Interfacial solvation-structure regulation for stable Li metal anode by a desolvation coating technique.

Rechargeable lithium (Li) metal batteries face challenges in achieving stable cycling due to the instability of the solid electrolyte interphase (SEI). The Li-ion solvation structure and its desolvation process are crucial for the formation of a stable SEI on Li metal anodes and improving Li plating/stripping kinetics. This research introduces an interfacial desolvation coating technique to actively modulate the Li-ion solvation structure at the Li metal interface and regulate the participation of the electrolyte solvent in SEI formation. Through experimental investigations conducted using a carbonate electrolyte with limited compatibility to Li metal, the optimized desolvation coating layer, composed of 12-crown-4 ether-modified silica materials, selectively displaces strongly coordinating solvents while simultaneously enriching weakly coordinating fluorinated solvents at the Li metal/electrolyte interface. This selective desolvation and enrichment effect reduce solvent participation to SEI and thus facilitate the formation of a LiF-dominant SEI with greatly reduced organic species on the Li metal surface, as conclusively verified through various characterization techniques including XPS, quantitative NMR, operando NMR, cryo-TEM, EELS, and EDS. The interfacial desolvation coating technique enables excellent rate cycling stability (i.e., 1C) of the Li metal anode and prolonged cycling life of the Li||LiCoO2 pouch cell in the conventional carbonate electrolyte (E/C 2.6 g/Ah), with 80% capacity retention after 333 cycles.

Parents' willingness to vaccinate themselves and their children with the booster vaccine against SARS-CoV-2: A cross-sectional study in Puyang city, China.

We aimed to investigate the hesitancy and willingness of parents to vaccinate themselves and their children with a booster dose against severe acute respiratory syndrome coronavirus 2 and related factors. We conducted a cross-sectional study in Puyang city, China. The information was collected, including demographic characteristics, willingness to receive a booster dose of coronavirus disease 2019 (COVID-19) vaccine, and attitudes and concerns toward COVID-19 and vaccines. Vaccine hesitancy was assessed in individuals completing the first two doses and booster eligible, while vaccine willingness was assessed in those completing the first two doses and not yet booster eligible. Among the participants completing two primary doses while not meeting the booster criteria, 95.4% (1465/1536) and 95.0% (1385/1458) had a willingness to a booster dose of COVID-19 vaccine for themselves and their children, respectively. Among the participants who met the booster criteria, 40.3% had vaccine hesitancy. Vaccine hesitancy and unwillingness tended to occur in people who were younger, less educated, less healthy, and with unsureness of vaccines' efficacy and adverse events (AE). The younger age of children, children in poorer health, and concern about the efficacy and AE of vaccines contributed to the participants' unwillingness to vaccinate their children. We observed a high willingness to the booster dose of COVID-19 vaccine both for the parents and their children, regardless of the eligibility to a booster dose. However, 40% of people had delayed vaccination behaviors. The promotion of scientific knowledge of vaccines' effectiveness and safety is needed, especially for people in poor health and parents with young children. Timely disclosure of AE caused by COVID-19 vaccines and proper aiding offered to people encountering AE are suggested.

Photoredox-Mediated Remote C(sp3)-H Heteroarylation of N-Alkyl Sulfonamides.

A Minisci-type δ-selective C(sp3)-H heteroarylation of sulfonyl-protected primary aliphatic amines with N-heteroarenes under photoredox-catalyzed conditions was developed. The reaction typically uses a slight excess of amine reactant. The use of benziodoxole acetate (BI-OAc) oxidant and hexafluoroisopropanol solvent is critical to achieve high yield. Besides methylene C-H bonds, heteroarylation reactions of δ methyl C-H bonds also worked under more forced conditions. The reactions show a broad scope for both amine and N-heteroarene substrates, offering a straightforward method for synthesis of complex δ-heteroarylalkylmines from simple precursors.

Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp3)-H Bonds.

