More than two‐thirds of patients with hepatocellular carcinoma (HCC) cannot receive curative therapy and have poor survival due to late diagnosis and few prognostic directions. In our study, ...nontargeted and targeted metabolomics analyses were conducted by liquid chromatography–mass spectrometry to characterize metabolic features of HCC and identify diagnostic and prognostic biomarker candidate incorporating liver tissue and serum metabolites. A total of 552 subjects, including 432 with liver tissue and 120 with serum specimens, were recruited in China. In the discovery cohort, a series of 138 metabolites were identified to discriminate HCC tissues from matched nontumor tissues. Retinol presented with the highest area under the curve (AUC) of 0.991 and associated with Edmondson grade. In the validation cohort, all metabolites in retinol metabolism pathway were examined and the levels of retinol and retinal in tumor tissue and serum decreased in the order of normal to cirrhosis to HCC of Edmondson Grades I to IV. Retinol and retinal levels could also differentiate between HCC and cirrhosis, with AUCs of 0.996 and 0.994, respectively, in tissue and 0.812 and 0.744, respectively, in serum. The AUC of the combined retinol and retinal panel in serum was 0.852. Univariate and multivariate Cox regression identified this panel as an independent predictor for HCC and showed that low expression of retinol and retinal correlated with decreased survival time. In conclusion, the retinol metabolic signature had considerable diagnostic and prognostic value for identifying HCC patients who would benefit from prompt therapy and optimal prognostic direction.
What's new?
Currently, α‐fetoprotein (AFP) is the most practical screening biomarker for early hepatocellular carcinoma (HCC) detection and prognostic tool for tumor recurrence and patient survival, but the relatively poor sensitivity and specificity remain unsatisfactory. Here, retinol metabolism was found to be closely associated with the malignant transformation of HCC. Retinol and retinal displayed great diagnostic ability for HCC both in liver tissue and serum samples. The two‐metabolite panel could serve as an independent predictor for HCC; low expression of retinol and retinal correlated with decreased survival time. Retinol metabolism thus hold great promise for clinical application in HCC diagnosis and prognosis.
A sensor with a red‐emission signal is successfully obtained by the solvothermal reaction of Eu3+ and heterofunctional ligand bpydbH2 (4,4′‐(4,4′‐bipyridine‐2,6‐diyl) dibenzoic acid), followed by ...terminal‐ligand exchange in a single‐crystal‐to‐single‐crystal transformation. As a result of treatments both before and after the metal–organic framework formation, accessible Lewis‐base sites and coordinated water molecules are successfully anchored onto the host material, and they act as signal transmission media for the recognition of analytes at the molecular level. This is the first reported sensor based on a metal–organic framework (MOF) with multi‐responsive optical sensing properties. It is capable of sensing small organic molecules and inorganic ions, and unprecedentedly it can discriminate among the homologues and isomers of aliphatic alcohols as well as detect highly explosive 2,4,6‐trinitrophenol (TNP) in water or in the vapor phase. This work highlights the practical application of luminescent MOFs as sensors, and it paves the way toward other multi‐responsive sensors by demonstrating the incorporation of various functional groups into a single framework.
Multi‐responsive fluorescent sensing is achieved using a Eu metal–organic framework (EuMOF). Accessible Lewis‐base sites and coordinated water molecules are successfully anchored on the EuMOF‐based sensor for the recognition of different analytes at the molecular level. This strategy paves the way for the practical application of luminescent MOF sensors in pollutant‐detection.
A tetraphenylethylene (TPE) Schiff‐base macrocycle showing an aggregation‐induced emission (AIE) effect has been synthesized, which could aggregate into nanospheres and emit yellow fluorescence in ...aqueous media. By virtue of its AIE effect, the macrocycle showed a sensitive and selective response to 2,4,6‐trinitrophenol (TNP) and 2,4‐dinitrophenol (DNP) among a number of nitroaromatic compounds, which could be used to detect TNP and DNP at nanomolar levels. Moreover, it exhibited a superamplified quenching effect with DNP but not with TNP, providing a possible means of discriminating these two compounds. In comparison with open‐chain TPE Schiff‐bases, the cavity of the macrocycle is essential for the selectivity for DNP over TNP. In addition, quantitative analyses of both DNP and TNP in real water samples and qualitative detection of these two analytes in the solid state by the macrocycle have been tested. The reliability of the quantitative analysis has been confirmed by HPLC. Our findings demonstrate that the TPE Schiff‐base macrocycle has great potential as an excellent sensor for DNP and TNP.
AIE‐based detection: A tetraphenylethylene Schiff‐base macrocycle (see scheme) displaying aggregation‐induced emission shows a sensitive and selective response to 2,4,6‐trinitrophenol (TNP) and 2,4‐dinitrophenol (DNP). This response can be exploited to detect TNP and DNP at nanomolar levels. Moreover, the macrocycle exhibits a superamplified quenching effect with DNP but not with TNP, providing a possible means of discriminating these compounds (AIE = aggregation induced emission).
New hindered tetraphenylethylene (TPE) helicates with substitution at 2,6‐position of phenyl rings were designed and synthesized. Due to the increased hindrance, the TPE helicates emit strong ...deep‐blue to violet fluorescence both in the solid state and in solution, and could be resolved into enantiomers that emit strong and multicolor circularly polarized luminescence (CPL), and exhibit a high enantioselective recognition of chiral tartaric acid and its derivatives. Surprisingly, the derived helicate tetramines possess amino groups with an unpredented planar structure and sp2‐hybridized nitrogen, arousing the change between AIE effect and ACQ phenomenon through photoinduced electron transfer (PET). With advantages of short synthetic route, many modification positions, deep‐blue to violet emission, wide CPL tuning, and high chiral recognition ability, the hindered TPE helicates show broad prospects as chiral materials.
