Notes

Road blocks and suggestions regarding Scientific Interpretation regarding Nanoparticle System-Based Focused Alpha-Particle Treatments.
Importance Indole is a relatively stable N-heterocyclic aromatic compound that is widely found in nature. To date, the correlations between indole-related bidirectional cell-to-cell communications and interspecies communal organization remain poorly understood. In this study, we used an experimental model, which consisted of indole-producing and indole-degrading bacteria, to evaluate how bidirectional cell-to-cell communication modulated interspecies biofilm formation via intrinsic and environmental cues. We identified a unique spatial patterning of indole-producing and indole-degrading bacteria within mixed-species biofilms. This spatial patterning was an active process mediated by bidirectional physico-chemical interactions. Our findings represent an important step in gaining a more thorough understanding of the process of polymicrobial biofilm formation and advance the possibility of using indole degrading bacteria to address biofilm-related health and industry issues.Nordic Seas are the subarctic seas connecting the Arctic Ocean and North Atlantic Ocean with complex water masses, experiencing an abrupt climate change. Though the knowledge of the marine virosphere has been expanded rapidly, the diversity of viruses and their relationships with host cells and water masses in the Nordic Seas remains to be fully revealed. Here we establish the Nordic Seas DNA viromes (NSVs) dataset of 55,315 viral contigs including 1,478 unique viral populations from seven stations influenced by both the warm Atlantic and cold Arctic water masses. Caudovirales dominated in the seven NSVs, especially in the warm Atlantic waters. The major giant nucleocytoplasmic large DNA viruses (NCLDVs) contributed a significant proportion of the classified viral contigs in the NSVs (32.2%), especially in the cold Arctic waters (44.9%). The distribution patterns of Caudovirales and NCLDVs were a reflection of the community structure of their hosts in the corresponding water masses and currents. Latitude, pH,ate change in the future.Cell-cell adhesion between oral bacteria plays a key role in the development of polymicrobial communities such as dental plaque. Oral streptococci such as Streptococcus gordonii and Streptococcus oralis are important early colonizers of dental plaque and bind to a wide range of different oral microorganisms, forming multispecies clumps or 'coaggregates'. S. gordonii actively responds to coaggregation by regulating gene expression. To further understand these responses, we assessed gene regulation in S. gordonii and S. oralis following coaggregation in 25% human saliva. Coaggregates were formed by mixing and, after 30 minutes, RNA was extracted for Dual RNASeq analysis. In S. oralis, 18 genes (6 upregulated and 12 downregulated) were regulated by coaggregation. Significantly downregulated genes encoded functions such as amino acid and antibiotic biosynthesis, ribosome and central carbon metabolism. In total, 28 genes were differentially regulated in Streptococcus gordonii (25 upregulated and 3 downregulated). d when oral streptococci bind to one another, as they do in the early stages of dental plaque formation. We show that specific genes are regulated in two different oral streptococci following the formation of mixed-species aggregates. The specific responses of S. gordonii to coaggregation with S. oralis are different from coaggregation with other oral bacteria. Targeting the key genes that are upregulated during interspecies interactions may be a powerful approach to control the developing biofilm and maintain oral health.The reaction sequence for aerobic degradation of bile salts by environmental bacteria resembles degradation of other steroid compounds. Recent findings show that bacteria belonging to the Sphingomonadaceae use a pathway variant for bile-salt degradation. This study addresses this so-called Δ4,6 -variant by comparative analysis of unknown degradation steps in Sphingobium sp. strain Chol11 with known reactions found