Reversible cleavage of C(sp3)-H bonds can enable racemization or epimerization, offering a valuable tool to edit the stereochemistry of organic compounds. While epimerization reactions operating via cleavage of acidic C(sp3)-H bonds, such as the Cα-H of carbonyl compounds, have been widely used in organic synthesis and enzyme-catalyzed biosynthesis, epimerization of tertiary carbons bearing a nonacidic C(sp3)-H bond is much more challenging with few practical methods available. Herein, we report the first synthetically useful protocol for the epimerization of tertiary carbons via reversible radical cleavage of unactivated C(sp3)-H bonds with hypervalent iodine reagent benziodoxole azide and H2O under mild conditions. These reactions exhibit excellent reactivity and selectivity for unactivated 3° C-H bonds of various cycloalkanes and offer a powerful strategy for editing the stereochemical configurations of carbon scaffolds intractable to conventional methods. Mechanistic study suggests that the unique ability of N3• to serve as a catalytic H atom shuttle is critical to reversibly break and reform 3° C-H bonds with high efficiency and selectivity.

Intramolecular etherification and polyene cyclization of π-activated alcohols promoted by hot water.

Hot water, acting as a mildly acidic catalyst, efficiently promoted intramolecular direct nucleophilic substitution reactions of unsaturated alcohols with heteroatom or carbon nucleophiles. In a mixed solvent of water and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), polyene cyclizations using allylic alcohols as initiators gave the desired cyclized products, and in neat HFIP, a tricyclization reaction gave a tetracyclic product in 51% chemical yield.

Facile Access to High Solid Content Monodispersed Microspheres via Dual-Component Surfactants Regulation toward High-Performance Colloidal Photonic Crystals.

Monodispersed microspheres play a major role in optical science and engineering, providing ideal building blocks for structural color materials. However, the method toward high solid content (HSC) monodispersed microspheres has remained a key hurdle. Herein, a facile access to harvest monodispersed microspheres based on the emulsion polymerization mechanism is demonstrated, where anionic and nonionic surfactants are employed to achieve the electrostatic and steric dual-stabilization balance in a synergistic manner. Monodispersed poly(styrene-butyl acrylate-methacrylic acid) colloidal latex with 55 wt% HSC is achieved, which shows an enhanced self-assembly efficiency of 280% compared with the low solid content (10 wt%) latex. In addition, Ag-coated colloidal photonic crystal (Ag@CPC) coating with near-zero refractive index is achieved, presenting the characteristics of metamaterials. And an 11-fold photoluminescence emission enhancement of CdSe@ZnS quantum dots is realized by the Ag@CPC metamaterial coating. Taking advantage of high assembly efficiency, easily large-scale film-forming of the 55 wt% HSC microspheres latex, robust Ag@CPC metamaterial coatings could be easily produced for passive cooling. The coating demonstrates excellent thermal insulation performance with theoretical cooling power of 30.4 W m-2, providing practical significance for scalable CPC architecture coatings in passive cooling.

Machine learning for identifying tumor stemness genes and developing prognostic model in gastric cancer.

