A convenient and real-time fluorometric assay with the assistance of copper ions based on aggregation and disaggregation of carbon quantum dots (CQDs) was developed to achieve highly sensitive ...detection of alkaline phosphatase activity. CQDs and pyrophosphate anions (PPi) were used as the fluorescent indicator and substrate for ALP activity assessment respectively. Richness of carboxyl groups on the surface of CQDs enables their severe aggregation triggered by copper ions, which results in effective fluorescence quenching. Under the catalytic hydrolysis of ALP, PPi can be rapidly transformed to phosphate ions. Stronger affinity of phosphate ions to copper ions than carboxyl groups is taken advantage of to achieve fluorescence recovery induced by re-dispersion of CQDs in the presence of ALP and PPi. Quantitative evaluation of ALP activity in a broad range from 16.7 to 782.6 U/L with the detection limit of 1.1 U/L can be realized in this way, which endows the assay with high enough sensitivity for practical detection in human serum. This strategy broadens the sensing application of fluorescent CQDs with excellent biocompatibility, and provides an example based on disaggregation in optical probe development.
The accurate state of charge (SOC) estimation plays a significant role in charge/discharge control, balance control, and safe management of lithium-ion batteries (LIBs). However, due to the model ...mismatch issues, either from battery inconsistency or battery dynamic characteristics difference, the accuracy of the model-based SOC estimation method is usually unsatisfactory. To solve this problem, a joint moving horizon estimation (joint-MHE) approach that can simultaneously estimate the model parameter and state is proposed here. In this paper, the circuit-equivalent battery model is first constructed by parameterizing the circuit parameters as polynomial function of SOC. Then, by the sensitivity analysis, the update parameters are selected and added to the state-space model as additional states. Finally, the joint-MHE strategy is conducted for the simultaneous parameter and SOC estimation. To investigate the performance of the proposed method thoroughly, three model mismatch conditions are considered, including battery inconsistency, battery dynamic characteristics difference, and the combination of both. The results demonstrate that the joint-MHE approach is an effective way to solve the model mismatch problem. Moreover, compared to joint extended Kalman filtering, the proposed approach can offer a more reliable, robust, and accurate SOC estimation of LIBs under various model mismatch conditions.
In recent years, the strategy of merging visible light photocatalysis and organocatalysis has been utilized and applied in a wide range of reactions. Taking advantage of synergistic visible light ...photocatalysis with organocatalysis, remarkable progress has recently been achieved in modern chemical synthesis. In these dual catalytic systems, photocatalysts or photosensitizers absorb visible light to induce their photo‐excited states which can activate unreactive substrates via electron or energy transfer mechanisms, and organocatalysts are usually employed to control the chemical reactivities of the other substrates. This review mainly focuses on the recent development of cooperative catalysis by the combination of organocatalysis and photocatalysis in recent organic synthesis.
The strategy of merging visible light photocatalysis and organocatalysis has been utilized and applied in a wide range of reactions. This review summarized the latest advances in the field of cooperative catalysis by the combination of organocatalysis and photocatalysis in recent organic synthesis.
(Deuterium‐labeled) CF2H‐ and CFH2‐moieties are of high interest in drug discovery. The high demand for the incorporation of these fluoroalkyl moieties into molecular structures has witnessed ...significant synthetic progress, particularly in the (deutero)hydrodefluorination of CF3‐containing compounds. However, the controllable replacement of fluorine atoms while maintaining high chemoselectivity remains challenging. Herein, we describe the development of a selective (deutero)hydrodefluorination reaction via electrolysis. The reaction exhibits a remarkable chemoselectivity control, which is enabled by the addition of different organoboron sources. The procedure is operationally simple and scalable, and provides access in one step to high‐value building blocks for application in medicinal chemistry. Furthermore, density functional theory (DFT) calculations have been carried out to investigate the reaction mechanism and to rationalize the chemoselectivity observed.
We herein reported an electrochemical selective (deutero)hydrodefluorination reaction of trifluoroacetamides. The reaction which exhibits a remarkable chemoselectivity control and delivers (deuterium‐labeled) CF2H‐ and CFH2‐products in good yields with high level of deuterium incorporation, respectively, is enabled by the addition of different organoboron sources and (deuterated)water as the deuterium or hydrogen source.
