The catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyls to their corresponding alcohols. Herein, a series of Zr-based metal−organic ...frameworks (Zr-MOFs) containing various types of metal node to ligand coordinations were synthesized and tested for CTH of furfural (FUR) to furfuryl alcohol (FOL). It was found that metal node coordination plays a more important role than porosity in Zr-MOFs. MOF-808 (synthesized using a scaled-up approach to achieve a higher batch yield), with the lowest metal node to ligand coordination (coordination number 6), was found to be the most active catalyst among the various tested Zr-MOFs. Furthermore, M-MOF-808, modified by simple methanol activation (M), outperformed the pristine MOF-808 in CTH of FUR to FOL even at 30 °C in the presence of 2-propanol (IPA) as the hydrogen source. The simple modification of the metal node in the Zr-MOF changed the acid–base properties of the MOF-808 surface through the development of coordinatively unsaturated sites (CUS), hydroxyl and methoxy groups in the framework of the Zr-MOF, which probably help to facilitate the adsorption of FUR and IPA onto the metal node surfaces of the catalyst. To evaluate the versatility of methanol activation in CTH, further substrates, including other types of biomass and representative carbonyl compounds over M-MOF-808, were tested. To demonstrate heterogeneous catalysis, the catalyst was recycled for five consecutive cycles, with little loss after the first cycle, and was fully characterized to observe any changes in its structure. Mechanistic insights were provided by isotopically labeled 2-propanol-d 8 experiments, indicating FUR reduction through transfer hydrogenation. Finally, the reaction mechanism for CTH of FUR to FOL was proposed in detail using density functional theory (DFT) calculations over metal node modified model systems of a 6-connected Zr-MOF.
Background and purpose - We aimed to evaluate the ability of artificial intelligence (a deep learning algorithm) to detect and classify proximal humerus fractures using plain anteroposterior shoulder ...radiographs.
Patients and methods - 1,891 images (1 image per person) of normal shoulders (n = 515) and 4 proximal humerus fracture types (greater tuberosity, 346; surgical neck, 514; 3-part, 269; 4-part, 247) classified by 3 specialists were evaluated. We trained a deep convolutional neural network (CNN) after augmentation of a training dataset. The ability of the CNN, as measured by top-1 accuracy, area under receiver operating characteristics curve (AUC), sensitivity/specificity, and Youden index, in comparison with humans (28 general physicians, 11 general orthopedists, and 19 orthopedists specialized in the shoulder) to detect and classify proximal humerus fractures was evaluated.
Results - The CNN showed a high performance of 96% top-1 accuracy, 1.00 AUC, 0.99/0.97 sensitivity/specificity, and 0.97 Youden index for distinguishing normal shoulders from proximal humerus fractures. In addition, the CNN showed promising results with 65-86% top-1 accuracy, 0.90-0.98 AUC, 0.88/0.83-0.97/0.94 sensitivity/specificity, and 0.71-0.90 Youden index for classifying fracture type. When compared with the human groups, the CNN showed superior performance to that of general physicians and orthopedists, similar performance to orthopedists specialized in the shoulder, and the superior performance of the CNN was more marked in complex 3- and 4-part fractures.
Interpretation - The use of artificial intelligence can accurately detect and classify proximal humerus fractures on plain shoulder AP radiographs. Further studies are necessary to determine the feasibility of applying artificial intelligence in the clinic and whether its use could improve care and outcomes compared with current orthopedic assessments.
Mortality difference by age, sex, body mass index (BMI) in gastric cancer (GC) has been controversial. We evaluated sex-specific mortality by age and BMI. A total of 5961 patients diagnosed with GC ...from 2005 to 2013 in a single tertiary center were included and were followed until December 2017. The plot in goodness-of-fit-test by sex was crossed, so we performed sex-specific analysis. Overall mortality was lower in women than in men (adjusted hazard ratio aHR, 0.72). Favor outcomes in women compared to men were observed among patients older than 60 yr (aHR, 0.64; 95% CI, 0.56–0.74), a BMI less than 25 kg/m2 (aHR, 0.69; 95% CI, 0.61–0.79), and stage I (aHR, 0.46; 95% CI, 0.38–0.56). In sex-specific analysis, mortality increased in age older than 60 yr in men, whereas it increased in both extreme ages (<40 yr and ≥ 70 yr) in women. Mortality by BMI was lowest at BMI of 25–29.9 kg/m2 and gradually increased according to decrease of BMI in men; aHR, 1.24 (23–24.9 kg/m2), 1.44 (18.5–22.9 kg/m2), and 2.54 (BMI<18.5 kg/m2). However, mortality decreased in patients with BMI ≥ 30 kg/m2 (aHR, 0.46) in women. The sex discrepancies in GC mortality by age and BMI suggest the need for sex-specific approaches to prognostic prediction.