Gastric cancer presents a formidable challenge, marked by its debilitating nature and often dire prognosis. Emerging evidence underscores the pivotal role of tumor stem cells in exacerbating treatment resistance and fueling disease recurrence in gastric cancer. Thus, the identification of genes contributing to tumor stemness assumes paramount importance. Employing a comprehensive approach encompassing ssGSEA, WGCNA, and various machine learning algorithms, this study endeavors to delineate tumor stemness key genes (TSKGs). Subsequently, these genes were harnessed to construct a prognostic model, termed the Tumor Stemness Risk Genes Prognostic Model (TSRGPM). Through PCA, Cox regression analysis and ROC curve analysis, the efficacy of Tumor Stemness Risk Scores (TSRS) in stratifying patient risk profiles was underscored, affirming its ability as an independent prognostic indicator. Notably, the TSRS exhibited a significant correlation with lymph node metastasis in gastric cancer. Furthermore, leveraging algorithms such as CIBERSORT to dissect immune infiltration patterns revealed a notable association between TSRS and monocytes and other cell. Subsequent scrutiny of tumor stemness risk genes (TSRGs) culminated in the identification of CDC25A for detailed investigation. Bioinformatics analyses unveil CDC25A's implication in driving the malignant phenotype of tumors, with a discernible impact on cell proliferation and DNA replication in gastric cancer. Noteworthy validation through in vitro experiments corroborated the bioinformatics findings, elucidating the pivotal role of CDC25A expression in modulating tumor stemness in gastric cancer. In summation, the established and validated TSRGPM holds promise in prognostication and delineation of potential therapeutic targets, thus heralding a pivotal stride towards personalized management of this malignancy.

Relationship between ambient fine particles and ventricular repolarization changes and heart rate variability of elderly people with heart disease in Beijing, China.

OBJECTIVE: To explore the effects of particulate matters less than 2.5 µm in aerodynamic diameter (PM2.5) on heart repolarization/depolarization and heart rate variability (HRV). METHODS: We conducted a panel study for elderly subjects with heart disease in Beijing from 2007 to 2008. PM2.5 was measured at a fixed station for 20 h continuously each day while electrocardiogram (ECG) indexes of 42 subjects were also recorded repeatedly. Meteorological data was obtained from the China Meteorological Data Sharing Service System. A mixed linear regression model was used to estimate the associations between PM2.5 and the ECG indexes. The model was adjusted for age, body mass index, sex, day of the week and meteorology. RESULTS: Significant adverse effects of PM2.5 on ECG indexes reflecting HRV were observed statistically and the strongest effect of PM2.5 on HRV was on lag 1 day in our study. However, there were no associations between PM2.5 and ECG indexes reflecting heart repolarization/depolarization. Additionally, the effects of PM2.5 on subjects with hypertension were larger than on the subjects without hypertension. CONCLUSION: This study showed ambient PM2.5 could affect cardiac autonomic function of the elderly people with heart disease, and subjects with hypertension appeared to be more susceptive to the autonomic dysfunction induced by PM2.5.

Association between ambient particulate matter and daily cause-specific mortality in Tanggu, Tianjin Binhai New Area, China.

The aim of the study was to determine whether the area of Tanggu, Tianjin Binhai New Economic Developing Area, China, is subject to similar effects of ambient particulate matter less than 10 micrometres in aerodynamic diameter (PM10) similar to other areas of China. This study was designed to investigate cause-specific mortality risks associated with air pollution in this geographical region. The present study used a time-series analysis to explore the relationship between PM10 and the cause-specific mortalities for non-accidental, cardiovascular, and cardiopulmonary mortality from 1 January 2006 to 31 December 2010. A 10 µg/m(3) increment of PM10 was associated with a 1.02% (95% confidence interval (CI): 0.48, 1.56) increase in cardiovascular mortality, and a 0.88% (95% CI: 0.36, 1.39) increase in cardiopulmonary mortality. In addition, the effects from PM10 appear to be consistent with multi-pollutant models. The results show that there are strong associations between daily cardiovascular and cardiopulmonary mortality and ambient PM10 exposure.

[Association between ambient PM10/PM2.5 levels and population mortality of circulatory diseases: a case-crossover study in Beijing].

