A Mechanistic Spectrum of O-H Bond Cleavage Observed for Reactions of Phenols with a Manganese Superoxo Complex.

Reaction of a rare and well-characterized MnIII-superoxo species, Mn(BDPBrP)(O2•) (1, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine), with 4-dimethylaminophenol at -80 °C proceeds via concerted proton electron transfer (CPET) to produce a MnIII-hydroperoxo complex, Mn(BDPBrP)(OOH) (2), alongside 4-dimethylaminophenoxy radical; whereas, upon treatment with 4-nitrophenol, complex 1 undergoes a proton transfer process to afford a MnIV-hydroperoxo complex, [Mn(BDPBrP)(OOH)]+ (3). Intriguingly, the reactions of 1 with 4-chlorophenol and 4-methoxyphenol follow two routes of CPET and sequential proton and electron transfer to furnish complex 2 in the end. UV-vis and EPR spectroscopic studies coupled with DFT calculations provided support for this wide mechanistic spectrum of activating various phenol O-H bonds by a single MnIII-superoxo complex, 1.

Precise Regulation on the Bond Dissociation Energy of Exocyclic C-N Bonds in Various N-Heterocycle Electron Donors via Machine Learning.

Heterocycles with saturated N atoms (HetSNs) are widely used electron donors in organic light-emitting diode (OLED) materials. Their relatively low bond dissociation energy (BDE) of exocyclic C-N bonds has been closely related to material intrinsic stability and even device lifetime. Thus, it is imperative to realize fast prediction and precise regulation of those C-N BDEs, which demands a deep understanding of the relationship between the molecular structure and BDE. Herein, via machine learning (ML), we rapidly and accurately predicted C-N BDEs in various HetSNs and found that five-membered HetSNs (5-HetSNs) have much higher BDEs than almost all 6-HetSNs, except emerging boron-N blocks. Thorough analysis disclosed that high aromaticity is the foremost factor accounting for the high BDE of 5-HetSNs, and introducing intramolecular hydrogen-bond or electron-withdrawing moieties could also increase BDE. Importantly, the ML models performed well in various realistic OLED materials, showing great potential in characterizing material intrinsic stability for high-throughput virtual-screening and material design efforts.

Eu3+-based InP/ZnS quantum dot fluorescence platform for multi-color and sensitive visualization of tetracycline.

A turn-on type ratiometric fluorescence sensing system of blue quantum dot Eu-MPA-InP/ZnS was established for multi-color visualization determination of tetracycline (TC). Mercaptopropionic acid (MPA)-capped InP/ZnS quantum dots (MPA-InP/ZnS QDs) both modify the hydrophilicity of InP/ZnS QDs and serve as a scaffold for coordinating of Eu3+ ions. The blue fluorescence of Eu-MPA-InP/ZnS at 478 nm is reduced by the TC through the inner filter effect (IFE) under a single excitation wavelength of 365 nm. Rich colour gradients and a highly discriminative colour change were features of this multicolour response to TC, which allowed visual quantification of TC in a dose-dependent manner. Furthermore, by cross-linking Eu-MPA-InP/ZnS with agarose (Aga.), a mouldable Eu-MPA-InP/ZnS@Aga 96-well gel sensing device was designed to serve as a handheld sensor for on-site detection of TC. This probe expands the use of InP QDs in analytical sensing and has been effectively applied to the visual detection of tetracycline in milk and the environment.

Convergent evolution of kidney sizes and supraorbital salt glands for birds living in saline habitats.

Only a small number of avian species inhabit salty environments. To understand how they adapted, we examined the evolution of kidney sizes, supraorbital salt glands (SSGs), and the utilization of salty habitats across 230 species spanning 25 avian orders. Phylogenetic analysis indicates that SSGs, large kidneys, and thriving in salty habitats emerged convergently in birds. Transition rate analysis reveals that species possessing SSGs and large kidneys tended to move from low-to high-salinity environments, while others moved in the opposite direction. However, habitat salinity also influenced kidney evolution; lineages residing in high-salinity environments tended to develop larger kidneys than those in low-salinity environments. Our findings suggest that SSGs and large kidneys may have evolved through adaptation to high salinity. Overall, habitat conditions and physiological traits influenced avian adaptation to salty environments in a reciprocal manner. These results shed the new light on the evolutionary mechanisms underlying functional diversity in birds.