in Pseudomonas stutzeri Chol1. Investigations with strain Chol11 revealed an essential function of the acyl-CoA dehydrogenase Scd4AB for growth with bile salts. Growth of the scd4AB deletion mutant was restored with a metabolite containing a double bond within the side chain which was produced by the Δ22-acyl-CoA dehydrogenase Scd1AB from P. stutzeri Chol1. Expression of scd1AB in the scd4AB deletion mutant fully restored growth with bile salts while expression of scd4AB only enabled constricted growth in P. stutzeri Chol1 scd1A or scd1B deletion mutants. Strain Chol11 Δscd4A accumulated hydroxylater broad metabolic capabilities. Moreover, it adds a so-far unknown hydroxylation of steroids to the reactions Rieske monooxygenases can catalyze with steroids. Additionally, it analyzes a proteobacterial ketosteroid-9α-hydroxylase and shows that this enzyme is able to catalyze side reactions with non-native substrates.We examined the impacts of warming, nitrogen (N) addition and suppression of arbuscular mycorrhizal fungi (AMF) on soil bacterial and fungal richness and community composition in a field experiment. AMF root colonization and the concentration of an AMF-specific phospholipid fatty acid (PLFA) were significantly reduced after the application of the fungicide benomyl as a soil drench. Warming and N addition had no independent effects but interactively decreased soil fungal richness, while warming, N addition and AMF suppression together reduced soil bacterial richness. Soil bacterial and fungal species diversity was lower with AMF suppression, indicating that AMF suppression have negative effect on microbial diversity. Warming and N addition decreased the net loss of plant species and the plant species richness, respectively. AMF suppression reduced plant species richness and the net gain of plant species but enhanced the net loss of plant species. Structural equation modeling (SEM) demonstrated that the soil baion to reduce bacterial and fungal richness. In addition, bacterial and fungal community compositions were determined by mycorrhizal colonization which was regulated by soil AN and ST. These results suggest that AMF suppression can aggravate the severe losses to native soil microbial diversity and functioning caused by global changes and thus AMF plays a vital role in maintaining belowground ecosystem stability in the future.
In patients with liver cirrhosis (LC), sarcopenia is correlated with frequent complications and increased mortality. Myostatin-a myokine-is a potential biomarker of skeletal mass and/or sarcopenia. The aim of this study was to examine the association between myostatin and muscle-mass and evaluate myostatin as a biomarker of sarcopenia in LC.

Skeletal-muscle-index (SMI) and myosteatosis were evaluated by computed tomography scan. Muscle quantity and quality along with muscle strength and function were used to diagnose sarcopenia. Serum myostatin was measured by ELISA.

115 consecutive patients with LC [72.2% male, median age 59-years (IQR 52-67), MELD 12 (8-16), 28.7% with compensated LC] were included. Low SMI was diagnosed in 49.6% and sarcopenia in 34.8% (21.7% severe). Myostatin levels were lower in low (p<0.001) compared to normal SMI patients and were strongly correlated with SMI in MELD score≥15 (r=0.571, p<0.001). Myostatin was also lower in patients with sarcopenia compared to those without (p<0.001) and even lower in severe sarcopenia (p<0.001). In multivariate analysis, myostatin, age and albumin remained significant predictors of low SMI after adjustment for sex, MELD and creatine phosphokinase(CPK). Similarly, myostatin and age predicted sarcopenia after adjustment for sex, MELD, CPK and albumin. The ratios log
myostatin-to-CPK or albumin-to-myostatin were found to have acceptable diagnostic accuracy in ruling out sarcopenia in total patients. However, the best diagnostic performance was shown in MELD≥15 (AUROC 0.829 or 0.801, respectively).

Myostatin is independently associated with both skeletal muscle mass and sarcopenia. Myostatin in combination with CPK or albumin are good surrogate markers in excluding sarcopenia.