OBJECTIVE: To explore the association between levels of ambient particulate matters (PM10 and PM2.5) and population mortality of circulatory diseases (ICD10: I00~I99) in Beijing. METHODS: The daily data of ambient PM2.5 levels were monitored by the research team in Peking University from Jan. 1, 2007 to Dec. 31, 2008, and the corresponding meteorological and other air quality data (PM10, SO2 and NO2) were collected from National Meteorological Information Center (NMIC) of China and Beijing Environmental Monitoring Center. The data of daily death for the circulatory diseases were collected from the local center for Disease Control and Prevention of Haidian District in Beijing. The symmetric bidirectional case-crossover design and conditional logistic regression model were used for the data analysis. The cases were stratified by gender, age and seasons. The lagged effect was analyzed and the related confounders from meteorological factors and other air pollutants were adjusted. RESULTS: For a 10 µg/m(3) increase of the ambient concentration of PM2.5, the corresponding increase of daily mortality of the circulatory diseases, cardiovascular diseases and cerebrovascular diseases was 0.78% (95% CI: 0.07% to 1.49%), 0.85% (95% CI: -0.28% to 1.99%), and 0.75% (95% CI: -0.17% to 1.68%), respectively, for a 10 µg/m(3) increase of the ambient concentration of PM10, the corresponding increase of daily mortality of the circulatory diseases, cardiovascular diseases and cerebrovascular diseases was 0.36% (95% CI: -0.07% to 0.78%), 0.63% (95% CI: -0.02% to 1.28%), and 0.33% (95% CI: -0.26% to 0.92%),respectively. The significant positive associations were observed statistically between PM2.5 and the circulatory diseases (P<0.05). The association between ambient PMs and the population mortality was stronger in "warm season (April to September)" than in "cool season (October to the next March)" in Beijing (P<0.05). CONCLUSION: The elevated levels of ambient PM2.5 and PM10 were positively associated with the increase of the population mortality of the circulatory diseases, and the association is stronger in warm season, and the adverse effect of PM2.5 is greater than that of PM10.

[Evaluation of excess mortality caused by PM2.5 in four typical Chinese big cities].

OBJECTIVE: To evaluate the adverse effects of particulate matter ≤ 2.5 µm in aerodynamic diameter (PM2.5) on public health in four typical cities: Beijing, Shanghai, Guangzhou and Xi'an. METHODS: Daily health and meteorological data (including ambient temperature and relative humidity) were collected in the past several years. For the relative risk of PM2.5 effects on mortalities, generalized additive model (GAM) was used to obtain the exposure-response coefficients between PM2.5 and non-accidental mortalities after controlling time trend, week effects and meteorological factors. Then excess mortalities were calculated according to coefficients, health data and air pollution level. RESULTS: The relative risks of PM2.5 effects on mortalities were 1.0027(1.0010-1.0044), 1.0020 (1.0007-1.0033) , 1.0056 (1.0022-1.0091), 1.0036 (1.0011-1.0061) for Beijing, Xi'an, Shanghai, Guangzhou respectively. Compared with relative risks in northern cities (Beijing and Xi'an), relative risks in southern cities (Shanghai and Guangzhou) were higher. The numbers of excess mortalities caused by PM2.5 in Beijing, Shanghai, Guangzhou, Xi'an were 2349, 2980, 1715, 726 and accounted for 1.9%, 1.6%, 2.2% and 1.6% of the total death number in 2010 respectively. CONCLUSIONS: Although relative health risks caused by PM2.5 vary geographically for urban residents, public health is endangered. More efforts should be devoted to reducing PM2.5 pollution.

Realizing high-capacity all-solid-state lithium-sulfur batteries using a low-density inorganic solid-state electrolyte.

Lithium-sulfur all-solid-state batteries using inorganic solid-state electrolytes are considered promising electrochemical energy storage technologies. However, developing positive electrodes with high sulfur content, adequate sulfur utilization, and high mass loading is challenging. Here, to address these concerns, we propose using a liquid-phase-synthesized Li3PS4-2LiBH4 glass-ceramic solid electrolyte with a low density (1.491 g cm-3), small primary particle size (~500 nm) and bulk ionic conductivity of 6.0 mS cm-1 at 25 °C for fabricating lithium-sulfur all-solid-state batteries. When tested in a Swagelok cell configuration with a Li-In negative electrode and a 60 wt% S positive electrode applying an average stack pressure of ~55 MPa, the all-solid-state battery delivered a high discharge capacity of about 1144.6 mAh g-1 at 167.5 mA g-1 and 60 °C. We further demonstrate that the use of the low-density solid electrolyte increases the electrolyte volume ratio in the cathode, reduces inactive bulky sulfur, and improves the content uniformity of the sulfur-based positive electrode, thus providing sufficient ion conduction pathways for battery performance improvement.

