Developing broadband and strong visible-light-absorbing photosensitizer is highly desired for dramatically improving the utilization of solar energy and boosting artificial photosynthesis. Herein, we ...develop a facile strategy to co-sensitize Ir-complex with Coumarins and boron dipyrromethene to explore photosensitizer with a broadband covering ca. 50% visible light region (Ir-4). This type of photosensitizer is firstly introduced into water splitting system, exhibiting significantly enhanced performance with over 21 times higher than that of typical Ir(ppy)
(bpy)
, and the turnover number towards Ir-4 reaches to 115840, representing the most active sensitizer among reported molecular photocatalytic systems. Experimental and theoretical investigations reveal that the Ir-mediation not only achieves a long-lived boron dipyrromethene-localized triplet state, but also makes an efficient excitation energy transfer from Coumarin to boron dipyrromethene to trigger the electron transfer. These findings provide an insight for developing broadband and strong visible-light-absorbing multicomponent arrays on molecular level for efficient artificial photosynthesis.
Red/near‐infrared (NIR) emissive carbon nanodots (CNDs) with photoluminescence (PL) quantum yield (QY) of 57% are prepared via an in situ solvent‐free carbonization strategy for the first time. ...1‐Photon and 2‐photon cellular imaging is demonstrated by using the CNDs as red/NIR fluorescence agent due to the high PL QY and low biotoxicity. Further study shows that the red/NIR CNDs exhibit multiphoton excited (MPE) upconversion fluorescence under excitation of 800–2000 nm, which involves three NIR windows (NIR‐I, 650–950 nm; NIR‐II, 1100–1350; NIR‐III, 1600–1870 nm). 2‐Photon, 3‐photon, and 4‐photon excited fluorescence of the CNDs under excitation of different wavelengths is achieved. This study develops an in situ solvent‐free carbonization method for efficient red/NIR emissive CNDs with MPE upconversion fluorescence, which may push forward the application of the CNDs in bioimaging.
Red/near‐infrared (NIR) emissive carbon nanodots (CNDs) with photoluminescence quantum yield of 57% are demonstrated via an in situ solvent‐free strategy. 1‐Photon and 2‐photon cellular imaging is demonstrated. Furthermore, multiphoton excited red/NIR fluorescence of the CNDs is achieved.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Abstract
Doping has been widely used to control the charge carrier concentration in organic semiconductors. However, in conjugated polymers, n-doping is often limited by the tradeoff between doping ...efficiency and charge carrier mobilities, since dopants often randomly distribute within polymers, leading to significant structural and energetic disorder. Here, we screen a large number of polymer building block combinations and explore the possibility of designing n-type conjugated polymers with good tolerance to dopant-induced disorder. We show that a carefully designed conjugated polymer with a single dominant planar backbone conformation, high torsional barrier at each dihedral angle, and zigzag backbone curvature is highly dopable and can tolerate dopant-induced disorder. With these features, the designed diketopyrrolopyrrole (DPP)-based polymer can be efficiently n-doped and exhibit high n-type electrical conductivities over 120 S cm
−1
, much higher than the reference polymers with similar chemical structures. This work provides a polymer design concept for highly dopable and highly conductive polymeric semiconductors.
This paper considers a multiple-input multiple-output (MIMO) receiver with very low-precision analog-to-digital convertors (ADCs) with the goal of developing massive MIMO antenna systems that require ...minimal cost and power. Previous studies demonstrated that the training duration should be relatively long to obtain acceptable channel state information. To address this requirement, we adopt a joint channel-and-data (JCD) estimation method based on Bayes-optimal inference. This method yields minimal mean square errors with respect to the channels and payload data. We develop a Bayes-optimal JCD estimator using a recent technique based on approximate message passing. We then present an analytical framework to study the theoretical performance of the estimator in the large-system limit. Simulation results confirm our analytical results, which allow the efficient evaluation of the performance of quantized massive MIMO systems and provide insights into effective system design.
The great success of ynones in synthesis is rooted in their multiple functional groups. Herein, reactions triggered by the reflex‐Michael addition, ynones in copper(I)‐catalyzed alkyne–azide ...cycloaddition (CuAAC), and formal cycloaddition as well as the use of ynones as nucleophilic enols, electrophilic ketones, and allenic precursors were thoroughly discussed and summarized. Multi‐component reactions, rearrangements, cycloadditions, regio‐ and stereoselective synthesis, coupling, and cycloaddition are depicted in detail. This review focused on advances of ynones chemistry in the last decade (2009–2019). We hope it will promote future research in this area.