Object-centered family interactions for young autistic children: a diary study.

Autistic Children often struggle with social interaction and communication, studies have found that many of them prefer to interact with objects than people. However, there is a lack of research exploring the specific characteristics and factors involved in interactions within families with autistic children where objects are the center of the interaction. This paper describes the process and findings of a diary study exploring how young autistic children interact with their families through objects in natural scenarios. A one-week diary study was conducted with six families with young autistic children. Diary videos were recorded onsite and coded later according to a social interaction behavior scheme with corresponding diary entries. Qualitative data analysis was conducted to reveal possible patterns. Results revealed ongoing difficulties in establishing and maintaining family interaction and identified influential factors of object-centered family interaction. The most prevalent pattern observed was parents taking the lead in interactions, followed by the child's confirmation response. Remarkably, daily necessities emerged as potential physical mediums for enhancing family interactions, opening avenues for exploring tangible designs in human-computer interaction. These findings offer valuable implications for future research and the development of innovative designs that promote enriching interactions for autistic children and their families.

Magneto-Structural Correlation of Five-Coordinate Trigonal Bipyramidal High Spin Cobalt(II) Complexes.

Here, we combined magnetometry, multi-frequency electronic paramagnetic resonance, and wave function based ab initio calculations to investigate magnetic properties of two high spin Co(II) complexes Co(BDPRP) (BDPRP=2,6-bis((2-(S)-di(4-R)phenylhydroxylmethyl-1-pyrrolidi-nyl)methyl)pyridine, R=H for 8; R=tBu for 9). Complexes 8 and 9 featuring effective D3h symmetry were found to possess D=24.0 and 32.0 cm-1, respectively, in their S=3/2 ground states of 1 e ' ' d x z / y z 4 1 e ' d x y / x 2 - y 2 2 1 a 1 ' d z 2 1 ${{\left(1{{\rm e}}^{{\rm { {^\prime}}}{\rm { {^\prime}}}}\right({d}_{xz/yz}\left)\right)}^{4}{\left(1{{\rm e}}^{{\rm { {^\prime}}}}\right({d}_{{xy/{x}^{2}-y}^{2}}\left)\right)}^{2}{\left(1{{\rm a}}_{1}^{{\rm { {^\prime}}}}\right({d}_{{z}^{2}}\left)\right)}^{1}}$ . Ligand field analyses revealed that the low-lying d-d excited states make either positive or vanishing contributions to D. Hence, total positive D values were measured for 8 and 9, as well as related D3h high spin Co(II) complexes. In contrast, negative D values are usually observed for C3v congeners. In-depth analyses suggested that lowering symmetry from D3h to C3v induces orbital mixing between 1 e d x z / y z ${1{\rm e}\left({d}_{xz/yz}\right)}$ and 2 e d x y / x 2 - y 2 ${2{\rm e}\left({d}_{{xy/{x}^{2}-y}^{2}}\right)}$ and admixes excited state 4 A 2 1 e → 2 e ${{}^{4}{{\rm A}}_{2}\left(1e\to 2e\right)}$ into the ground state. Both factors turn the total D value progressively negative with the increasing distance (δ) of the Co(II) center out of the equatorial plane. Therefore, δ determines the sign and magnitude of final D values of five-coordinate trigonal bipyramidal S=3/2 Co(II) complexes as measured for a series of such species with varying δ.

An efficient CRISPR/Cas9 genome editing system based on a multiple sgRNA processing platform in Trichoderma reesei for strain improvement and enzyme production.