Myostatin is independently associated with both skeletal muscle mass and sarcopenia. Myostatin in combination with CPK or albumin are good surrogate markers in excluding sarcopenia.Studying dielectric properties of heterogeneous systems is challenged by a problem of uncertainty of the ratio between dielectric permittivity of the system and dielectric permittivities of its components. Such ratios can be obtained in some cases using theoretical effective medium models. However, such models have not yet been developed for all the systems possible. Particularly, there is no effective medium model with filamentary inclusions. Such a theoretical model elaborated based on the fundamental principles of electrodynamics of continuous media is suggested in the present work. Any point of a filamentary inclusion with a length that is significantly greater than the thickness can be regarded as being located in a long cylinder-like fragment of the inclusion with stochastic direction of the cylinder axis relative to the external electric field. With this regard, electric field strength and electric induction values were averaged across the entire volume of a two-phase dielectric material. As a result, a model linking the dielectric permittivity of the two-phase system and the dielectric permittivities of both phases was elaborated. The model appears to be highly relevant for studying solutions of biopolymers, such as nucleic acids, fibrillar proteins and protein aggregates, polysaccharides, by means of electrical impedance spectroscopy, dielectric spectroscopy, and terahertz time-domain spectroscopy. The suggested theoretical model was successfully validated on a DNA solution within the terahertz region.Streptococcus suis is an important bacterial pathogen in pigs that may also cause zoonotic disease in humans. The aim of the study was to evaluate MALDI-TOF MS identification of S. suis case isolates from diseased pigs and tonsil isolates from healthy pigs and wild boar, using sequence analysis methods. Isolates (n=348) which had been classified as S. suis by MALDI-TOF MS were whole-genome sequenced and investigated using analysis of i) the 16S rRNA gene, ii) the recN gene, and iii) whole-genome average nucleotide identity (ANI). Analysis of the 16S rRNA gene indicated that 82.8% (288 out of 348) of the isolates were S. suis, while recN-gene analysis indicated that 75.6% (263 out of 348) were S. suis. ANI analysis classified 44.3% (154 out of 348) as S. suis. In total, 44% (153 out of 348) of the investigated isolates were classified as S. suis by all of the species identification methods employed. The mean MALDI-TOF MS score was significantly higher for the S. suis case isolates compared to the tonsil isolates, however, the difference is of limited practical use. The results show that species confirmation beyond MALDI-TOF MS is needed for S. suis isolates. Since the resolution of 16S rRNA gene analysis is too low for Streptococcus spp., ANI analysis with a slightly lowered cutoff of 94% may be used instead of, or in addition to, recN-gene analysis. Supplementation of the MALDI-TOF MS reference library with mass spectra from S. orisratti, S. parasuis, S. ruminantium, and additional S. suis serotypes, should be considered in order to produce more accurate classifications.Serologic, point-of-care tests to detect antibodies against SARS-CoV-2 are an important tool in the COVID-19 pandemic. The majority of current point-of-care antibody tests developed for SARS-CoV-2 rely on lateral flow assays, but these do not offer quantitative information. To address this, we developed a novel antibody test leveraging hemagglutination, employing a dry card format currently used for typing ABO blood groups. 200 COVID-19 patient and 200 control plasma samples were reconstituted with O-negative RBCs to form whole blood and added to dried viral-antibody fusion protein, followed by a stirring step and a tilting step, 3-minute incubation, and a second tilting step. The sensitivity for the hemagglutination test, Euroimmun IgG ELISA test and RBD-based CoronaChek lateral flow assay was 87.0%, 86.5%, and 84.5%, respectively, using samples obtained from recovered COVID-19 individuals. Testing pre-pandemic samples, the hemagglutination test had a specificity of 95.5%, compared to 97.3% and 98.9% for the ELISA and CoronaChek, respectively. A distribution of agglutination strengths was observed in COVID-19 convalescent plasma samples, with the highest agglutination score (4) exhibiting significantly higher neutralizing antibody titers than weak positives (2) (p less then 0.0001). Strong agglutinations were observed within 1 minute of testing, and this shorter assay time also increased specificity to 98.5%. In conclusion, we developed a novel rapid, point-of-care RBC agglutination test for the detection of SARS-CoV-2 antibodies that can yield semi-quantitative information on neutralizing antibody titer in patients. The five-minute test may find use in determination of serostatus prior to vaccination, post-vaccination surveillance and travel screening.The utility of rapid