This review focused on advances of ynones chemistry in the last decade (2009‐2019). Multi‐component reactions, rearrangements, cycloadditions, regio‐ and stereoselective synthesis, coupling, and cycloaddition are depicted in detail.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Optical physical unclonable functions (PUFs) have been proven to be one of the most effective anti‐counterfeiting strategies. However, optical PUFs endowed with flexibility and biocompatibility have ...not been developed, limiting their application scenarios. Herein, biocompatible and flexible optical PUF labels are developed by randomly embedding microdiamonds in silk fibroin films. The PUF labels can be conformally attached onto the surface of complex shaped objects, providing the desired protection against fake and interior products. In this system, silk fibroin films serve as a flexible and biocompatible substrate, while the Raman signal of the microdiamonds serves as response of the excitation. The extremely high stability and random distribution of the microdiamonds ensure the performance of PUFs, and the maximum encoding capability of 210000 is finally realized. The cytotoxicity analysis results also verify the biosafety of the PUF system. In addition, the as‐prepared PUF labels are attached onto the surface of polyethylene material, and human skin, and even have been implanted under chicken skin tissue, promising their practical applications.
Flexible and biocompatible physical unclonable function labels are designed and demonstrated by using microdiamonds as the response of the excitation and silk fibroin films as a flexible and biocompatible substrate, which have been applied for protection against fake objects with complex shapes.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
A procedure for the transition‐metal‐free three‐component reaction of 1,3,5‐triazines, diazo compounds and tert‐butyl nitrite has been described. This reaction goes through tandem nucleophilic attack ...to generate synthetically important β‐aminonitroso‐α‐diazocarbonyl compounds in moderate to good yields. This protocol is distinguished by the use of readily available starting materials, wide substrate scope and operational simplicity. Notably, a N−N bond and a C−C bond were formed simultaneously.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Clear cell renal cell carcinoma (ccRCC) is the most common and highly malignant pathological type of kidney cancer. We sought to establish a metabolic signature to improve post‐operative risk ...stratification and identify novel targets in the prediction models for ccRCC patients. A total of 58 metabolic differential expressed genes (MDEGs) were identified with significant prognostic value. LASSO regression analysis constructed 20‐mRNA signatures models, metabolic prediction models (MPMs), in ccRCC patients from two cohorts. Risk score of MPMs significantly predicts prognosis for ccRCC patients in TCGA (P < 0.001, HR = 3.131, AUC = 0.768) and CPTAC cohorts (P = 0.046, HR = 2.893, AUC = 0.777). In addition, G6PC, a hub gene in PPI network of MPMs, shows significantly prognostic value in 718 ccRCC patients from multiply cohorts. Next, G6Pase was detected high expressed in normal kidney tissues than ccRCC tissues. It suggested that low G6Pase expression significantly correlated with poor prognosis (P < 0.0001, HR = 0.316) and aggressive progression (P < 0.0001, HR = 0.414) in 322 ccRCC patients from FUSCC cohort. Meanwhile, promoter methylation level of G6PC was significantly higher in ccRCC samples with aggressive progression status. G6PC significantly participates in abnormal immune infiltration of ccRCC microenvironment, showing significantly negative association with check‐point immune signatures, dendritic cells, Th1 cells, etc. In conclusion, this study first provided the opportunity to comprehensively elucidate the prognostic MDEGs landscape, established novel prognostic model MPMs using large‐scale ccRCC transcriptome data and identified G6PC as potential prognostic target in 1,040 ccRCC patients from multiply cohorts. These finding could assist in managing risk assessment and shed valuable insights into treatment strategies of ccRCC.
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Electron‐withdrawing groups (EWG) have emerged as a powerful tool for the activation of various arenes to promote nucleophilic dearomative additions for the construction of complicated chiral cyclic ...structures under asymmetric catalytic systems. Nitro‐indoles, nitro‐benzofurans/benzothiophenes, and related nitro‐heteroarenes are widely applied in the reaction with various nucleophiles to construct various enantioenriched polycyclic skeletons via the asymmetric dearomatization process. Meanwhile, the electron‐deficient azo‐group and nitroso‐group are an alternative powerful tool for the activation of arenes, which enable formal nucleophilic aromatic arylations with various electrophilic aromatics to construct novel chiral biaryl atropisomers. Besides, azo‐naphthanenes are served as dipolar surrogates in the reaction with nucleophilic dipolarophiles to proceed asymmetric cycloadditions to construct chiral polycyclic skeletons. The EWG‐tethered arene has proven to be a versatile protocol for the construction of structurally diversified chiral backbones. This review summarizes the latest progress of the EWG‐tethered arenes involved asymmetric transformations under organo‐ or transition metal catalysis.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
A convenient method was developed via an NHC mediated three‐component cascade reaction for the construction of medicinally important spirobenzofuranone derivatives. The reaction features mild ...reaction conditions and generates three consecutive stereocenters, one of which is an all‐carbon substitution. The protocol can accommodate various substituents and substitution patterns, afford the products in moderate to good yields with excellent diastereoselectivities and moderate enantioselectivity.
An NHC‐catalyzed reaction with benzofuran‐2‐one type compounds as the starting materials for the synthesis of medicinally important spirobenzofuranone derivatives with four new bonds, three consecutive stereocenters and one all‐carbon quaternary carbon is reported.
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