Abstract
The zeolite Cu(I)Y is promising for adsorptive removal of thiophenic sulfur compounds from transportation fuels. However, its application is seriously hindered by the instability of Cu(I), ...which is easily oxidized to Cu(II) even under atmospheric environment due to the coexistence of moisture and oxygen. Here, we report the adjustment of zeolite microenvironment from hydrophilic to superhydrophobic status by coating polydimethylsiloxane (yielding Cu(I)Y@P), which isolates moisture entering the pores and subsequently stabilizes Cu(I) despite the presence of oxygen. Cu(I) in Cu(I)Y@P is stable upon exposure to humid atmosphere for 6 months, while almost all Cu(I) is oxidized to Cu(II) in Cu(I)Y for only 2 weeks. The optimized Cu(I)Y@P material after moisture exposure can remove 532 μmol g
−1
of thiophene and is much superior to Cu(I)Y (116 μmol g
−1
), regardless of similar uptakes for unexposed adsorbents. Remarkably, Cu(I)Y@P shows excellent adsorption capacity of desulfurization for water-containing model fuel.
To identify the predictive role of sarcopenia in long-term survival among rectal cancer patients who underwent surgery based on available evidence.
The Medline, EMBASE and Web of Science databases ...were searched up to October 20, 2023, for relevant studies. Overall survival (OS), disease-free survival (DFS) and cancer-specific survival (CSS) were the endpoints. Hazard ratios (HRs) and 95% confidence intervals (CIs) were combined to evaluate the association between sarcopenia and survival.
Fifteen studies with 4283 patients were included. The pooled results demonstrated that preoperative sarcopenia significantly predicted poorer OS (HR = 2.07, 95% CI = 1.67-2.57, P<0.001), DFS (HR = 1.85, 95% CI = 1.39-2.48, P<0.001) and CSS (HR = 1.83, 95% CI = 1.31-2.56, P<0.001). Furthermore, subgroup analysis based on neoadjuvant therapy indicated that sarcopenia was a risk factor for worse OS and DFS in patients who received (OS: HR = 2.44, P<0.001; DFS: HR = 2.16, P<0.001) but not in those who did not receive (OS: HR = 2.44, P<0.001; DDFS: HR = 1.86, P = 0.002) neoadjuvant chemoradiotherapy. In addition, subgroup analysis based on sample size and ethnicity showed similar results.
Preoperative sarcopenia is significantly related to poor survival in surgical rectal cancer patients and could serve as a novel and valuable predictor of long-term prognosis in these patients.
An electrochemical Reformatsky‐type reaction of bromodifluoroamides with aldehydes/ketones via electron reductive umpolung is reported, leading to the generation of a series of β‐hydroxy‐α,α‐difluoro ...amides in moderate to good yields. This protocol tolerated a variety of commercially available alkyl ketone, alkyl and aromatic aldehydes, featuring broad substrate scope and good functional group tolerance under transition metal‐free conditions without metal reduction reagents. Control experiment indicated that the reaction proceeded via an electron reductive umpolung pathway.
Besides generating vision, light modulates various physiological functions, including mood. While light therapy applied in the daytime is known to have anti-depressive properties, excessive light ...exposure at night has been reportedly associated with depressive symptoms. The neural mechanisms underlying this day-night difference in the effects of light are unknown. Using a light-at-night (LAN) paradigm in mice, we showed that LAN induced depressive-like behaviors without disturbing the circadian rhythm. This effect was mediated by a neural pathway from retinal melanopsin-expressing ganglion cells to the dorsal perihabenular nucleus (dpHb) to the nucleus accumbens (NAc). Importantly, the dpHb was gated by the circadian rhythm, being more excitable at night than during the day. This indicates that the ipRGC→dpHb→NAc pathway preferentially conducts light signals at night, thereby mediating LAN-induced depressive-like behaviors. These findings may be relevant when considering the mental health effects of the prevalent nighttime illumination in the industrial world.
Bone morphogenetic protein-2 (BMP-2) is currently the only Food and Drug Administration (FDA)-approved osteoinductive growth factor used as a bone graft substitute. However, with increasing clinical ...use of BMP-2, a growing and well-documented side effect profile has emerged. This includes postoperative inflammation and associated adverse effects, ectopic bone formation, osteoclast-mediated bone resorption, and inappropriate adipogenesis. Several large-scale studies have confirmed the relative frequency of adverse events associated with the clinical use of BMP-2, including life-threatening cervical spine swelling. In fact, the FDA has issued a warning of the potential life-threatening complications of BMP-2. This review summarizes the known adverse effects of BMP-2, including controversial areas such as tumorigenesis. Next, select animal models that replicate BMP-2's adverse clinical effects are discussed. Finally, potential molecules to mitigate the adverse effects of BMP-2 are reviewed. In summary, BMP-2 is a potent osteoinductive cytokine that has indeed revolutionized the bone graft substitute market; however, it simultaneously has accrued a worrisome side effect profile. Better understanding of these adverse effects among both translational scientists and clinicians will help determine the most appropriate and safe use of BMP-2 in the clinical setting.
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