antigen testing for SARS-CoV-2 is measured within the context for which it is applied; diagnostic accuracy must be considered in determining if rapid antigen testing is appropriate for the clinical situation. In this issue of the Journal of Clinical Microbiology, J.N. Kanji et al (J Clin Microbiol 59e01411-21, 2021, https//doi.org/10.1128/JCM.01411-21) evaluate two rapid antigen tests that demonstrate high false-positive rates in asymptomatic healthcare workers. The assays may not be useful in situations where there is a shortage of staff, such as healthcare, since isolation would occur unnecessarily for these employees.Chagas disease is a neglected disease caused by Trypanosoma cruzi parasites. Most of diagnosis is based on serological tests but the lack of a gold standard test complicates the measurement of test performance. To overcome this limitation, we used samples from a cohort of well-characterized T. cruzi infected women to evaluate the reactivity of two rapid diagnostic tests and one ELISA assay. Our cohort derived from a previous study on congenital transmission of T. cruzi, and consisted in 481 blood/plasma samples from Argentina (n=149), Honduras (n=228) and Mexico (n=104) with at least one positive T. cruzi PCR. Reactivity of the three tests ranged from 70.5% for the Wiener ELISA to 81.0% for the T-Detect and 90.4% for the Stat-Pak rapid tests. Test reactivity varied significantly among countries, and was highest in Argentina, and lowest in Mexico. When considering at least two reactive serological tests to confirm seropositivity, over 12% of T. cruzi infection cases from Argentina were missed by serological tests, over 21% in Honduras, and an alarming 72% in Mexico. Differences in test performance among countries were not due to differences in parasitemia, but differences in antibody levels against ELISA test antigens were observed. Geographic differences in T. cruzi parasite strains as well as genetic differences among human populations may both contribute to the discrepancies in serological testing. Improvements in serological diagnostics for T. cruzi infections are critically needed to ensure an optimum identification of cases.Background Tuberculosis lymphadenitis (TBL) is the most common extrapulmonary TB (EPTB) manifestation. Xpert MTB/RIF Ultra (Ultra) is a World Health Organization-endorsed diagnostic test, but performance data for TBL, including on non-invasive specimens, are limited. Methods Fine needle aspiration biopsies (FNABs) from outpatients (≥18 years) with presumptive TBL (n=135) underwent 1) routine Xpert (later Ultra once programmatically available), 2) a MGIT 960 culture (if Xpert- or Ultra-negative, or rifampicin-resistant), and 3) study Ultra. Concentrated paired urine underwent Ultra. Primary analyses used a microbiological reference standard (MRS). Results In a head-to-head comparison (n=92) of FNAB study Ultra and Xpert, Ultra had increased sensitivity [91% (95% confidence interval 79, 98) vs. 72% (57, 84); p=0.016] and decreased specificity [76% (61, 87) vs. 93% (82, 99); p=0.020], and detected patients not on treatment. HIV nor alternative reference standards affected sensitivity and specificity. In patients with both routine and study Ultras, the latter detected more cases [+20% (0, 42); p=0.034] and, further indicative of potential laboratory-based room-for-improvement (e.g., specimen processing optimisation), false-negative study Ultras were more inhibited than true-positives. Study Ultra false-positives had less mycobacterial DNA than true-positives [trace-positive proportions 59% (13/22) vs. 12% (5/51); p less then 0.001]. "Trace" exclusion or recategorization removed potential benefits offered over Xpert. Urine Ultra had low sensitivity [18% (7, 35)]. Conclusions Ultra on FNABs is highly sensitive and detects more TBL than Xpert. Patients with FNAB Ultra-positive "trace" results, most of whom will be culture-negative, may require additional clinical investigation. Urine Ultra could reduce the number of patients needing invasive sampling.The purpose of this manuscript is to invite a revisiting of the concept of the "discipline" of Nursing, with attention to the spiritual consciousness of "Nurse" within the sacred concept of self-caring and caring-healing consciousness. The notion of including the spiritual, evolving consciousness of "Nurse," in harmony with evolution of Professional Nursing, is congruent with a mature disciplinary matrix of caring science as sacred science. This congruence between Nurse/Nursing contributes to the evolution of Nursing, Holistic Practices and Era III unitary transformative disciplinary thinking.Emergency department visits and hospitalizations are common among people receiving cancer treatment, accounting for a large proportion of spending in oncology care and negatively affecting quality of life. As oncology care shifts toward value- and quality-based payment models, there is a need to develop interventions that can prevent these costly and low-value events among people receiving cancer treatment. Risk stratification programs have the potential to