Developing a new strategy to improve the self‐assembly efficiency of functional assemblies in a confined space and construct hybrid functional materials is a significant and fascinating endeavor. ...Herein, we present a highly efficient strategy for achieving the supramolecular self‐assembly of well‐defined metallacages in microdroplets through continuous‐flow microfluidic devices. The high efficiency and versatility of this approach are demonstrated by the generation of five representative metallacages in different solvents containing water, DMF, acetonitrile, and methanol in a few minutes with nearly quantitative yields, in contrast to the yields obtained with the hour‐scale reaction time in a batch reactor. A ring‐opening catalytic reaction of the metallacages was selected as a model reaction for exploring supramolecular catalysis in microdroplets, whereby the catalytic yield was enhanced by 2.22‐fold compared to that of the same reaction in the batch reactor. This work illustrates a new promising approach for the self‐assembly of supramolecular systems.
Supramolecular self‐assembly of well‐defined metallacages in microdroplets was achieved through a continuous‐flow microfluidic approach. The high efficiency and diversity of this strategy were illustrated by the generation of five representative metallacages with nearly quantitative yields in a few minutes. This approach is promising for the self‐assembly of supramolecular systems in a confined space.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Structurally well‐defined graphene nanoribbons (GNRs) have attracted great interest because of their unique optical, electronic, and magnetic properties. However, strong π–π interactions within GNRs ...result in poor liquid‐phase dispersibility, which impedes further investigation of these materials in numerous research areas, including supramolecular self‐assembly. Structurally defined GNRs were synthesized by a bottom‐up strategy, involving grafting of hydrophilic poly(ethylene oxide) (PEO) chains of different lengths (GNR‐PEO). PEO grafting of 42–51 % percent produces GNR‐PEO materials with excellent dispersibility in water with high GNR concentrations of up to 0.5 mg mL−1. The “rod–coil” brush‐like architecture of GNR‐PEO resulted in 1D hierarchical self‐assembly behavior in the aqueous phase, leading to the formation of ultralong nanobelts, or spring‐like helices, with tunable mean diameters and pitches. In aqueous dispersions the superstructures absorbed in the near‐infrared range, which enabled highly efficient conversion of photon energy into thermal energy.
Supramolecular nanostructures of structurally well‐defined graphene nanoribbons grafted with hydrophilic poly(ethylene oxide) chains present excellent dispersibility in the aqueous phase. Aqueous dispersions of graphene nanoribbon superstructures absorb in the near‐infrared range, thereby enabling highly efficient conversion of photon energy into thermal energy.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Alpha-band (8-13 Hz) oscillations have been shown to phasically inhibit perceptual reports in human observers, yet the underlying physiological mechanism of this effect is debated. According to ...contrasting models, based primarily on animal experiments, alpha activity is thought to either originate from specialized cells in the visual thalamus and periodically inhibit the relay of visual information to the primary visual cortex (V1) in a feedforward manner, or to propagate from higher visual areas back to V1 in a feedback manner. Human neurophysiological evidence in favor of either hypothesis, both, or neither, has been limited. To help address this issue, we explored the link between pre-stimulus alpha phase and visual electroencephalography (EEG) responses thought to arise from afferent input onto human V1. Specially-designed visual stimuli were used to elicit large amplitude C1 event-related potentials (ERP), with polarity, topography, and timing indicative of striate genesis. Single-trial circular-linear associations between pre-stimulus phase and post-stimulus global field power (GFP) during the C1 time window revealed significant effects peaking in the alpha frequency band. Control analyses ruling out the potential confound of post-stimulus data bleeding into the pre-stimulus window demonstrated that GFP amplitude decreases as pre-stimulus alpha phase deviates from an individual's preferred phase. These findings demonstrate an early locus – suggesting that the phase of pre-stimulus alpha oscillations could modulate visual processing by gating the feedforward flow of sensory input between the thalamus and V1, although other models are potentially compatible.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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Fluorescent probes have emerged as indispensable chemical tools to the field of chemical biology and medicine. The ability to detect intracellular species and monitor physiological ...processes has not only advanced our knowledge in biology but has provided new approaches towards disease diagnosis. In this review, we detail the design criteria and strategies for some recently reported fluorescent probes that can detect a wide range of biologically important species in cells and in vivo. In doing so, we highlight the importance of each biological species and their role in biological systems and for disease progression. We then discuss the current problems and challenges of existing technologies and provide our perspective on the future directions of the research area. Overall, we hope this review will provide inspiration for researchers and prove as useful guide for the development of the next generation of fluorescent probes.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
5.