Hindered tetraphenylethylene (TPE) helicates, with a completely immobilized propeller‐like conformation through substitution at the 2,6‐positions of the phenyl rings, were prepared by a short synthetic route. These helicates, with their many modification positions, show deep‐blue to violet emission, circularly polarized luminescence (CPL) that can be tuned over a wide range, and highly enantioselective chiral recognition.
Hierarchical CoS2 microspheres were prepared and modified with a cationic ionic liquid (IL). The composite shows enhanced oxygen evolution reaction (OER) performances attributed to the fact that the ...OER equilibrium is driven forward by the IL, according to Le Chatelier's principle, and by the electrostatic affinity generated at the CoS2/electrolyte interface.
Accurate detection of trace biomarkers in biological samples is a key task in diagnostic testing, but it remains challenging due to the high concentration of other physiologically relevant ...interferences. This work presents a new electrochemiluminescence (ECL) sensing device based on a bio‐inspired nanochannel membrane (NM) guarded with two differential gates. The recognition event at the aptamer gate is followed by the permitting of stimulator transport toward the metal‐organic framework (MOF) gate. Proof of concept application is evaluated using cytochrome C (Cytc) as the analyte, and glucose, a commonly existing nutriment as the stimulator. The oxidase‐mimic plasmonic nanoparticles induce an effective release of ECL luminophore from the MOF gate. This cascade‐gates guarded NM can effectively separate biological matrices from the detection cell. Consequently, the proposed system can achieve direct sensing of 1.0 nm Cytc in undiluted serum within the threshold concentrations of leukemia and lymphoma, making it attractive for point‐of‐care applications.
An electrochemiluminescence biosensing strategy using a cascade‐gates guarded membrane is developed for eliminating matrix interference and regulating the delivery of signal reporters from two separate but correlated binding events. Using cytochrome C as the model analyte, the membrane demonstrates outstanding performance for direct analysis of trace biomarker in undiluted serum.
Due to their abundant resources and potential price advantage, potassium-ion batteries (KIBs) have recently drawn increasing attention as a promising alternative to lithium-ion batteries (LIBs) for ...their applications in electrochemical energy storage applications. Despite the continuous progress in identifying possible electrode materials, the development of KIBs has been challenged by different problems including low reversible capacities, unsatisfactory cycling stability, and insufficient energy density, which become serious concerns for the practical application of KIBs. In this review, we will summarize the recent advancements in both cathode and anode materials with focus on their structure-performance relationship. Meanwhile, challenges and opportunities related to the future development of KIBs are also discussed.
Due to their abundant resources and potential price advantage, potassium-ion batteries (KIBs) have recently drawn increasing attention as a promising alternative to lithium-ion batteries (LIBs) for their applications in electrochemical energy storage applications.
Organic molecules with an aggregation-induced emission (AIE) effect have recently been attracting more and more attention due to their colossal potential in solid emitters and chemo/biosensors. The ...number and variety of AIEgen compounds are expanding very rapidly to obtain better application performance and a wider area of application. Among AIEgen systems, tetraphenylethylene (TPE) and its derivatives are the class that have received the most extensive study and the most rapid development because of their facile synthesis. Due to its
C
2
symmetry and at least tetratopic reaction positions, the TPE unit is also an ideal building block for constructing macrocycles and cages. The resultant cyclic TPE compounds have exhibited many exceptional performances that are difficult to access in their open chain counterparts, such as AIE enhancement, improvement in selectivity and sensitivity as sensors, emission tuning by guests, supramolecular catalysis, further disclosure of the AIE mechanism, molecular adsorption, storage and release, the propeller-like conformation exploitation of the TPE unit in chiral materials and so on. Recently, therefore, a large variety of studies about the synthesis, properties and application research of TPE macrocycles and cages have been reported. These TPE macrocycles and cages significantly expand the research area for the AIE phenomenon and its applications, and represent a development of the AIE area. However, up to now, no review of TPE macrocycles and cages has been available. Thus, this review serves as a summary of the designs, synthesis, photophysical properties, self-assembly, applications and prospects of TPE macrocycles and cages.
Syntheses, photophysical properties and applications of macrocycles and cages based on tetraphenylethylene with aggregation-induced emission (AIE) effect.
As a highly electrochemically active transition-metal oxide (TMO), cobalt monoxide (CoO) has been extensively investigated for applications in lithium-ion batteries and electrochemical oxygen ...evolution. However, its capacitive performance has been rarely studied due to the intrinsic low conductivity and poor stability. Here, we report an asymmetric supercapacitor with excellent electrochemical capacity based on an ultrathin carbon shell entrapped Co-doped CoO heterostructure (CoO/Co@C). The metallic conductivity and mesoporous configuration make the as-prepared CoO/Co@C deliver a dramatic specific capacitance of 2165.7 F g
−1
at a scan rate of 10 mV s
−1
. Besides the contribution to double-layer capacitance, more importantly, the amorphous carbon shell effectively prevents the CoO/Co heterostructure from further oxidation, thus resulting in a significantly improved long-term storage stability in air. An asymmetric supercapacitor cell fabricated using CoO/Co@C and active carbon achieves a maximum energy density of 146.3 W h kg
−1
at a power density of 1800 W kg
−1
, and the maximum of 27 000 W kg
−1
can be obtained with a remaining energy density of 63.0 W h kg
−1
. The easy preparation, high performance, and excellent cycling stability of the CoO/Co@C nanocomposite make it a promising material for catalyst and battery applications.