BACKGROUND: The CRISPR/Cas9 technology is being employed as a convenient tool for genetic engineering of the industrially important filamentous fungus Trichoderma reesei. However, multiplex gene editing is still constrained by the sgRNA processing capability, hindering strain improvement of T. reesei for the production of lignocellulose-degrading enzymes and recombinant proteins. RESULTS: Here, a CRISPR/Cas9 system based on a multiple sgRNA processing platform was established for genome editing in T. reesei. The platform contains the arrayed tRNA-sgRNA architecture directed by a 5S rRNA promoter to generate multiple sgRNAs from a single transcript by the endogenous tRNA processing system. With this system, two sgRNAs targeting cre1 (encoding the carbon catabolite repressor 1) were designed and the precise deletion of cre1 was obtained, demonstrating the efficiency of sgRNAs processing in the tRNA-sgRNA architecture. Moreover, overexpression of xyr1-A824V (encoding a key activator for cellulase/xylanase expression) at the ace1 (encoding a repressor for cellulase/xylanase expression) locus was achieved by designing two sgRNAs targeting ace1 in the system, resulting in the significantly enhanced production of cellulase (up to 1- and 18-fold on the Avicel and glucose, respectively) and xylanase (up to 11- and 41-fold on the Avicel and glucose, respectively). Furthermore, heterologous expression of the glucose oxidase gene from Aspergillus niger ATCC 9029 at the cbh1 locus with the simultaneous deletion of cbh1 and cbh2 (two cellobiohydrolase coding genes) by designing four sgRNAs targeting cbh1 and cbh2 in the system was acquired, and the glucose oxidase produced by T. reesei reached 43.77 U/mL. Besides, it was found the ER-associated protein degradation (ERAD) level was decreased in the glucose oxidase-producing strain, which was likely due to the reduction of secretion pressure by deletion of the major endogenous cellulase-encoding genes. CONCLUSIONS: The tRNA-gRNA array-based CRISPR-Cas9 editing system was successfully developed in T. reesei. This system would accelerate engineering of T. reesei for high-level production of enzymes including lignocellulose-degrading enzymes and other recombinant enzymes. Furthermore, it would expand the CRISPR toolbox for fungal genome editing and synthetic biology.

DNA-induced assembly of biocatalytic nanocompartments for sensitive and selective aptasensing of aflatoxin B1.

Enzyme cascade with high specificity and catalytic efficiency has significant applications for developing efficient bioanalysis methods. In this work, a sensitive and selective aptasensor was constructed based on the DNA-induced assembly of biocatalytic nanocompartments. Different from the conventional co-immobilization in one pot, the cascade enzymes of glucose oxidase (GOX) and horseradish peroxidase (HRP) were separately encapsulated in ZIF-90 nanoparticles. After conjugating complementary DNA or aptermer on enzyme@ZIF-90, DNA hybridization drove enzyme@ZIF-90 connected into clusters or linked on other DNA modified biocatalytic nanocompartment (such as invertase loaded Fe3O4@SiO2). Owing to the shortened distance between enzymes, the catalytic efficiency of connected clusters was significantly enhanced. However, the specifically interaction between the substrate molecule and aptermer sequence would lead to the disassembly of DNA duplexes, resulting in the gradual "switching-off" of cascade reactions. With aflatoxin B1 (AFB1) as the model substrate, the compartmentalized three-enzyme nanoreactors showed good analytical performance in the linear range from 0.01 ng mL-1 to 50 ng mL-1 with a low detection limit (3.3 pg mL-1). In addition, the proposed aptasensor was applied to detect AFB1 in corn oil and wheat powder samples with total recoveries ranging from 94 % to 109 %. As a result, this DNA-induced strategy for enzyme cascade nanoreactors opens new avenues for stimuli-responsive applications in biosensing.

Role of n-DAMO in Mitigating Methane Emissions from Intertidal Wetlands Is Regulated by Saltmarsh Vegetations.