address this need and optimally would consist of three components (1) a risk stratification algorithm that accurately identifies patients with modifiable risk(s), (2) intervention(s) that successfully reduce this risk, and (3) the ability to implement the risk algorithm and intervention(s) in an adaptable and sustainable way. Predictive modeling is a common method of risk stratification, and although a number of predictive models have been developed for use in oncology care, they have rarely been tested alongside corresponding interventions or developed with implementation in clinical practice as an explicit consideration. In this article, we review the available published predictive models for treatment-related toxicity or acute care events among people receiving cancer treatment and highlight challenges faced when attempting to use these models in practice. To move the field of risk-stratified oncology care forward, we argue that it is critical to evaluate predictive models alongside targeted interventions that address modifiable risks and to demonstrate that these two key components can be implemented within clinical practice to avoid unplanned acute care events among people receiving cancer treatment.Purpose This study aimed to examine the Stroop effects of verbal and nonverbal cues and their relative impacts on gender differences in unisensory and multisensory emotion perception. Method Experiment 1 investigated how well 88 normal Chinese adults (43 women and 45 men) could identify emotions conveyed through face, prosody and semantics as three independent channels. Experiments 2 and 3 further explored gender differences during multisensory integration of emotion through a cross-channel (prosody-semantics) and a cross-modal (face-prosody-semantics) Stroop task, respectively, in which 78 participants (41 women and 37 men) were asked to selectively attend to one of the two or three communication channels. Results The integration of accuracy and reaction time data indicated that paralinguistic cues (i.e., face and prosody) of emotions were consistently more salient than linguistic ones (i.e., semantics) throughout the study. Additionally, women demonstrated advantages in processing all three types of emotional signals in the unisensory task, but only preserved their strengths in paralinguistic processing and showed greater Stroop effects of nonverbal cues on verbal ones during multisensory perception. Conclusions These findings demonstrate clear gender differences in verbal and nonverbal emotion perception that are modulated by sensory channels, which have important theoretical and practical implications. Supplemental Material https//doi.org/10.23641/asha.16435599.The purpose of this study was to quantify radiation dose from the XTG (Xray2Go) handheld X-ray device for bitewing and maxillary anterior occlusal projections using a pediatric phantom. The aim was to evaluate effects of thyroid shielding on total effective dose (E) and tissue equivalent doses (HT) and assess operator backscatter radiation. MethodsA pediatric phantom head with 24 tissue site dosimeters was exposed to radiation from the x-ray device. Exposures included (1) right and left bitewing (BW) without thyroid collar on phantom, (2) BW with thyroid collar, (3) maxillary anterior occlusal (AO) without thyroid collar, (4) AO with thyroid collar. With each exposure type, new dosimeter sets were used and 30 exposures completed. The operator wore dosimeters on the forehead and right hand to quantify backscatter radiation. Average values of HT and E were calculated. Conclusions Thyroid shielding made a statistically significant difference for radiation dose with the Xray2Go for BW projections at specific tissue sites, including the thyroid, lymph nodes, and muscle, and for overall effective dose. Radiation to the operator from the device was very low and indistinguishable from background radiation.The wear of dentures carries with it the possibility of an inflammatory response by the denture-bearing tissues. Lack of or improper hygiene has been shown to contribute to denture stomatitis (DS). Although essential, denture hygiene is often overlooked by patients or performed improperly. As professional caregivers dentists must instruct patients and ensure that they understand the relevance and importance of denture hygiene. In light of this, the authors conducted a critical review of the literature on protocols and procedures to highlight the importance of denture hygiene and clinically show the effects of lack of denture care. A literature search was done through Google, PubMed, and Google Scholar that focused on publications published in English that dealt with denture hygiene and the disinfection process and on the protocols used. Relevant articles for protocols for denture disinfections were reviewed, and the results of different disinfection techniques were assessed, including manual, chemical, microwave, and a combination of techniques. The authors conclude that dentists must take time to instruct patients on proper denture disinfection procedures and the importance