Methionine sulfoxide reductase B3 (MsrB3), which stereospecifically repairs methionine-R-sulfoxide, is an important Msr protein that is associated with auditory function in mammals. MsrB3 deficiency ...leads to profound congenital hearing loss due to the degeneration of stereociliary bundles and the apoptotic death of cochlear hair cells. In this study, we investigated a fundamental treatment strategy in an MsrB3 deficiency mouse model and confirmed the biological significance of MsrB3 in the inner ear using MsrB3 knockout (MsrB3(-/-)) mice.
We delivered a recombinant adeno-associated virus encoding the MsrB3 gene directly into the otocyst at embryonic day 12.5 using a transuterine approach. We observed hearing recovery in the treated ears of MsrB3(-/-) mice at postnatal day 28, and we confirmed MsrB3 mRNA and protein expression in cochlear extracts. Additionally, we demonstrated that the morphology of the stereociliary bundles in the rescued ears of MsrB3(-/-) mice was similar to those in MsrB3(+/+) mice.
To our knowledge, this is the first study to demonstrate functional and morphological rescue of the hair cells of the inner ear in the MsrB3 deficiency mouse model of congenital genetic sensorineural hearing loss using an in utero, virus-mediated gene therapy approach.
Our results provide insight into the role of MsrB3 in hearing function and bring us one step closer to hearing restoration as a fundamental therapy.
This article introduces a 16-Gb T-coil-based graphics double-data-rate 6 (GDDR6) dynamic random access memory (DRAM) with merged-multiplexer (MUX) transmitter (TX), optimized data clock (WCK) ...operation to enhance I/O bandwidth. T-coil is implemented for the first time in a DRAM process. Moreover, an alternative-data-bus (ADB) is employed to solve the frequency limit of the data bus. The proposed T-coil-based GDDR6 DRAM achieves 27 Gb/s/pin with 1.35 V in a DRAM process.
Mass spectrometry (MS) based proteomics is widely used for biomarker discovery. However, often, most biomarker candidates from discovery are discarded during the validation processes. Such ...discrepancies between biomarker discovery and validation are caused by several factors, mainly due to the differences in analytical methodology and experimental conditions. Here, we generated a peptide library which allows discovery of biomarkers in the equal settings as the validation process, thereby making the transition from discovery to validation more robust and efficient. The peptide library initiated with a list of 3393 proteins detectable in the blood from public databases. For each protein, surrogate peptides favorable for detection in mass spectrometry was selected and synthesized. A total of 4683 synthesized peptides were spiked into neat serum and plasma samples to check their quantifiability in a 10 min liquid chromatography-MS/MS run time. This led to the PepQuant library, which is composed of 852 quantifiable peptides that cover 452 human blood proteins. Using the PepQuant library, we discovered 30 candidate biomarkers for breast cancer. Among the 30 candidates, nine biomarkers, FN1, VWF, PRG4, MMP9, CLU, PRDX6, PPBP, APOC1, and CHL1 were validated. By combining the quantification values of these markers, we generated a machine learning model predicting breast cancer, showing an average area under the curve of 0.9105 for the receiver operating characteristic curve.