Coastal wetlands are hotspots for methane (CH4) production, reducing their potential for global warming mitigation. Nitrite/nitrate-dependent anaerobic methane oxidation (n-DAMO) plays a crucial role in bridging carbon and nitrogen cycles, contributing significantly to CH4 consumption. However, the role of n-DAMO in reducing CH4 emissions in coastal wetlands is poorly understood. Here, the ecological functions of the n-DAMO process in different saltmarsh vegetation habitats as well as bare mudflats were quantified, and the underlying microbial mechanisms were explored. Results showed that n-DAMO rates were significantly higher in vegetated habitats (Scirpus mariqueter and Spartina alterniflora) than those in bare mudflats (P < 0.05), leading to an enhanced contribution to CH4 consumption. Compared with other habitats, the contribution of n-DAMO to the total anaerobic CH4 oxidation was significantly lower in the Phragmites australis wetland (15.0%), where the anaerobic CH4 oxidation was primarily driven by ferric iron (Fe3+). Genetic and statistical analyses suggested that the different roles of n-DAMO in various saltmarsh wetlands may be related to divergent n-DAMO microbial communities as well as environmental parameters such as sediment pH and total organic carbon. This study provides an important scientific basis for a more accurate estimation of the role of coastal wetlands in mitigating climate change.

Reduced length of intensive care unit stay and early mechanical ventilator weaning with enhanced recovery after surgery (ERAS) in free fibula flap surgery.

This study aimed to evaluate the effects of the enhanced recovery after surgery (ERAS) program on postoperative recovery of patients who underwent free fibula flap surgery for mandibular reconstruction. This retrospective study included 188 patients who underwent free fibula flap surgery for complex mandibular and soft tissue defects between January 2011 and December 2022. We divided them into two groups: the ERAS group, consisting of 36 patients who were treated according to the ERAS program introduced from 2021 to 2022. Propensity score matching was used for the non-ERAS group, which comprised 36 cases selected from 152 patients between 2011 and 2020, based on age, sex, and smoking history. After propensity score matching, the ERAS and non-ERAS groups included 36 patients each. The primary outcome was the length of intensive care unit (ICU) stay; the secondary outcomes were flap complications, unplanned reoperation, 30-day readmission, postoperative ventilator use length, surgical site infections, incidence of delirium within ICU, lower-limb comorbidities, and morbidity parameters. There were no significant differences in the demographic characteristics of the patients. However, the ERAS group showed the lower length of intensive care unit stay (ERAS vs non-ERAS: 8.66 ± 3.90 days vs. 11.64 ± 5.42 days, P = 0.003) and post-operative ventilator use days (ERAS vs non-ERAS: 1.08 ± 0.28 days vs. 2.03 ± 1.05 days, P < 0.001). Other secondary outcomes were not significantly different between the two groups. Additionally, patients in the ERAS group had lower postoperative morbidity parameters, such as postoperative nausea, vomiting, urinary tract infections, and pulmonary complications (P = 0.042). The ERAS program could be beneficial and safe for patients undergoing free fibula flap surgery for mandibular reconstruction, thereby improving their recovery and not increasing flap complications and 30-day readmission.

Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation.

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp3)-C(sp3) coupling with broad substrate availability and high functional group compatibility. However, auxiliary groups, a conjugated group or a chelation-directing group, are commonly required to attain high regio- and enantioselectivities. Herein, we reported a ligand-controlled cobalt-hydride-catalyzed regio-, enantio-, and diastereoselective oxyheterocyclic alkene hydroalkylation without chelation-directing groups. This reaction enables the hydroalkylation of conjugated and unconjugated oxyheterocyclic alkenes to deliver C2- or C3-alkylated tetrahydrofuran or tetrahydropyran in uniformly good yields and with high regio- and enantioselectivities. In addition, hydroalkylation of C2-substituted 2,5-dihydrofuran resulted in the simultaneous construction of 1,3-distereocenters, providing convenient access to polysubstituted tetrahydrofuran with multiple enantioenriched C(sp3) centers.

Comparison of pharmacokinetics and safety of albuvirtide in healthy subjects after intravenous drip and bolus injection.