Cage-based sensors for circular dichroism analysis Zhao, Jianjian; Yang, Chang-Yin; Hu, Lianrui ...
Dalton transactions : an international journal of inorganic chemistry,
10/2023, Volume:
52, Issue:
42
Journal Article
Peer reviewed
Quantitative chiral sensing relying on circular dichroism (CD) is very important for determining the enantiomeric excess or concentration of small molecules without strong chromophores, because they ...form chiral complexes with sensors, yielding strong CD signals. Three-dimensional cages are promising platforms for chiral CD due to their stereochemical flexibility and their variety of cavity and external binding sites that can be used as chiral CD sensors. In this minireview, we discuss recent advances, future challenges, and opportunities in the quantitative sensing of small molecules in host-guest and peripheral complexes with cage sensors by chiral CD. We aim to provide inspiration for the rational design of cage sensors for quantitative chiral sensing of small molecules based on CD.
Three-dimensional cages are promising platforms for chiral CD due to their stereochemical flexibility and cavity. In this minireview, we discuss recent advances, future challenges, and opportunities in the quantitative sensing of small molecules.
Fast growth of macroscaled single-layered graphene (MSLG) is crucial for massive fabrication of graphene with the chemical vapor deposition (CVD) method. The conventional CVD process of MSLG ...fabrication is time-consuming since the dosage rate of carbon precursors such as methane is usually very low in order to decrease the nucleation density of graphene grains. A few and even over 10 h are usually needed to grow graphene grains with a macroscale. Simply increasing the flow rate of the carbon precursor results in the increase of nucleation density of graphene grains, which in turn leads to a sharp decrease of the graphene grain size. Here, we report a modified CVD method which substantially accelerates the growth rate of graphene without increasing the nucleation density of graphene grains. Ceramic plates and defect-rich vertical graphene are used synergistically to assist the growth of MSLG. The ceramic plate acts as a persistent oxygen supplement which constrains the nucleation density of graphene grains, while defect-rich vertical graphene serves as complementary catalysis which can accelerate the growth speed of graphene grains. Only a few minutes are needed for the growth of millimeter-sized graphene grains with this modified CVD method.
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IJS, KILJ, NUK, PNG, UL, UM
Background
Open surgery remains the preferred surgical treatment of adrenocortical carcinoma (ACC), while the role of minimally invasive adrenalectomy surgery (MIS) in ACC is still controversial. The ...present study was conducted to compare MIS with open adrenalectomy (OA) in ACC.
Methods
The Embase, PubMed, and Cochrane Library databases were comprehensively searched. The weighted mean difference (WMD), relative risk (RR), and hazard ratio (HR) were pooled.
Results
A total of 15 studies incorporating 2207 patients were included in the present study. MIS approaches were likely to have a comparable operation time (WMD − 17.77;
p
= 0.150) and postoperative complications (RR 0.74;
p
= 0.091) compared with OA, and were significantly associated with less blood loss (WMD − 1761.96;
p
= 0.016) and shorter length of stay (WMD − 2.96;
p
< 0.001). MIS approaches were also more likely to have an earlier recurrence (WMD − 8.42;
p
= 0.048) and more positive surgical margin (RR 1.56;
p
= 0.018) and peritoneal recurrence (RR 2.63;
p
< 0.001), while the overall recurrence (RR 1.07;
p
= 0.559) and local recurrence (RR 1.33;
p
= 0.160) were comparable between the two groups. Furthermore, surgical approaches did not differ in overall survival (HR 0.97;
p
= 0.801), cancer-specific survival (HR 1.04;
p
= 0.869), and recurrence/disease-free survival (HR 0.96;
p
= 0.791).
