Synthesis and characterization of new fluorescent boro-β-carboline dyes

The first representatives of the new fluorescent boro-β-carboline family were synthesized by the insertion of the difluoroboranyl group into the oxaza or diaza core. The resulting compounds showed good photophysical properties with fine Stokes-shifts in the range of 38–85 nm with blue and green emission. The energetics of the excitation states and molecular orbitals of two members were investigated by quantum chemical computations suggesting effects for the improved properties of diazaborinino-carbolines over oxazaborolo-carbolines. These properties nominated this chemotype as a new fluorophore for the development of fluorescent probes. As an example, diazaborinino-carbolines were used for the specific labeling of anti-Her2 antibody trastuzumab. The fluorescent conjugate showed a high fluorophore-antibody ratio and was confirmed as a useful tool for labeling and confocal microscopy imaging of tumour cells in vitro together with the ex vivo two-photon microscopy imaging of tumour slices.

The first representatives of fluorescent boro-β-carbolines were applied for labeling trastuzumab. The antibody fluorophore conjugate was confirmed as a useful tool for labeling and imaging tumour cells in confocal and two-photon microscopy.     

A mild and metal-free synthesis of 2- and 1-alkyl/aryl/dialkyl-aminoquinolines and isoquinolines

A simple synthetic strategy has been developed for the synthesis of 2- and 1-alkyl/aryl/dialkylaminoquinolines and isoquinolines from the easily available quinoline and isoquinoline-N-oxides, different amines, triflic anhydride as activating agent and acetonitrile as solvent in a one-pot reaction under metal-free conditions at 0 °C to room temperature.

A synthetic strategy has been developed for synthesis of 2 and 1-aminoquinolines and isoquinolines from quinoline and isoquinoline-N-oxides, amines and triflic anhydride in acetonitrile at 0 °C to room temperature.     

An efficient route to N-alkylated 3,4-dihydroisoquinolinones with substituents at the 3-position

A facile synthetic procedure for the production of N-alkylated 3,4-dihydroisoquinolinone derivatives is described. The desired products were obtained by N-alkylation of 3,3′-dimethyl-3,4-dihydroisoquinoline derivatives followed by oxidation of the resulting iminium salts. Reaction conditions for both steps were very mild and the desired cyclization products could be obtained in good yield. This strategy allows the generation of N-substituted 3,4-dihydroisoquinolinone derivatives with substituents at the 3-position.

N-Alkylated 3,4-dihydroisoquinolinone derivatives could be synthesized by N-alkylation of 3,3′-dimethyl-3,4-dihydroisoquinoline derivatives followed by oxidation of the resulting iminium salts.     

Highly efficient synthesis of 3,4-diarylbutadiene sulfones using Heck–Matsuda reaction

For the first time we describe a general method for the synthesis of previously not synthesized unsymmetrical 3,4-diarylbutadiene sulfones which can be stable convenient precursors for 2,3-diaryl-1,3-butadienes. Our method for arylation of butadiene sulfones via Heck–Matsuda reaction allows to obtain unsymmetrical 3,4-diarylbutadiene sulfones with a variety of alkyl, alkoxy, nitro, ethoxycarbonyl, perfluoroalkyl and halogen substituents (30 examples) in very good yields using readily available reagents and catalysts.

An efficient and facile Pd-catalyzed synthesis of 3,4-diarylbutadiene sulfones with high regioselectivity from aryldiazonium salts and butadiene sulfone was developed.     

Syntheses of new chiral chimeric photo-organocatalysts

A new family of chiral chimeric photo-organocatalysts derived from phosphoric acid were synthesized and their spectroscopic and electrochemical properties were investigated. Then, the ability of these photo-activable molecules to catalyse an asymmetric tandem electrophilic β-amination of enecarbamates was evaluated.

A new family of chimeric chiral photocatalysts in which a BINOL derived phosphoric acid embeds one or two photosensitizer dyes was prepared. We have demonstrated their ability to catalyse an enantioselective electrophilic amination reaction.     

