Selective C−F bond functionalization of CF3 group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant ...advancement attained in the functionalization of Ar‐CF3 molecules, prescriptions amenable for alkenyl‐CF3 congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C−F bond elaboration of trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF2‐bridged 1,5‐dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic SN2′ defluorinative allylation and electronically promoted Cope rearrangement.
By capitalizing on the unique fluorine effects, a mono‐selective C−F bond allylation of trifluoromethylalkenes, which proceeds through a cascade of nucleophilic SN2′ defluorinative allylation and Cope rearrangement, was achieved under operationally convenient conditions.
Gut microbial dysbiosis and alteration of microbial metabolites in Parkinson's disease (PD) have been increasingly reported. Dysbiosis in the composition and abundance of gut microbiota can affect ...both the enteric nervous system and the central nervous system (CNS), indicating the existence of a microbiota-gut-brain axis and thereby causing CNS diseases. Disturbance of the microbiota-gut-brain axis has been linked to specific microbial products that are related to gut inflammation and neuroinflammation. Future directions should therefore focus on the exploration of specific gut microbes or microbial metabolites that contribute to the development of PD. Microbiota-targeted interventions, such as antibiotics, probiotics and fecal microbiota transplantation, have been shown to favorably affect host health. In this review, recent findings regarding alterations and the role of gut microbiota and microbial metabolites in PD are summarized, and potential molecular mechanisms and microbiota-targeted interventions in PD are discussed.
Abstract
Background
Post-traumatic hydrocephalus (PTH) is a complication of traumatic brain injury (TBI) that requires treatment and postoperative care. The shunt is one of the main treatments for ...PTH, which presents with dysfunction and infection. Considering brain injury, hydrocephalus shunt malfunction, and infection, family caregivers need to be responsible for caring for PTH patients, recognizing shunt malfunction and infection, and managing those patients accordingly from hospital to home. Understanding the experiences and needs of caregivers is beneficial for knowing their competency and quality of health care, ameliorating and ensuring future transition care. The study aimed to explore the feelings, experiences, and needs of family caregivers when caring for patients with TBI, PTH and shunts.
Methods
This was exploratory research of a purposive sample of 12 family caregivers of adult patients with TBI, PTH and shunts in five neurosurgery departments at a general hospital in Zhengzhou, Henan Province, China, using a semi-structured interview method. Data were collected from October 2021 to March 2022 before being analyzed by content analysis methods.
Results
Caregivers required professional and social knowledge and support in the areas of TBI, PTH and shunts, caregiving interventions, psychological care needs, and health insurance, just as caregivers do, but unlike other general caregivers, care for patients with TBI, PTH, and shunt is fraught with uncertainty and the need to manage shunt setting, and caregivers often experience 'complex emotional reaction' during the transitional period, where care needs and complex emotions may lead to a lack of caregiver confidence, which in turn may affect caregiving behaviors, and experiences that affect care may be mediated through caregiving confidence. The perceived availability of resources, particularly those that are still available to them when they return home, has a significant impact on participants' emotional response and sense of confidence.
Conclusions
The emotional response and the impact of stressor caregivers after TBI, PTH, and shunt was important, and sometimes confidence in care appeared to be an intermediate and useful factor that needed to be considered as health professionals prepared to develop care resources on how to manage and empower patients with TBI, PTH, and shunt. Meanwhile, there may be gaps and inequities in supportive care for patients diagnosed with TBI, PTH, and shunt in China.
Exploring high‐efficiency and stable halide perovskite‐based photocatalysts for the selective reduction of CO2 to methane is a challenge because of the intrinsic photo‐ and chemical instability of ...halide perovskites. In this study, halide perovskites (Cs3Bi2Br9 and Cs2AgBiBr6) were grown in situ in mesoporous TiO2 frameworks for an efficient CO2 reduction. Benchmarked CH4 production rates of 32.9 and 24.2 μmol g−1 h−1 with selectivities of 88.7 % and 84.2 %, were achieved, respectively, which are better than most reported halide perovskite photocatalysts. Focused ion‐beam sliced‐imaging techniques were used to directly image the hyperdispersed perovskite nanodots confined in mesopores with tunable sizes ranging from 3.8 to 9.9 nm. In situ X‐ray photoelectronic spectroscopy and Kelvin probe force microscopy showed that the built‐in electric field between the perovskite nanodots and mesoporous titania channels efficiently promoted photo‐induced charge transfer. Density functional theory calculations indicate that the high methane selectivity was attributed to the Bi‐adsorption‐mediated hydrogenation of *CO to *HCO that dominates CO desorption.
Halide perovskites (Cs3Bi2Br9, Cs2AgBiBr6) are grown in situ in a mesoporous titania framework for efficient CO2 reduction reaction (CO2RR). A benchmarked production rate of CH4 (32.9 and 24.2 μmol g−1 h−1) is achieved with selectivity values of 88.7 % and 84.2 %, respectively. In situ X‐ray photoelectronic spectroscopy and Kelvin probe force microscopy reveal that the inner surface built‐in electric field between the perovskite nanodots and mesoporous titania channels can efficiently promote photo‐induced charge transfer.
The international trade of waste has been an important and growing part of the global economy during the last two decades, which imposes regulatory challenges to governments in the South to protect ...the environment. This paper investigates the effect of border controls with a difference-in-difference design by exploiting a unique natural experiment, China's Operation Green Fence (OGF) implemented in 2013. We find that the OGF exerted a significant deterrent effect on the waste imported into China. Specifically, we find that the import weight of waste grew by 9.48 percentage less and the import price declined by 7.6 percentage more compared to those of the non-waste. The results are robust to a series of robustness checks, and there is no similar reaction in other regions, where the OGF was not initiated.