HE@PCL/PCE Gel-Nanofiber Dressing with Robust Self-Adhesion toward High Wound-Healing Rate via Microfluidic Electrospinning Technology.

Hydrogels have attracted increasing attention in the biomedical field due to their similarity in structure and composition to natural extracellular matrices. However, they have been greatly limited by their low mechanical strength and self-adhesion for further application. Here, a gel-nanofiber material is designed for wound healing, which synergistically combines the benefits of hydrogels and nanofibers and can overcome the bottleneck of poor mechanical strength and self-adhesion in hydrogels and inadequate healing environment created by nanofibers. First, a nanofiber scaffold composed of polycaprolactone/poly(citric acid)-ε-lysine (PCL/PCE) nanofibers is fabricated via a new strategy of microfluidic electrospinning, which could provide a base for hyaluronic acid-polylysine (HE) gel growth on nanofibers. The prepared HE@PCL/PCE gel-nanofiber possesses high tensile strength (24.15 ± 1.67 MPa), excellent air permeability (656 m3/m2 h kPa), outstanding self-adhesion property, and positive hydrophilicity. More importantly, the prepared gel-nanofiber dressing shows good cytocompatibility and antibacterial properties, achieving a high wound-healing rate (92.48%) and 4.685 mm granulation growth thickness within 12 days. This material may open a promising avenue for accelerating wound healing and tissue regeneration, providing potential applications in clinical medicine.

Trend of glaucoma internal filtration surgeries in a tertiary hospital in China.

AIM: To evaluate the trend of glaucoma internal filtration surgeries for inpatients between 2015 and 2021 at the Eye Hospital of Wenzhou Medical University. METHODS: A review of the medical records of inpatients who had been diagnosed with glaucoma and received anti-glaucoma surgery between January 1, 2015 and December 31, 2021 was conducted. The glaucoma diagnosis in this study included primary open angle glaucoma, primary angle-closure glaucoma, secondary glaucoma, and paediatric glaucoma. The types of surgeries were categorised as internal filtration, external filtration, and cyclodestruction surgery based on the pathway of aqueous humor outflow. The trend of these glaucoma surgeries in the sample of patients with different types of glaucoma was then analysed. RESULTS: The number of patients hospitalised for glaucoma surgery increased yearly, from 752 in 2015 to 1373 in 2021, at the Eye Hospital of Wenzhou Medical University. Regarding the patients diagnosed with primary open angle glaucoma, internal filtration surgery increased from 27.40% of the sample to 54.40% of the sample, while external filtration surgery decreased from 71.50% to 44.20% between 2015 and 2021. For paediatric glaucoma, internal filtration surgery increased from 37.50% in 2015 to 88.20% in 2021. Whilst different types of surgeries were performed on the sample of patients with secondary glaucoma, the proportion of internal filtration surgery also showed an increase from 18.20% in 2015 to 40.90% in 2021. Meanwhile, internal filtration surgery in the patient sample with primary angle-closure glaucoma already accounted for over 70.00% in 2015, and showed a small increase by 2021. CONCLUSION: As surgical technology and surgical experience continue to elevate and improve, the range of glaucoma surgeries are correspondingly evolving. This study find that internal filtration surgeries accounted for an increasing proportion of treatments in the surgical management of glaucoma between 2015 and 2021.

[Relationship between daily mean temperature and emergency department visits for respiratory diseases: a time-series analysis].

