]PBC and Et₂-α-1-α-[70]PBC with PCDTBT showed open-circuit voltages of 0.844 V and 0.864 V, respectively, which were higher than that of a device with typical [70]fullerene mono-adduct, [70]PCBM (0.831 V) with a lower LUMO level. However, the short-circuit current densities and resultant power conversion efficiencies of the devices with Et₂-cis-1-[70]PBC (9.24 mA cm⁻², 4.60%) and Et₂-α-1-α-[70]PBC (6.35 mA cm⁻², 3.25%) were lower than those of the device with [70]PCBM (10.8 mA cm⁻², 5.8%) due to their inferior charge collection efficiencies. The results obtained here reveal that cis-1 [70]fullerene bis-adducts do not guarantee better OPV performance and that further optimization of the substituent structures is necessary.

cis-1 Isomers of [70]fullerene bis-adducts were utilized as electron-acceptors in organic photovoltaic devices for the first time.     

Constructing a TiO2/PDA core/shell nanorod array electrode as a highly sensitive and stable photoelectrochemical glucose biosensor

Developing stable PEC glucose biosensors with high sensitivity and low detection limit is highly desirable in the biosensor field. Herein, a highly stable and sensitive enzymatic glucose photoelectrochemical biosensor is rationally designed and fabricated by constructing TiO₂/PDA core/shell nanorod arrays. The TiO₂ nanorod as the core has the advantages of increasing charge transportation towards interfaces and enhancing the absorption of incident sunlight due to its single-crystal nature and one dimensional array structure. The PDA shell not only induces a rapid charge transfer across the interfaces but also stabilizes the biosensor performance by avoiding the decomposition of enzymes induced by the strong oxidizing holes from the TiO₂ core. A remarkable performance with an ultrahigh sensitivity of 57.72 μA mM⁻¹ cm⁻², a linear range of 0.2–1.0 mM, a glucose detection limit of 0.0285 mM (S/N = 3) and a high sensitivity of 8.75 μA mM⁻¹ cm⁻² in a dynamic range of 1.0–6.0 mM were obtained for the glucose detection. This study might provide a strategy for constructing inorganic/organic core/shell structures with a satisfactory PEC performance.

Developing stable PEC glucose biosensors with high sensitivity and low detection limit is highly desirable in the biosensor field.     

Facile synthesis of picenes incorporating imide moieties at both edges of the molecule and their application to n-channel field-effect transistors

Picene derivatives incorporating imide moieties along the long-axis direction of the picene core (C_n-PicDIs) were conveniently synthesized through a four-step synthesis. Photochemical cyclization of dinaphthylethenes was used as the key step for constructing the picene skeleton. Field-effect transistor (FET) devices of C_n-PicDIs were fabricated by using ZrO₂ as a gate substrate and their FET characteristics were investigated. The FET devices showed normally-off n-channel operation; the averaged electron mobility (μ) was evaluated to be 2(1) × 10⁻⁴, 1.0(6) × 10⁻¹ and 1.4(3) × 10⁻² cm² V⁻¹ s⁻¹ for C₄-PicDI, C₈-PicDI and C₁₂-PicDI, respectively. The maximum μ value as high as 2.0 × 10⁻¹ cm² V⁻¹ s⁻¹ was observed for C₈-PicDI. The electronic spectra of C_n-PicDIs in solution showed the same profiles irrespective of the alkyl chain lengths. In contrast, in thin films, the UV absorption and photoelectron yield spectroscopy (PYS) indicated that the lowest unoccupied molecular orbital (LUMO) level of C_n-PicDIs gradually lowered upon the elongation of the alkyl chains, suggesting that the alkyl chains modify intermolecular interactions between the C_n-PicDI molecules in thin films. The present results provide a new strategy for constructing a high performance n-channel organic semiconductor material by utilizing the electronic features of phenacenes.