•The deterrent effect of China's Operation Green Fence campaign is investigated.•The waste imports exposed to the campaign are compared to the other imports.•The import weight of waste grew by 9.48 percentage less.•The import price of waste declined by 7.6 percentage more.•There is no similar reaction in other regions.
Multidrug resistance (MDR) is a major impediment to the success of cancer chemotherapy. Through the development of a drug delivery system that tethers doxorubicin onto the surface of gold ...nanoparticles with a poly(ethylene glycol) spacer via an acid-labile linkage (DOX-Hyd@AuNPs), we have demonstrated that multidrug resistance in cancer cells can be significantly overcome by a combination of highly efficient cellular entry and a responsive intracellular release of doxorubicin from the gold nanoparticles in acidic organelles. DOX-Hyd@AuNPs achieved enhanced drug accumulation and retention in multidrug resistant MCF-7/ADR cancer cells when it was compared with free doxorubicin. It released doxorubicin in response to the pH of acidic organelles following endocytosis, opposite to the noneffective drug release from doxorubicin-tethered gold nanoparticles via the carbamate linkage (DOX-Cbm@AuNPs), which was shown by the recovered fluorescence of doxorubicin from quenching due to the nanosurface energy transfer between the doxorubicinyl groups and the gold nanoparticles. DOX-Hyd@AuNPs therefore significantly enhanced the cytotoxicity of doxorubicin and induced elevated apoptosis of MCF-7/ADR cancer cells. With a combined therapeutic potential and ability to probe drug release, DOX-Hyd@AuNPs represent a model with dual roles in overcoming MDR in cancer cells and probing the intracellular release of drug from its delivery system.
Noncoding RNAs (ncRNAs) represent a large segment of the human transcriptome and have been shown to play important roles in cellular physiology and disease pathogenesis. Increasing evidence on the ...functional roles of ncRNAs in cancer progression emphasizes the potential of ncRNAs for cancer treatment. Here, we summarize the roles of ncRNAs in disease relapse and resistance to current standard chemotherapy and radiotherapy; the current research progress on ncRNAs for clinical and/or potential translational applications, including the identification of ncRNAs as therapeutic targets; therapeutic approaches for ncRNA targeting; and ncRNA delivery strategies in potential clinical translation. Several ongoing clinical trials of novel RNA-based therapeutics were also emphasized. Finally, we discussed the perspectives and obstacles to different target combinations, delivery strategies, and system designs for ncRNA application. The next approved nucleic acid drug to treat cancer patients may realistically be on the horizon.
Summary
Vegetable oil is a major edible oil and an important industrial raw material. However, breeders have found it challenging to improve the oil content of crop seeds, and little is known about ...regulators with the potential to increase oil content via molecular engineering in modern oil crop breeding.
We reported an F‐box protein, Arabidopsis thaliana MYB Interaction Factor 1 (AtMIF1), which is a member of the ubiquitin‐protein ligase E3 complex involved in the 26S proteasome protein degradation pathway. AtMIF1 physically interacts with MYB domain protein 5 (MYB5), which results in MYB5 degradation, so that transcriptional activation of the MYB/bHLH/WD‐repeat (MBW) complex does not occur normally and GLABRA2 (GL2), encoding an inhibitor of oil content and functioning as a direct downstream gene of MBW, is not properly transcribed.
AtMIF1 functioned as a positive regulator that increases oil content by attenuating GL2 inhibition. We overexpressed AtMIF1 and obtained transgenic plants with significantly higher seed oil contents. Importantly, both vegetative and reproductive growth of the transgenic plants appeared normal.
In summary, this work reveals a novel regulator, AtMIF1, and a new regulatory pathway, 26S proteasome‐AtMIF1‐MYB5, for increasing the oil content of seeds without affecting plant growth, thus facilitating oil crop breeding.
Noncoding RNAs (ncRNAs) are a large segment of the transcriptome that do not have apparent protein-coding roles, but they have been verified to play important roles in diverse biological processes, ...including disease pathogenesis. With the development of innovative technologies, an increasing number of novel ncRNAs have been uncovered; information about their prominent tissue-specific expression patterns, various interaction networks, and subcellular locations will undoubtedly enhance our understanding of their potential functions. Here, we summarized the principles and innovative methods for identifications of novel ncRNAs that have potential functional roles in cancer biology. Moreover, this review also provides alternative ncRNA databases based on high-throughput sequencing or experimental validation, and it briefly describes the current strategy for the clinical translation of cancer-associated ncRNAs to be used in diagnosis.
The cereal endosperm is a major factor determining seed size and shape. However, the molecular mechanisms of endosperm development are not fully understood. Long noncoding RNAs (lncRNAs) function in ...various biological processes. Here we show a lncRNA, MISSEN, that plays an essential role in early endosperm development in rice (Oryza sativa). MISSEN is a parent-of-origin lncRNA expressed in endosperm, and negatively regulates endosperm development, leading to a prominent dent and bulge in the seed. Mechanistically, MISSEN functions through hijacking a helicase family protein (HeFP) to regulate tubulin function during endosperm nucleus division and endosperm cellularization, resulting in abnormal cytoskeletal polymerization. Finally, we revealed that the expression of MISSEN is inhibited by histone H3 lysine 27 trimethylation (H3K27me3) modification after pollination. Therefore, MISSEN is the first lncRNA identified as a regulator in endosperm development, highlighting the potential applications in rice breeding.
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