Albuvirtide (ABT) is the first long-acting HIV fusion inhibitor developed in China, blocking the invasion of HIV-1 virus into target cells. This study aimed to compare the pharmacokinetics (PK), tolerability, and safety of ABT following a single intravenous (IV) bolus injection or intravenous drip in healthy Chinese subjects. A single-center, randomized, open-label, single-period, parallel phase I clinical trial was conducted. Thirty subjects were randomly divided into three groups in a ratio of 1:1:1. After an overnight fast, all subjects received a single dose of 320 mg ABT either by intravenous drip for 45 min (group A) or bolus injection for 0.5 min (group B), or bolus injection for 3 min (group C). ABT plasma concentrations were analyzed using a validated enzyme-linked immunosorbent assay (ELISA). Non-compartmental analysis was used to evaluate PK parameters. The median time to reach maximum concentration was 0.75 h in group A and 0.16 h in both groups B and C. Elimination half-life, mean residence time, apparent clearance, and apparent volume of distribution were similar among the three groups. The 90% confidence intervals (CI) of geometric mean ratios of PK parameters for groups B and C relative to group C were within 85-120%. All adverse events (AEs) reported in this study were mild, according to the CTCAE guidelines and the study investigator's judgement. ABT bolus injections for 0.5 min and 3 min are expected to be well tolerated and to exhibit similar PK characteristics as IV drip for 45 min, offering potential clinical benefits.

Free Dermal Fat Grafting: A Novel Technique for the Correction of Nasolabial Folds During Facelift Surgery.

BACKGROUND: Traditional facelift surgery does not behave well in the correction of nasolabial folds, which is a common clinical problem and needed to be improved. OBJECTIVES: To investigate the effect of free dermal fat grafting during facelift surgery for the treatment of nasolabial folds. METHODS: This prospective cohort study involved 80 patients with moderate to severe nasolabial folds and facial skin dermatolysis. Fifty of them underwent facelift surgery combined with free dermal fat grafting, and 30 of them underwent traditional facelift surgery. These patients were followed up 2 months, 6 months, and 1 year after the surgery to evaluate the effect. RESULTS: The difference in Wrinkle Severity Rating Scale (WSRS) scores, assessed at each follow-up, between the patients who underwent and did not undergo free dermal fat grafting during facelift surgery, was statistically significant. For patients who underwent free dermal fat grafting during facelift surgery, the WSRS scores assessed at 2 months, 6 months, and 1 year after the surgery were significantly different from those before the surgery. The analytic results of FACE-Q indicated a high level of overall satisfaction rate. No major complications were recorded. CONCLUSIONS: Free dermal fat as a filler for nasolabial folds can achieve excellent therapeutic effect. The combination of facelift surgery with free dermal fat grafting for the treatment of nasolabial folds can provide very good long-term results and a high patient satisfaction rate for patients with symptoms of facial aging such as facial dermatolysis, obvious wrinkles, and deep nasolabial folds.

Correction: Kang et al. Anticolon Cancer Effect of Korean Red Ginseng via Autophagy- and Apoptosis-Mediated Cell Death. Nutrients 2022, 14, 3558.

In the original publication [...].

Involvement of free-space optics in Raman distributed temperature sensing.

This Letter demonstrates the successful use of free-space optics (FSO) as a transition channel for an air segment in transmitting Raman backscattering signals for distributed temperature sensing (DTS). A barrier-free air segment link shaped by an FSO is part of the Raman-based DTS (RDTS) fiber optic transmission route. For this plan, the FSO enables delivery of the RDTS's pulse with the low-loss transmission over the air segment while also returning to the RDTS the varied Raman backscattered signals from the probing temperature variations for signal interpretation. The difference between various temperatures sensed and the referential air temperature remains nearly the same before and after passing the FSO. The viability of this technology provides a crucial basis for tackling the high expense of installing and repairing DTS cables and the challenges associated with doing so owing to topographical restrictions.