Picenediimide derivatives serve as the active layer of n-channel thin-film field-effect transistors displaying a maximum charge carrier mobility as high as 2.0 × 10⁻¹ cm² V⁻¹ s⁻¹.     

Synthesis of cyclic α-pinane carbonate – a potential monomer for bio-based polymers

This work reports the first known synthesis of α-pinane carbonate from an α-pinene derivative. Pinane carbonate is potentially useful as a monomer for poly(pinane carbonate), which would be a sustainable bio-based polymer. α-Pinene is a major waste product from the pulp and paper industries and the most naturally abundant monoterpene in turpentine oil. α-Pinene is routinely converted to pinene oxide and pinanediol, but no study has yet demonstrated the conversion of pinanediol into α-pinane carbonate. Here, α-pinane carbonate was synthesised via carboxylation of α-pinanediol with dimethyl carbonate under base catalysis using triazabicyclodecene guanidine (TBD). 81.1 ± 2.8% α-pinane carbonate yield was achieved at 98.7% purity. The produced α-pinane carbonate was a white crystalline solid with a melting point of 86 °C. It was characterised using FTIR, NMR, GCMS and a quadrupole time-of-flight (QTOF) mass spectrometer. The FTIR exhibited a C O peak at 1794 cm⁻¹ confirming the presence of a cyclic carbonate. GCMS showed that the α-pinane carbonate fragments with loss of CO₂, forming pinene epoxide. Base hydrolysis of the α-pinane carbonate using NaOH/ethanol/water regenerated the pinanediol with formations of Na₂CO₃.

Synthesis of α-pinane carbonate from an α-pinene derivative.     

Steps towards highly-efficient water splitting and oxygen reduction using nanostructured β-Ni(OH)2

β-Ni(OH)₂ nanoplatelets are prepared by a hydrothermal procedure and characterized by scanning and transmission electron microscopy, X-ray diffraction analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. The material is demonstrated to be an efficient electrocatalyst for oxygen reduction, oxygen evolution, and hydrogen evolution reactions in alkaline media. β-Ni(OH)₂ shows an overpotential of 498 mV to reach 10 mA cm⁻² towards oxygen evolution, with a Tafel slope of 149 mV dec⁻¹ (decreasing to 99 mV dec⁻¹ at 75 °C), along with superior stability as evidenced by chronoamperometric measurements. Similarly, a low overpotential of −333 mV to reach 10 mA cm⁻² (decreasing to only −65 mV at 75 °C) toward hydrogen evolution with a Tafel slope of −230 mV dec⁻¹ is observed. Finally, β-Ni(OH)₂ exhibits a noteworthy performance for the ORR, as evidenced by a low Tafel slope of −78 mV dec⁻¹ and a number of exchanged electrons of 4.01 (indicating direct 4e⁻-oxygen reduction), whereas there are only a few previous reports on modest ORR activity of pure Ni(OH)₂.

β-Ni(OH)₂ nanoplatelets produced via a hydrothermal method exhibit good performance as trifunctional electrocatalysts for the ORR, OER, and HER in alkaline media along with excellent stability under cathodic/anodic polarisation conditions.     

Stereoselective synthesis and application of isopulegol-based bi- and trifunctional chiral compounds

A new family of isopulegol-based bi- and trifunctional chiral ligands was developed from commercially available (−)-isopulegol. Nucleophilic addition of primary amines towards (+)-α-methylene-γ-butyrolactone was accomplished, followed by reduction of the obtained β-aminolactones to provide aminodiols in highly stereoselective reactions. Epoxidation of (−)-isopulegol and subsequent oxirane ring opening with primary amines resulted in N-substituted aminodiols. The regioselective ring closure of these aminodiols with formaldehyde was also investigated. Benzylation of isopulegol furnished O-benzyl-protected isopulegol, which was transformed into aminoalcohols via epoxidation and ring opening of the corresponding epoxides. First benzyl-protected isopulegol was subjected to hydroxylation and epoxidation, then aminolysis of the served oxiranes delivered aminodiols. On the other hand, (−)-isopulegol was oxidised to diol, which was again converted into both dibenzyl- and monobenzyl-protected diol derivatives. The products were transformed into aminoalcohols and aminodiols, respectively, by aminolysis of their epoxides. The ring opening of epoxides, derived from diols with primary amines was also performed producing aminotriols. Dihydroxylation of (−)-isopulegol or derivatives with OsO₄/NMO gave isopulegol-based di-, tri- and tetraols. The antimicrobial activity and antioxidant property, measuring DPPH˙ free radical scavenging activity of aminodiol and aminotriol derivatives as well as di-, tri- and tetraols were also explored. In addition, structure–activity relationships were examined from the aspects of substituent effects and stereochemistry on the aminodiol and aminotriol systems.