Design and synthesis of proton-dopable organic semiconductors

This paper shows how protonated 3,4-ethylene dioxythiophene moieties can be used as an end group to make organic conductors. An organic semiconductor 2,5-bis(5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene is designed and synthesized. This molecule could be doped by protonic acid in both solution and solid-state, resulting in a broad absorption in the near-infrared range corresponding to polaron and bipolaron absorption. Electrical conductivity of ca. 0.1 S cm⁻¹ was obtained at 100 °C (to avoid the water uptake by the acid). The adducts with protons bound at the end-thiophene α-position were confirmed by ¹H Nuclear Magnetic Resonance spectra.

The use of protonated 3,4-ethylenedioxythiophene moieties as an end group could be a promising approach to prepare organic conductors.     

A molten salt-based nitridation approach for synthesizing nanostructured InN electrode materials

Single-phase InN nanocrystals were synthesized for the first time by a molten salt-based nitridation approach using InCl₃ and LiNH₂ as indium and nitrogen sources, respectively. A molten salt, KCl–LiCl, during nitridation, enabled us to obtain InN nanocrystals at relatively low temperatures ranging from 400 °C to 500 °C. SEM and HR-TEM measurements coupled with XRD data revealed that InN nanocrystals were formed with average grain sizes of approximately 50–60 nm. Notably, the photoelectrochemical cell fabricated using the InN nanocrystals synthesized at 450 °C exhibited a photocurrent response under light irradiation from 400 nm to 880 nm. The precise control of the growth of InN particles using our synthetic approach provides opportunities for developing versatile nitride nanocrystals.

Single-phase InN nanocrystals were synthesized for the first time by a molten salt-based nitridation approach using InCl₃ and LiNH₂ as indium and nitrogen sources, respectively.     

Efficient solid-state emission and reversible mechanofluorochromism of a tetraphenylethene-pyrene-based β-diketonate boron complex

A new twisted donor–acceptor (D–A) dye (BF₂-TP) that was composed of tetraphenylethene and pyrene connected with a β-diketonate boron moiety has been synthesized and characterized. Such a dye showed unique intramolecular charge transfer (ICT) features, which were evidenced by spectral analysis and theoretical calculations. More importantly, BF₂-TP solid samples exhibited an obvious mechanofluorochromic (MFC) behavior. Upon grinding with a spatula, the as-prepared powder sample illustrated a remarkable red shift of 62 nm, with considerable color contrast from yellow (562 nm) to orange red (624 nm). Its fluorescence color can be reversibly switched by repeating both the grinding–fuming and grinding–annealing processes. The mechanochromism is attributed to the phase transformation between amorphous and crystalline states. The results obtained would be helpful for designing novel MFC materials.

A new twisted dye (BF₂-TP) was synthesized, it possesses distinct mechanofluorochromism with large spectral shift of 62 nm.     

Amino-acid functionalized porous silicon nanoparticles for the delivery of pDNA

Porous silicon nanoparticles as a novel platform in gene therapy, have shown to be an efficient vehicle for the delivery of nucleic acids in cells. For the first time, a family of porous silicon nanoparticles has been produced featuring an amino-acid functionalized cationic external surface aiming at pDNA complexation. The amino acid-based pDNA nanocarriers, displaying an average diameter of 295 nm, succeeded in transfection of HEK293 cells with an efficiency 300 times superior to “bare” porous silicon nanoparticles.

Scheme of gene transfer into a cell nucleus using a porous silicon nanoparticle based non viral vector.     

A novel diarylethene-based fluorescent “turn-on” sensor for the selective detection of Mg2+

A new photochromic diarylethene derivative with a 4-methylphenol unit has been designed and synthesized. It displayed distinct photochromism and fluorescent ‘‘turn on’’ features to Mg²⁺ in acetonitrile solution. With the addition of Mg²⁺, there was an obvious increase of fluorescent emission intensity at 552 nm, accompanied by a clear change of fluorescent color from dark purple to green. Meantime, the 1 : 1 stoichiometry between the derivative and Mg²⁺ was verified by Job''s plot and HRMS. Furthermore, the sensor was successfully applied in the detection of Mg²⁺ in practical samples. Moreover, based on the multiple-responsive fluorescence switching behaviors, it also could be used to construct a molecular logic circuit with UV/vis lights and Mg²⁺/EDTA as input signals and the emission at 552 nm as the output signal.

