A highly efficient new protocol has been developed for the formation of C-Te bonds, leading to both symmetrical and unsymmetrical diaryl tellurides. This protocol utilizes sodium aryltellurites (4), which can be easily prepared from low-cost aryltelluride trichlorides and NaOH. The synthesis involves the use of 4 and arylazo sulfones as starting materials in the presence of (MeO)2P(O)H. A variety of diaryl tellurides are obtained in moderate to good yields using this method. Importantly, this innovative protocol eliminates the need for traditional, highly toxic aryltellurolating reagents such as diaryl ditellurides and elemental tellurium. This study will bring new vitality to the synthesis of tellurides.

Aminopeptidases, enzymes with critical roles in human body, are emerging as vital biomarkers for metabolic processes and diseases. Aberrant aminopeptidase levels are often associated with diseases, particularly cancer. Small-molecule probes, such as fluorescent, fluorescent/photoacoustics, bioluminescent, and chemiluminescent probes, are essential tools in the study of aminopeptidases-related diseases. The fluorescent probes provide real-time insights into protein activities, offering high sensitivity in specific locations, and precise spatiotemporal results. Additionally, photoacoustic probes offer signals that are able to penetrate deeper tissues. Bioluminescent and chemiluminescent probes can enhance in vivo imaging abilities by reducing the background. This comprehensive review is focused on small-molecule probes that respond to four key aminopeptidases: aminopeptidase N, leucine aminopeptidase, Pyroglutamate aminopeptidase 1, and Prolyl Aminopeptidase, and their utilization in imaging tumors and afflicted regions. In this review, the design strategy of small-molecule probes, the variety of designs from previous studies, and the opportunities of future bioimaging applications are discussed, serving as a roadmap for future research, sparking innovations in aminopeptidase-responsive probe development, and enhancing our understanding of these enzymes in disease diagnostics and treatment.

Tributyl citrate (TBC) plays a crucial role as a plasticizer, enhancing the flexibility of polymers like polyvinyl chloride. Its biodegradability and non-toxic nature contribute to its eco-friendly appeal, making it a preferred additive in diverse industries, including food packaging, medical devices, toys, and consumer goods. Herein, a method for the synthesis of TBC using inexpensive Brønsted acidic protic ionic liquids (ILs) in a two-phase reaction system is presented. The esterification process is carried out with high yield (>99%), selectivity (up to 98%) and short reaction time of 2h. The catalyst in the form of IL shows excellent performance and stability, desirable for industrial applications.

Ferroptosis is a recently identified form of regulated cell death characterized by iron accumulation and lipid peroxidation. Numerous functions for ferroptosis have been identified in physiological as well as pathological processes, most notably in the treatment of cancer. The intricate balance of redox homeostasis is profoundly altered during ferroptosis, leading to alteration in cellular microenvironment. One such microenvironment is viscosity among others such as pH, polarity, and temperature. Therefore, understanding the dynamics of ferroptosis associated viscosity levels within organelles is crucial. To date, there are a very few reviews that detects ferroptosis assessing reactive species. In this review, we have summarized organelle’s specific fluorescent probes that detects dynamics of microviscosity during ferroptosis. Also, we offer the readers an insight of their design strategy, photophysics and associated bioimaging concluding with the future perspective and challenges in the related field.

Severe dendrite growth on Zn anodes poses a significant challenge to the development of Zn-based batteries. An effective strategy for inhibiting the formation of Zn dendrites involves electrode modification. In this study, hollow nitrogen-doped carbon spheres (HNCS) are synthesized and used as electrodes to regulate Zn deposition in Zn-based flow batteries. The electrochemical performance of HNCS reveals that the pyrrole nitrogen of HNCS changes the electrode surface state. Therefore, HNCS can inhibit the hydrogen evolution reaction and achieve uniform Zn deposition. HNCS can effectively inhibit dendrite growth and improve the reversibility of the Zn plating/stripping process to regulate the reversibility of Zn-based batteries. The zinc–bromine redox flow battery assembled with HNCS significantly reduces the hydrogen evolution reaction and exhibits a coulombic efficiency of 90% and energy efficiency of 73% at a current density of 60 mA cm–2. Similarly, an alkaline zinc–iron flow battery can maintain high Coulombic efficiency and energy efficiency of 83%.

By introducing main-group elements such as boron and bismuth to π-conjugated systems, it is possible to modify the optical properties of π-conjugated materials through orbital interactions between the orbital on the elements and π/π*-orbitals, and the heavy atom effect. Moreover, bismuth, which is the heaviest stable element, induces a significant heavy atom effect, making organobismuth compounds promising for applications as phosphorescent materials. In this study, we synthesized new room-temperature phosphorescent materials by incorporating bismuth into thiophene units. The phosphorescence properties of these materials, such as emission lifetime and wavelength, could be further controlled by combining tricoordinate boron with the thienylbismuth structures. The synthesized bismuth- and boron-containing thiophene compounds exhibited phosphorescence at room temperature in both solution and solid states. Furthermore, the introduction of boron raised the energy of the triplet state in the π-conjugated system, resulting in a blue shift of the phosphorescence wavelength. The analysis of photoluminescence properties and TD-DFT calculations revealed that the introduction of bismuth enhances phosphorescence properties, whereas the introduction of boron further promotes intersystem crossing.