OBJECTIVE: To quantitatively evaluate the influences of daily mean air temperature (DMT) on Emergency Department Visits (EDVs) for the respiratory diseases. METHODS: The EDV data from medical records for respiratory diseases in Peking University Third Hospital between January 2004 and June 2009 were collected. The data of the air pollutants (SO(2), NO(2) and PM(10)) and meteorological factors at the same time periods were also collected from the local authorities of Beijing. Time-series analysis and generalized additive models (GAM) were used to explore the exposurrre-response relationship between DMT and EDVs for respiratory diseases. RESULTS: A total of 35 073 patients [males 14 707(41.93%,14 707/35 073), females 19 122(54.52%,19 122/35 073) and gender missing 1 244(3.55%, 1 244/35 073)] EDVs for respiratory diseases were included. The relationship between DMT and EDVs for the respiratory diseases was mainly of "V" shape, the optimum temperature(OT) was about 4 °C and the effect of DMT was significant with a 0-3 day lag structure for most of the models. When DMT≤OT, each 1°C decrease in DMT corresponded to 3.75% (95% CI of RR: 0.938 3-0.965 3), 3.10% (95% CI of RR:0.949 2-0.989 1), 4.09% (95% CI of RR:0.940 7-0.977 8) increase of EDVs for the overall, male, and female, respectively. When DMT>OT, the value caused by each increase in 1°C in DMT was 1.54% (95% CI of RR:1.006 6-1.024 3), 1.80% (95% CI of RR:1.005 3-1.030 9), and 1.51 (95% CI of RR:1.003 2- 1.027 2), respectively. The effect was statistically significant within the 0-3 day lag. When DMT≤OT, the effect was stronger for the older people, while the effect was strongest for the 45-59 years old people. CONCLUSION: The relationship between DMT and EDVs for respiratory diseases is mainly of "V" type, with an optimum temperature of 4 °C.Both DMT decrease when DMT≤OT and increase when DMT>OT correspond to different increase of EDVs for respiratory diseases. Low DMT has stronger effect than high DMT. Different age group and gender have different effects.

Modeling and Predicting Pulmonary Tuberculosis Incidence and Its Association with Air Pollution and Meteorological Factors Using an ARIMAX Model: An Ecological Study in Ningbo of China.

The autoregressive integrated moving average with exogenous regressors (ARIMAX) modeling studies of pulmonary tuberculosis (PTB) are still rare. This study aims to explore whether incorporating air pollution and meteorological factors can improve the performance of a time series model in predicting PTB. We collected the monthly incidence of PTB, records of six air pollutants and six meteorological factors in Ningbo of China from January 2015 to December 2019. Then, we constructed the ARIMA, univariate ARIMAX, and multivariate ARIMAX models. The ARIMAX model incorporated ambient factors, while the ARIMA model did not. After prewhitening, the cross-correlation analysis showed that PTB incidence was related to air pollution and meteorological factors with a lag effect. Air pollution and meteorological factors also had a correlation. We found that the multivariate ARIMAX model incorporating both the ozone with 0-month lag and the atmospheric pressure with 11-month lag had the best performance for predicting the incidence of PTB in 2019, with the lowest fitted mean absolute percentage error (MAPE) of 2.9097% and test MAPE of 9.2643%. However, ARIMAX has limited improvement in prediction accuracy compared with the ARIMA model. Our study also suggests the role of protecting the environment and reducing pollutants in controlling PTB and other infectious diseases.

Dose-response relationship of blood flow restriction training on isometric muscle strength, maximum strength and lower limb extensor strength: A meta-analysis.