A new photochromic diarylethene derivative with a 4-methylphenol unit has been designed and synthesized.     

Total synthesis of the plant alkaloid racemic microthecaline A: first example of a natural product bearing a tricyclic quinoline-serrulatane scaffold

The first total synthesis of racemic microthecaline A, a quinoline serrulatane alkaloid, isolated from the Australian desert plant Eremophila microtheca is described. The natural product was synthesized in ten steps, starting from ethyl 4-bromo-6-methoxy-8-methylquinoline-3-carboxylate in 8% overall yield.

First total synthesis of quinoline-serrulatane alkaloid microthecaline A.     

Synthesis of lamellarin R,lukianol A,lamellarin O and their analogues

Three lamellarin alkaloids type III (lamellarin R, lukianol A and lamellarin O) were synthesized using the Barton–Zard reaction as a key step to construct the central pyrrole core. Some of their corresponding 4-benzoyl and 5-phenyl substituted pyrrole analogues were also prepared via an initial three-component reaction of glycine methyl ester, benzaldehyde, and chalcone to generate the pyrrolidine scaffold, and followed by DDQ oxidation and N-alkylation.

Several lamellarin alkaloids type III and analogues were synthesized using Barton–Zard and three-component reactions to construct the central pyrrole core.     

Synthesis of graphene quantum dot-stabilized gold nanoparticles and their application

Herein, we report an in situ synthesis of graphene quantum dots (GQDs), which have been synthesized from only starch and water and stabilize AuNPs in water. The construction of six gold nanocomposites, i.e. AuNPs 1–6, with sizes ranging from 13.4 nm to 32.6 nm, was accomplished by only mixing the GQDs and chloroauric acid in different amounts without any additional reductants and surfactants. HRTEM has confirmed that the AuNPs have been stabilized by the GQDs, and a core/shell AuNPs@GQD structure has formed. In addition, the as-synthesized AuNPs show excellent catalytic performance in the reduction of 4-nitrophenol, a pertinacious pollutant occurring in industrial wastewater.

Herein, we report an in situ synthesis of graphene quantum dots (GQDs), which have been synthesized from only starch and water and stabilize AuNPs in water.     

Novel oligopeptide nanoprobe for targeted cancer cell imaging

Here we designed and constructed a tryptophan-phenylalanine-phenylalanine-tryptophan (WFFW) tetrapeptide, which generated photostable and tunable fluorescence emission signals from 340 nm to 500 nm. The WFFW tetrapeptide could self-assemble into a spherical nanostructure with enhanced fluorescence intensity. Driven by π–π stacking and hydrogen bond interaction, WFFW co-assembled with arginine-glycine-aspartic acid (RGD) modified WFFW to form a cancer-targeted fluorescent nanoprobe, which could selectively image the cancer cells.

Co-assembly of WFFW tetrapeptide and RGDWFFW heptapeptide generated the photostable and fluorescence-tunable nanoprobe, which could selectively image the cancer cells.     

5-Bromo-norborn-2-en-7-one derivatives as a carbon monoxide source for palladium catalyzed carbonylation reactions

Norbornenone (5b), obtained from the reaction of 2,5-dimethyl-3,4-diphenylcyclopentadienone dimer (3) with bromomaleic anhydride (4b), provides an excellent base-triggered source of carbon monoxide for palladium-catalysed carbonylation reactions. Aminocarbonylation, ketoamide synthesis, and Suzuki–Miyaura reactions of aryl iodides carried out in a two-chamber reaction vessel gave good to excellent yields of carbonylated products.

Norbornenone (5b), obtained from the reaction of 2,5-dimethyl-3,4-diphenylcyclopentadienone dimer (3) with bromomaleic anhydride (4b), provides an excellent base-triggered source of carbon monoxide for palladium-catalysed carbonylation reactions.     

Synthesis and self-assembly of a penta[60]fullerene bearing benzo[ghi]perylenetriimide units

A benzo[ghi]perylenetriimide (BPTI) derivative bearing a terminal azido group on the expanded π-conjugated backbone has been synthesized and characterized. This promising photo- and electroactive BPTI motif has been used to obtain an original penta(organo)fullerene as a promising multi-electron acceptor system. Our studies show its self-assembly resulting from aggregation via π–π stacking interaction in solution and in the solid state.