A benzannulated double aza[9]helicene 1 was successfully synthesized via a one-pot oxidative fusion reaction. 1 was derivatized to N-alkylated double aza[9]helicene 1-Et and 1-Bu, whose structures were determined by X-ray diffraction analysis. 1-Et and 1-Bu exhibited red-shifted absorption and fluorescence spectra compared to single aza[9]helicene. The double aza[9]helicenes were expected to have two different conformers. Consistent with solid-state structure, the chiral-isomer was estimated to be more stable by 16 kcal/mol relative to meso-isomer. Indeed, enantiomers of 1-Et and 1-Bu were optically resolved by HPLC and showed mirror-imaged CD and CPL spectra with the CPL brightness up to 19.2 M–1cm–1 for 1-Bu.

In light of the important biological activities and widespread applications of organic disulfides, dithiocarbamates, xanthates, thiocarbamates and thiocarbonates, the continual persuit of efficient methods for their synthesis remains crucial. Traditionally, the preparation of such compounds heavily relied on intricate multi-step syntheses and the use of highly prefunctionalized starting materials. Over the past two decades, the direct sulfuration of C–H bonds has evolved into a straightforward, atom- and step-economical method for the preparation of organosulfur compounds. This review aims to provide an up-to-date discussion on direct C–H disulfuration, dithiocarbamation, xanthylation, thiocarbamation and thiocarbonation, with a special focus on describing scopes and mechanistic aspects. Moreover, the synthetic limitations and applications of some of these methodologies, along with the key unsolved challenges to be addressed in the future are also discussed. The majority of examples covered in this review are accomplished via metal-free, photochemical or electrochemical approaches, which are in alignment with the overraching objectives of green and sustainable chemistry.  This comprehensive review aims to consolidate recent advancements, providing valuable insights into the dynamic landscape of efficient and sustainable synthetic strategies for these crucial classes of organosulfur compounds.

Ln(III) complexes display sensitized Ln(III) emissions by energy transfer from excited ligands. The long-lived Ln(III) emissions, rangings from visible to NIR region, hold great application potential in biomedical fields. This mini–review highlights recent advances in developing Ln(III) complexes for bioimaging, biosensing, and biodiagnosis. The mentioned Ln(III) emission colors include Sm(III) pink–purple, Eu(III) red, Tb(III) green, Dy(III) yellow/gray, and Yb(III) near–IR.

Abstract

Luminescent molecule–based bioimaging system is widely used for precise localization and distinction of cancer/tumor cells. Luminescent lanthanide (Ln(III)) complexes offer long–lived (sub–millisecond time scale) and sharp (FWHM <10 nm) emission, arising from the forbidden 4f–4f electronic transitions. Luminescent Ln(III) complex–based bioimaging has emerged as a promising option for both in vitro and in vivo visualizations. In this mini–review, the historical development and recent significant progress of luminescent Ln(III) probes for bioapplications are introduced. The recent studies are mainly focused on three points: (i) the structural modifications of Ln(III) complexes in both macrocyclic and small ligands, (ii) the acquirement of high resolution luminescence images of cancer/tumor cells and (iii) the constructions of ratiometric biosensors. Furthermore, our recent study is explained as a new Cancer GPS (cancer grade probing for determining tumor grade through photophysical property analyses of intracellular Eu(III) complex.

Solid-state supramolecular organization of bipyrimidine cores functionalized with alkoxystyryl moieties bearing short chiral chains allows for the emergence of strong high order harmonic signals from thin films obtained without any corona-poling process.

Abstract

An original series of bipyrimidine-based chromophores featuring alkoxystyryl donor groups bearing short chiral (S)-2-methylbutyl chains in positions 4, 3,4 and 3,5, connected to electron-accepting 2,2-bipyrimidine rings, has been developed. Their linear and non-linear optical properties were studied using a variety of techniques, including one- and two-photon absorption spectroscopy, fluorescence measurements, as well as Hyper-Rayleigh scattering to determine the first hyperpolarizabilities. Their electronic and geometrical properties were rationalized by TD-DFT calculations. The thermal properties of the compounds were also investigated by a combination of polarized light optical microscopy, differential scanning calorimetry measurements and small-angle X-ray scattering experiments. The derivatives were found not to have mesomorphic properties, but to exhibit melting temperatures or cold crystallization behavior that enabled the isolation of well-organized thin films. The nonlinear optical properties of amorphous or crystalline thin films were studied by wide-field second harmonic generation and multiphoton fluorescence imaging, confirming that non-centrosymmetric crystal organization enables strong second and third harmonic generation. This new series confirms that our strategy of functionalizing 3D organic octupoles with short chiral chains to generate non-centrosymmetric organized thin films enables the development of highly second order nonlinear optical active materials without the use of corona-poling or tedious deposition techniques.