Latest ArticlesThe 2-hydroxy-4-methoxybenzyl (Hmb) backbone modification can prevent amide bond-mediated side-reactions (e.g., aspartimide formation, peptide aggregation) by installing the removable Hmb group into a peptide bond, thus improving the synthesis of long and challenging peptides and proteins. However, its use is largely precluded by the limited Hmb's installation sites. In this report, an improved installation of Hmb (iHmb) method was developed to achieve the flexible installation and the convenient removal of Hmb. The iHmb method involves two critical steps: (1) oxidative diazotization of the readily installed 2-hydroxy-4-methoxy-5-amino-benzyl (Hmab) to give 2-hydroxy-4-methoxy-5-diazonium-benzyl (Hmdab) by combining soamyl nitrite (IAN)/HBF4, and (2) reductive elimination of Hmdab to give the desired Hmb by 1,2-ethanedithiol (EDT). The iHmb method enables the installation of Hmb at any primary amino acid including the highly sterically hindered amino acids (e.g., valine and isoleucine). The practicality and utility of the iHmb method was demonstrated by one-shot solid-phase synthesis of a challenging aspartimide-prone peptide, the mirror-image version of a hydrophobic peptide and a long-chain peptide up to 76-residue. Furthermore, the iHmb method can be utilized to facilitate chemical protein ligation, as exemplified by the synthesis of the single-spanning membrane protein sarcolipin. The iHmb method expands the toolkit for peptide synthesis and ligation and facilitates the preparation of peptides/proteins.
Antibiotic abuse now poses a grave threat to global ecology and bestirs public concerns about the residue issue in daily necessities. The traceability measurements along supply chain or logistic circulation have become increasingly essential given the labile nature of diverse synthetic residuals on site. In an attempt to answer this urgency, here a miniaturized fluorometric aptasensor prototype was contrived that catered to the point-of-care screening norm for two typical additives: chloramphenicol and enrofloxacin. The key target-indicating module worked in vitro based on the competitive binding-induced fluorescence recovery of fluorescein-labeled aptamers, which were photobleached beforehand in the format of double helix on burlike nanogold carriers. The “prickly” geometry of the latter not just enriched the capture probes at preferentially substrate-accessible spires; but also contributed to a tip-enhanced surface plasmon effect, sensitizing the signal-on during the duplex dissociation even at nanomolar threshold of the analytes. On the other hand, to encompass a full portable, a set of optical devices were mounted within a 3D-printed cartridge (adaptor) to converge the light beam and route it towards the detector, for which the smartphone camera came up in handy with a home-developed App for calibrating the emissive brightness. Enlightened by the high-dynamic-range compression, an imaging diagnostic algorithm was built in to grid and digitize each slide in the album for augmented detection performance. Thus, a novel bio-to-silico integration was invented that capable of in situ rapid reporting on the antibiotic presence with high sensitivity and selectivity. Further field practices in spiked milk on sales proved the precision and rudimentary feasibility of the well-assembled model of appliance, thus holding nice prospects in nonexpert (e.g., family and local community) utilities for foodborne antibiotic identification.
Electrocatalytic synthesis of ammonia as an environment-friendly and sustainable development method has received widespread attention in recent years. Two-dimensional (2D) materials are a promising catalyst for ammonia synthesis due to their large surface area. In this work, we have constructed a series of 2D metal borides (MBenes) with transition metal (TM) defects (TMd-MBenes) and comprehensively calculated the reactivity of electrocatalytic synthesis of ammonia-based on density functional theory. The results have demonstrated that the TMd-MBenes can effectively activate nitrogen oxide (NO) and nitrogen (N2) molecules thermodynamically. Particularly interesting, the co-chemisorption of O atoms, dissociated from NO, can facilitate the spilled of the inert N2 molecules into single N atoms, which can further hydrogenate into ammonia easily with an ultralow limiting potential of 0.59 V on TMd-MnB. Our research has not only provided clues for catalyst design for experimental study but also paved the way for the industrial application of electrocatalytic ammonia synthesis.
Herein, we report the facile synthesis of a highly strained hexabenzocoronene-containing carbon nanoring, cyclo[4]-paraphenylene[2]-2,11-hexabenzocoronenylene ([4,2]CPHBC), as the segment of a [10,10] single-walled carbon nanotube ([10,10]SWNT). [4,2]CPHBC was synthesized based on the platinum-mediated assembly of diborylbiphenyl and diborylhexabenzocoronene, forming a tetranuclear platinum complex, followed by reductive elimination. This nanoring molecule was confirmed by NMR and HR-MS, and its photophysical properties were studied using steady-state and time-resolved spectroscopies. Moreover, the selective supramolecular host-guest interaction between [4,2]CPHBC and C60 was also investigated.