Veterinary antibiotics (VAs) administered to livestock are introduced into the soil through livestock manure and compost. These antibiotics can run off to surface water or leach into groundwater ...during rainfall, causing problems such as antibiotic contamination or the occurrence of antibiotic-resistant bacteria. In this study, an analytical method for detecting four classes of VAs (penicillin, tetracyclines, macrolides, and sulfonamides) in river water and soil was developed, and the occurrence of residual antibiotics in the agricultural environment was monitored. Soil samples were extracted with the McIlvain buffer solution and pretreatment was conducted using solid-phase extraction, followed by liquid chromatography-tandem mass spectrometry to quantify target VAs. The results of this study showed that the recovery ranged from 62 to 121% in river water and 40.2–149.3% in soil. Among the other VAs, amoxicillin and spiramycin were observed to have low recoveries in all the samples. The method detection limit (MDL) was calculated in the range of 2.1–12.3 ng L
−1
in river water and 1.2–13.2 ng kg
−1
in soil, and the limit of quantification was 6.6–39.2 ng L
−1
and 4.0–42.0 ng kg
−1
, respectively. This optimal method was then applied to measure the residual concentrations of VAs in river water, sediment, and soil samples around the Muhan watershed in Korea. A total of seven antibiotics were detected, and their concentrations ranged from 0.014 to 0.309 μg L
−1
in river water, and 1.45–9.04 μg kg
−1
in sediment and arable soil. This method can be used to screen VAs in river water and soil and is expected to be used as primary data for examining the occurrence and fate of antibiotics in agricultural environments.
Digital health technologies have been used to enhance adherence to TB medication, but the cost-effectiveness remains unclear.
We used the real data from the study conducted from April 2014 to ...December 2020 in Morocco using a smart pillbox with a web-based medication monitoring system, called Medication Event Monitoring Systems (MEMS). Cost-effectiveness was evaluated using a decision analysis model including Markov model for Multi-drug resistant (MDR) TB from the health system perspective. The primary outcome was the incremental cost-effectiveness ratio (ICER) per disability adjusted life-year (DALY) averted. Two-way sensitive analysis was done for the treatment success rate between MEMS and standard of care.
The average total per-patient health system costs for treating a new TB patient under MEMS versus standard of care were $398.70 and $155.70, respectively. The MEMS strategy would reduce the number of drug-susceptible TB cases by 0.17 and MDR-TB cases by 0.01 per patient over five years. The ICER of MEMS was $434/DALY averted relative to standard of care, and was most susceptible to the TB treatment success rate of both strategies followed by the managing cost of MEMS.
MEMS is considered cost-effective for managing infectious active TB in Morocco.
Stable, high-performance noble-metal catalysts have proven effective for obtaining lactate (LA) and formate (FA) from simultaneous conversion of glycerol and carbonate as a CO2 source. For this ...purpose, we developed a novel method reported herein for the synthesis of Ru nanoparticles (NPs) supported on graphitic nanoporous carbon (Ru/NCT, T = pyrolysis temperature). The Ru/NCT catalysts were prepared by in situ encapsulation of trimeric ruthenium clusters in ZIF-11 pores, with a subsequent pyrolysis process. The pyrolysis temperature affected the size and crystallinity of Ru NPs and the textural properties of the ZIF-11-derived carbon. Optimization of reaction parameters such as CO2 source, reaction temperature, reaction time, and glycerol/carbonate ratio resulted in Ru/NCTs with significantly higher turnover number (TON) and space-time yield (STY) of the desired products (LA and FA). Moreover, these Ru/NCTs were stable even after three consecutive recycle tests without leaching of active metal or notable structural change. The correlation of reaction performance and detailed characterization revealed that large Ru NPs with high crystallinity exhibit superior catalytic activity for the combined dehydrogenation–hydrogenation reactions that yield the desired products.
•FAPO4-5 adsorbents synthesized and characterized.•Adsorption properties of adsorbents examined by binder type.•Adhesion strength determined by cross-cut tests.•Addition of 5.0 wt% epoxy binder found ...to be optimum.
To overcome the problem of peak electricity demand caused by the use of air-conditioning in the summer, researchers have been focusing their interest on adsorption chillers, which are an environmentally friendly technology in that they use waste heat as their power source and water as a refrigerant. In the present study, to improve the performance of an adsorption chiller, FAPO4-5 adsorbents were synthesized using two hydrothermal synthetic methods, and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption/desorption isotherms and water adsorption isotherms.
Coatings of the adsorbent were applied to an aluminum substrate. Six different coating solutions were used, with a 5.0 wt%, 10.0 wt%, and 15.0 wt% content of epoxy-based and silicone-based binders, respectively. The surface features of adsorbent coating were observed with scanning electron microscopy (SEM). To determine the variation in the water adsorption properties of the adsorbents according to the binder type, each adsorbent was subjected to water adsorption isotherm analysis at 25 °C. The coating thickness was calculated by three dimension coordinate measuring machine. Cross-cut tests (performed according to ISO 2409:2013) were carried out to assess the strength of the adhesion of the coating to the aluminum substrate.
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