Objective: To perform a meta-analysis on the efficacy and dose-response relationship of blood flow restriction training on muscle strength reported worldwide. Methods: Thirty-four eligible articles with a total sample size of 549 participants were included in the meta-analysis. This study was performed using the method recommended by the Cochrane Handbook (https://training.cochrane.org/handbook), and the effect size was estimated using the standardized mean difference (SMD) and using RevMan 5.3 software (The Nordic Cochrane Centre, The Cochrane Collaboration, Copenhagen, 2014). Results: The meta-analysis showed that blood flow restriction training increased the lower limb extensor muscle strength [SMD = 0.72, 95%; confidence interval (CI): 0.43 to 1.00, p < 0.01], knee extensor isokinetic torque SMD = 0.48 [95% CI: 0.24 to 0.73, p < 0.01], knee flexor isokinetic torque SMD = 0.39 [95% CI: 0.11 to 0.67, p < 0.01], and squat one-repetition maximum [SMD = 0.28, 95% CI: 0.01 to 0.55, p < 0.01]. There was no publication bias. Evaluation of dose-response relationship showed that the training load, mode, frequency, duration, and maximum cuff pressure affected the muscle function. Conclusion: blood flow restriction training. 16 significantly improved lower limb muscle strength, and the optimal training conditions consisted of a weight load smaller or equal to 30% of one-repetition maximum, training duration longer than 4 weeks, frequency of more than 3 times/week, and maximum cuff pressure lower than 200 mmHg. Systematic Review Registration: website, identifier registration number.

Clovamide, a Hydroxycinnamic Acid Amide, Is a Resistance Factor Against Phytophthora spp. in Theobroma cacao.

The hydroxycinnamic acid amides (HCAAs) are a diverse group of plant-specialized phenylpropanoid metabolites distributed widely in the plant kingdom and are known to be involved in tolerance to abiotic and biotic stress. The HCAA clovamide is reported in a small number of distantly related species. To explore the contribution of specialized metabolites to disease resistance in cacao (Theobroma cacao L., chocolate tree), we performed untargeted metabolomics using liquid chromatography - tandem mass spectrometry (LC-MS/MS) and compared the basal metabolite profiles in leaves of two cacao genotypes with contrasting levels of susceptibility to Phytophthora spp. Leaves of the tolerant genotype 'Scavina 6' ('Sca6') were found to accumulate dramatically higher levels of clovamide and several other HCAAs compared to the susceptible 'Imperial College Selection 1' ('ICS1'). Clovamide was the most abundant metabolite in 'Sca6' leaf extracts based on MS signal, and was up to 58-fold higher in 'Sca6' than in 'ICS1'. In vitro assays demonstrated that clovamide inhibits growth of three pathogens of cacao in the genus Phytophthora, is a substrate for cacao polyphenol oxidase, and is a contributor to enzymatic browning. Furthermore, clovamide inhibited proteinase and pectinase in vitro, activities associated with defense in plant-pathogen interactions. Fruit epidermal peels from both genotypes contained substantial amounts of clovamide, but two sulfated HCAAs were present at high abundance exclusively in 'Sca6' suggesting a potential functional role of these compounds. The potential to breed cacao with increased HCAAs for improved agricultural performance is discussed.

Photoredox-mediated remote C(sp3)-H heteroarylation of free alcohols.

We report an efficient and economical method for remote δ C(sp3)-H heteroarylation of free aliphatic alcohols using a hypervalent iodine PFBI-OH oxidant under photoredox catalysis. The reaction sequence involves in situ alcoholysis of PFBI-OH with alcohol, generation of an alkoxy radical intermediate by SET reduction, 1,5-HAT, and Minisci-type C-C bond formation. This method uses a slight excess of alcohols, can facilitate reaction at δ methyl and methylene positions, and has been successfully applied to modification of complex drug molecules.

Kinetic resolution of racemic alcohols using thioamide modified 1-methyl-histidine methyl ester.

The low-molecular-weight and easily prepared N-thiobenzoyl 1-methyl-histidine methyl ester 3k was utilized to efficiently catalyze the kinetic resolution of racemic secondary alcohols. Comparison of the conformations of amide catalyst 3c and thioamide catalyst 3k was made to understand the origin of the improvement of the enantioselectivity by thioamide modification.