An efficient synthesis of the electrophilic reagent, S-(1,3-dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate (SDDP) is described. Moreover, the synthetic applications of SDDP wherein the transfer of the SP(O)(OEt)2 moiety occurs were investigated. In this manner, SDDP underwent facile SP(O)(OEt)2 transfer with electron-rich substrates such as ketones, indoles, and thiols to form α-phosphorothiolated ketones, 3-phosphorothiolated indoles and S-phosphorothiolated thioethers, respectively.
Presented here is a one-pot strategy starting from rationally designed macrocyclic precursors for the diverse construction of sophisticated ultracycles. The type and amount of the base were found to significantly influence the macrocyclization outcome. The use of 4.0 equiv. CsF resulted in ultracycles of both types A and B while the presence of CsF larger than 6.0 equiv. produced only type B ultracycles. Existence of anion template increased the total yields and affected the distribution of the ultracycles. The ultracycles can accommodate large organic dicarboxylates anions via multiple anion–π and hydrogen bonds, and show selectivity to the size-matched heptanedioate (C72−). Based on all possible species and relevant equilibrium constants as well as material and charge balances, a numerical iterative algorithm was developed and applied to fit the association constants of B2H with dicarboxylates from glutarate (C52−) to octanedioate (C82−), which gave association constants up to 103 L/mol.
The galactomannan from Antrodia cinnamomea (AC) is characterized as one of the important bioactive components that exhibits potential immunostimulatory propriety. The biological function of its corresponding oligosaccharide fragments has not been revealed yet. In this study, we reported the first chemical synthesis of the series of oligosaccharide fragments related to AC galactomannan via the convergent glycosylation strategy. The preliminary immunological evaluation of these synthesized AC oligosaccharides disclosed that the backbone tetrasaccharide 1d showed the best immunomodulatory ability on enhancing proliferation, phagocytosis and cytokines secretion of Raw264.7 macrophages in vitro, indicating its immense potential as an immunostimulant candidate.
This review explores the concept of life-on-a-chip, which involves the creation of miniaturized biological systems, such as organs, tissues, and model organisms, on microscale platforms called microfluidic chips. These chips consist of intricately etched channels, wells, and chambers that enable precise control and observation of fluids, cells, and biochemical reactions, facilitating the simulation of various aspects of human or animal physiology and the study of responses to different stimuli, drugs, or disease conditions. The review highlights the application of a novel technology, "Beyond Limit Manufacturing" (BLM), in the development of sophisticated three-dimensional cell models and model organism microchips. Model-organism-on-a-chip and organ-on-a-chip (OoC) are among the thriving developments in the field of microfluidics, allowing for the reconstruction of living microenvironments and implementation of multiple stimuli. The review discusses the latest advancements in life-on-a-chip technology using BLM and outlines potential future research directions, emphasizing the significant role of these chips in studying complex biological processes in a controlled and scalable manner.
To develop efficient sensitizers for dye-sensitized solar cells (DSSCs), we recently reported doubly concerted companion (DCC) dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain, which exhibits panchromatic absorption and excellent anti-aggregation ability. To further improve the absorption, we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor, respectively. For the corresponding organic dyes Z3 and Z4, the introduced ethynyl group improves their absorption, but induces aggravated charge recombination, leading to lowered power conversion efficiencies (PCEs). Similar to the organic dyes, the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well. In addition, the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit. As a result, XW88 affords the highest JSC (21.84 mA/cm2), VOC (782 mV) and PCE (12.2%) among the DCC dyes. These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.
Water pollution caused by global population growth, urban expansion and industrialization development is one of the urgent issues that need to be addressed in the 21st century. Up to now, it was challenging for metal-organic frameworks (MOFs) to be used in the actual water treatment due to that the powder MOFs suffered from difficult reuse, poor water stability and easy corrosion. It is an effective strategy to immobilize MOFs powder onto porous sponge foam carriers for accomplishing large flux, facile recycling, easy processing water treatment setups. In this review article, the fabrication approaches and applications of different MOFs/sponge composites were highlighted, in which the fluorescence detection of pollutants, adsorption and separation of pollutants, catalytic reduction and oxidation of pollutants were included. Finally, the future challenges and opportunities of MOF/sponge for water treatment are proposed, aiming to provide in-depth guidance for the future design and manufacture of the immobilized MOFs onto sponge foams.