Conclusions
In the present study, MIS approaches were likely to have a better recovery. Although MIS approaches were associated with earlier recurrence and more positive surgical margin and peritoneal recurrence, no significant differences in survival outcomes were found. OA should still be considered as the standard treatment, but MIS approaches could be offered for selected ACC cases, and performed by surgeons with appropriate laparoscopic expertise, ensuring an improved survival for patients.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Tin oxide (SnO2) is currently the dominating electron transport material (ETL) used in state‐of‐the‐art perovskite solar cells (PSCs). However, there are amounts of defects distributed at the ...interface between ETL and perovskite to deteriorate PSC performance. Herein, a molecule bridging layer is built by incorporating 2,5‐dichloroterephthalic acid (DCTPA) into the interface between the SnO2 and perovskites to achieve better energy level alignment and superior interfacial contact. The multifunctional molecular bridging layer not only can passivate the trap states of Sn dangling bonds and oxygen vacancies resulting in improved conductivity and the electron extraction of SnO2 but also can regulate the perovskite crystal growth and reduce defect‐assisted nonradiative recombination due to its strong interaction with undercoordinated lead ions. As a result, the DCTPA‐modified PSCs achieve champion power conversion efficiencies (PCEs) of 23.25% and 20.23% for an active area of 0.15 cm2 device and 17.52 cm2 mini‐module, respectively. Moreover, the perovskite films and PSCs based on DCTPA modification show excellent long‐term stability. The unencapsulated target device can maintain over 90% of the initial PCE after 1000 h under ambient air. This strategy guides design methods of molecule bridging layer at the interface between SnO2 and perovskite to improve the performance of PSCs .
A multifunctional molecular bridging layer using 2,5‐dichloroterephthalic acid as a pre‐buried additive on the tin oxide (SnO2) electron transport layer enables interfacial energy level alignment and defect passivation. As a result of the method, the high power conversion efficiencies of 23.25% and 20.23% for the active area of 0.15 cm2 device and 17.52 cm2 mini‐module are achieved, respectively.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The unique high surface area and tunable cavity size endow metal-organic cages (MOCs) with superior performance and broad application in gas adsorption and separation. Over the past three decades, ...for instance, numerous MOCs have been widely explored in adsorbing diverse types of gas including energy gases, greenhouse gases, toxic gases, noble gases,
etc.
To gain a better understanding of the structure-performance relationships, great endeavors have been devoted to ligand design, metal node regulation, active metal site construction, cavity size adjustment, and function-oriented ligand modification, thus opening up routes toward rationally designed MOCs with enhanced capabilities. Focusing on the unveiled structure-performance relationships of MOCs towards target gas molecules, this review consists of two parts, gas adsorption and gas separation, which are discussed separately. Each part discusses the cage assembly process, gas adsorption strategies, host-guest chemistry, and adsorption properties. Finally, we briefly overviewed the challenges and future directions in the rational development of MOC-based sorbents for application in challenging gas adsorption and separation, including the development of high adsorption capacity MOCs oriented by adsorbability and the development of highly selective adsorption MOCs oriented by separation performance.
In this highlight, we summarize the design principle and representative examples of MOCs for gas adsorption and separation, with the aim of providing a theoretical basis for designing more MOCs that can adsorb and purify gas.
A series of 3-hydroxyflavone (3-HF) ESIPT (excited-state intramolecular proton transfer) boronate-based fluorescent probes have been developed for the detection of peroxynitrite (ONOO–). The dyes are ...environmentally sensitive, and each probe exhibited a ratiometric response toward ONOO– in a micellar environment. The probes were used to image different aggregation states of amyloid-β (Aβ) in the presence of ONOO–. The 3-HF-OMe probe was found to produce a ratiometric response toward ONOO– when bound to Aβ aggregates, resulting in a novel host–guest ensemble, which adds insight into the development of other ESIPT-based probes for the simultaneous sensing of fibrous proteins/peptides and environmental ROS/RNS.
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