Integrated Sensor-Optics Communication System Using Bidirectional Fiber and FSO Channels and Hybrid Deep Learning Techniques.

This paper introduces a new bidirectional integration approach that combines fiber sensor/free space optics (FSO) communication using an intensity and wavelength division multiplexer (IWDM) techniques-based long-distance fiber Bragg grating (FBG) sensor strain-sensing system. By implementing coarse wavelength division multiplexing (CWDM), the system achieves the simultaneous transmission of optical communication and fiber optical sensor (FOS) sensing signals, resulting in a highly capable, flexible, and cost-effective solution. The proposed FSO transmission technique addresses complex fiber cable installation concerns with topographical limitations. This bidirectional structure ensures the reliability and stability of the long-distance FBG sensor system, supported by extensive research and experimentation. A hybrid stacked gated recurrent units and long short-term memory (SGRU-LSTM) model is proposed to enhance strain measurement accuracy by predicting and measuring the central wavelength of overlapped strain-sensing FBG sensor signals. The results demonstrate the superiority of the proposed model in peak wavelength detection accuracy. The primary benefit of integrating communication and sensing is the significant reduction in construction costs by eliminating the requirement for two individual fiber optic systems, as the integration allows for a single system to fulfill both functions, resulting in more efficient and cost-effective implementation. Overall, this paper contributes to advancing long-distance FBG sensor systems by integrating fiber sensor/FSO communication and deep learning techniques, improving transmission distance, multiplexing capacity, measurement accuracy, system survivability, and cost-effectiveness.

Recent Advances in Natural Products with Anti-Leukemia and Anti-Lymphoma Activities.

Leukemia and lymphoma are the most common blood cancers, which pose a critical threat to the health of adults and children. The total incidence and mortality rates of both are approximately 6% globally. Compared with the expensive cost of CAR T cell therapy, natural products from animals, plants and microorganisms have the characteristics of wide-range sources and costeffectiveness in the treatment of cancer. Moreover, the drug resistance that emerged in leukemia and lymphoma treatments shows an urgent need for new drugs. However, in addition to the natural products that have been marketed in the treatment of leukemia and lymphoma, there have been a large number of studies on natural products that fight blood cancer in recent years. This review summarized the recent studies on natural compounds with anti-lymphoma and anti-leukemia activities, hoping to provide novel weapons into the drug development arsenal.

Dynamics of Benthic Nitrate Reduction Pathways and Associated Microbial Communities Responding to the Development of Seasonal Deoxygenation in a Coastal Mariculture Zone.

Intensive mariculture activities result in eutrophication and enhance coastal deoxygenation. Deoxygenation profoundly influences nitrate reduction processes and further the fate of nitrogen (N) in coastal systems. Herein, 15N isotope labeling, real-time PCR, and high-throughput sequencing techniques were jointly used to investigate the participation and seasonal dynamics of sediment nitrate reduction pathways and the succession of functional microbial communities during the development of seasonal deoxygenation in a coastal aquaculture zone. Denitrification dominated benthic nitrate reduction (46.26-80.91%). Both denitrification and dissimilatory nitrate reduction to ammonium were significantly enhanced by summer deoxygenation (dissolved oxygen levels fell to 2.94 ± 0.28 mg L-1), while anammox remained unchanged. The abundance of the nitrous oxide reductase gene nosZ increased during deoxygenation. The community of the nosZ gene was sensitive to deoxygenation, with Azospirillum and Ruegeria accounting for the majority. Pelobacter was overwhelming in the nrfA gene (encoding dissimilatory nitrite reductase) community, which was less affected by deoxygenation. The variations of benthic nitrate reduction processes were driven by bottom water oxygen combined with temperature, chlorophyll a, and microbial gene abundances and community compositions. Our results implicated that seasonal oxygen-deficient zones could be substantial N sinks of coastal ecosystems and important for N balance. Effective management measures need to be developed to avoid further exacerbation of coastal deoxygenation and maintain the sustainable development of mariculture.