New penta(organo)fullerene bearing five benzo[ghi]perylenetriimide units has been synthesized to form self-assemblies through π–π interactions.     

Ligand compatibility of salacinol-type α-glucosidase inhibitors toward the GH31 family

We show that salacinol-type α-glucosidase inhibitors are ligand-compatible with the GH 31 family. Salacinol and its 3′-O-benzylated analogs inhibit human lysosomal α-glucosidase at submicromolar levels. Simple structure-activity relationship studies reveal that the salacinol side-chain stereochemistry significantly influences binding to GH31 α-glucosidases.

Salacinol-type α-glucosidase inhibitors are ligand-compatible with the GH 31 family. Salacinol and its 3′-O-benzylated analogs inhibit human lysosomal α-glucosidase at submicromolar levels.     

Ultra-small palladium nano-particles synthesized using bulky S/Se and N donor ligands as a stabilizer: application as catalysts for Suzuki–Miyaura coupling

Two chalcogenated ligands L1 and L2 containing anthracene core and amine functionality have been synthesized. Both the ligands have been characterized using ¹H and ¹³C{¹H} NMR techniques. The structure of L1 has also been corroborated by single crystal X-ray diffraction. Application of L1 and L2 as stabilizers for palladium nano-particles (NPs) has been explored and six different types of NPs 1–6 have been prepared by varying the quantity of stabilizer. The nano-particles have been characterized by PXRD, EDX, and HRTEM techniques. The size of NPs has been found to be in the range of ∼1–2 nm, 2–3 nm, 4–6 nm, 1–2 nm, 1–2 nm and 3–5 nm for 1–6 respectively. The catalytic activities of 1–6 have been explored for Suzuki–Miyaura coupling of phenyl boronic acid with various aryl halides. These NPs showed good catalytic activity for various aryl chlorides/bromides at low catalyst loading (5 mg). Among 1–6, the highest activity has been observed for NPs 1, probably due to their relatively small size and high uniformity in the dispersion. The recyclability of the NPs upto 5 catalytic cycles is a distinct advantage.

Monodispersed ultrasmall Pd nanoparticles synthesized utilizing bulky organochalcogen secondary amines as stabilizers and application in Suzuki coupling of aryl chlorides at low catalyst loading.     

Development of methodologies for the regioselective synthesis of four series of regioisomer isoxazoles from β-enamino diketones

Four methodologies are reported for the regioselective synthesis of four series of regioisomer isoxazoles from cyclocondensation of β-enamino diketones and hydroxylamine hydrochloride. Regiochemical control was achieved by varying reaction conditions and substrate structure. The mild reaction conditions used to access 4,5-disubstituted, 3,4-disubtituted, and 3,4,5-trisubstituted regioisomer isoxazoles, as well as the pharmacological and synthetic potential of the products, make these novel methodologies very powerful.

Efficient and regioselective synthesis of isoxazoles was demonstrated through cyclocondensation of β-enamino diketones with hydroxylamine: four of the six possible regioisomers were obtained.     

Pyridine-2-carboxylic acid as an effectual catalyst for rapid multi-component synthesis of pyrazolo[3,4-b]quinolinones

Green synthesis of pyrazolo[3,4-b]quinolinones was designed using bioproduct pyridine-2-carboxylic acid (P2CA) as a green and efficient catalyst. The multi-component reaction of aldehydes, 1,3-cyclodiones and 5-amino-1-phenyl-pyrazoles regioselectively produced pyrazolo[3,4-b]quinolinones in excellent yield (84–98%). Recyclization of the catalyst was also investigated. The electronic effect of the various substituents in aromatic rings indicated that the reaction proceeded through the carbocation intermediate. This newly designed protocol very quickly constructed products conventionally under milder conditions.

Green synthesis of pyrazolo[3,4-b]quinolinones was designed using bioproduct pyridine-2-carboxylic acid (P2CA) as a green and efficient catalyst.