A new family of isopulegol-based bi- and trifunctional chiral ligands such as triols, tetrols, aminodiols and aminotriols was developed from commercially available (−)-isopulegol with antibacterial, antifungal and antioxidant activities.     

Zinc(ii)-based coordination polymer encapsulated Tb3+ as a multi-responsive luminescent sensor for Ru3+, Fe3+, CrO42−, Cr2O72− and MnO4−

A zinc(ii)-based coordination polymer (CP), namely [Zn(modbc)₂]_n (Zn-CP) (modbc = 2-methyl-6-oxygen-1,6-dihydro-3,4′-bipyridine-5-carbonitrile), has been synthesized and characterized. Single-crystal structural determination reveals that Zn-CP is a two-dimensional framework structure with tetranuclear homometallic Zn₄(modbc)₄ units cross-linked by modbc. The excellent luminescence as well as good stability of Zn-CP do not enable it to have selective sensing capability for different ions. After encapsulation of Tb³⁺ in Zn-CP, the as-obtained fluorescent functionalized Tb³⁺@Zn-CP maintained excellent luminescence as well as stability, which made it a highly selective and sensitive multiresponsive luminescent sensor for Ru³⁺, Fe³⁺, CrO₄²⁻, Cr₂O₇²⁻, and MnO₄⁻ with high sensitivity, good anti-interference performance, and quick response time (∼10 s). The detection limits are 0.27 μM, 0.57 μM, 0.10 μM, 0.43 μM and 0.15 μM, respectively. A possible sensing mechanism was discussed in detail.

A composite, Tb³⁺@Zn-CP, for sensing Ru³⁺, Fe³⁺, CrO₄²⁻, Cr₂O₇²⁻ and MnO₄⁻ with fast response times was reported.     

Gum acacia-based silver nanoparticles as a highly selective and sensitive dual nanosensor for Hg(ii) and fluorescence turn-off sensor for S2− and malachite green detection

A facile and green method was adopted to synthesize highly selective gum acacia-mediated silver nanoparticles as dual sensor (fluorescence turn-on and colorimetric) for Hg(ii) and fluorescence turn-off sensor for S²⁻ and malachite green. The mechanism proposed for a dual response towards Hg(ii) is the redox reaction between Ag(0) and Hg(ii), resulting in the formation of Ag(i) and Hg(0) and electron transfer from gum acacia to Ag(i), which further leads to the formation of an Ag@Hg nanoalloy. The enhanced fluorescence signal was quenched selectively by S²⁻ owing to the formation of Ag₂S and HgS. The reported nanosensor was found to be useful for sensing malachite green via the inner filter effect. The linear ranges were 3 nmol L⁻¹ to 13 μmol L⁻¹ for Hg(ii), 3–170 μmol L⁻¹ for S²⁻ and 7–80 μmol L⁻¹ for malachite green, and the corresponding detection limits were 2.1 nmol L⁻¹ for Hg(ii), 1.3 μmol L⁻¹ for S²⁻ and 1.6 μmol L⁻¹ for malachite green.

Gum acacia-stabilized silver nanoparticles for the detection of Hg(ii), S²⁻ and malachite green.