of cleaning the dentures well at least once daily. Denture hygiene and removal prior to sleeping is beneficial in preventing DS and allowing the tissue to achieve a state of homeostasis.Caffeine is not only a widely consumed active stimulant, but it is also a model molecule commonly used in pharmaceutical sciences. In this work, by performing quartz-crystal microbalance and neutron reflectometry experiments we investigate the interaction of caffeine molecules with a model lipid membrane. We determined that caffeine molecules are not able to spontaneously partition from an aqueous environment, enriched in caffeine, into a bilayer. Caffeine could be however included in solid-supported lipid bilayers if present with lipids during self-assembly. In this case, thanks to surface-sensitive techniques, we determined that caffeine molecules are preferentially located in the hydrophobic region of the membrane. These results are highly relevant for the development of new drug delivery vectors, as well as for a deeper understanding of the membrane permeation role of purine molecules.The determination of efficient collective variables is crucial to the success of many enhanced sampling methods. As inspired by previous discrimination approaches, we first collect a set of data from the different metastable basins. The data are then projected with the help of a neural network into a low-dimensional manifold in which data from different basins are well-discriminated. This is here guaranteed by imposing that the projected data follows a preassigned distribution. The collective variables thus obtained lead to an efficient sampling and often allow reducing the number of collective variables in a multibasin scenario. We first check the validity of the method in two-state systems. We then move to multistep chemical processes. In the latter case, at variance with previous approaches, one single collective variable suffices, leading not only to computational efficiency but also to a very clear representation of the reaction free-energy profile.Sn-based halide perovskites are promising for thermoelectric (TE) device applications because of their high electrical conductivity as well as the low thermal conductivity associated with their soft lattices. However, conventional three-dimensional Sn-based perovskites are not stable under typical TE device operating conditions. Here, we report a stable two-dimensional Sn-based perovskite for thermoelectric energy conversion by incorporating bulky conjugated ligands. We demonstrate a thin film with a large power factor of 5.42 ± 3.07 (average) and 7.07 (champion) μW m-1 K-2 at 343 K with an electrical conductivity of 5.07 S cm-1 and a Seebeck coefficient of 118.1 μV K-1. Importantly, these thin films show excellent operational stability (i.e., for over 100 h) at 313 K. This work suggests that the novel hybrid two-dimensional perovskites are a promising platform for thermoelectric energy conversion applications.The efficient protocol for the estimation of gas-phase enthalpies of formation developed previously for C, H, O, N, and F elements was extended to sulfur. The protocol is based on a local coupled cluster with single, double, and perturbative triple excitation [CCSD(T)] approximation and allows rapid evaluation of compounds with sizes computationally prohibitive to canonical CCSD(T) using quadruple zeta basis sets. As a part of model development, a comprehensive review and critical evaluation of experimental data were performed for 87 sulfur-containing organic and inorganic compounds. A compact model with only three empirical parameters for sulfur introduced to address the effects beyond frozen core CCSD(T) was developed. The model exhibits approximately 2 kJ·mol-1 standard deviation over a set of experimental values for a diverse collection of sulfur-containing compounds. The complete basis set version of the model demonstrates a similar performance and requires only one empirical parameter. Multiple problems with the existing experimental data were identified and discussed. In addition, a lack of reliable data for certain important classes of sulfur compounds was found to impede the model generalization and confident performance assessment.Chronic low-dose exposure to organophosphorus pesticides is associated with the risk of neurodegenerative disease. The mechanism of neurotoxicity is independent of acetylcholinesterase inhibition. Adducts on tyrosine, lysine, threonine, and serine can occur after exposure to organophosphorus pesticides, the most stable being adducts on tyrosine. Rabbit monoclonal 1C6 to diethoxyphosphate-modified tyrosine (depY) was created by single B cell cloning. The amino acid sequence and binding constant (Kd 3.2 × 10-8 M) were determined. Cultured human neuroblastoma SH-SY5Y and mouse neuroblastoma N2a cells incubated with a subcytotoxic dose of 10 μM chlorpyrifos oxon contained depY-modified proteins detected by monoclonal 1C6 on Western blots. depY-labeled peptides from tryptic digests of cell lysates were immunopurified by binding to immobilized 1C6. Peptides released with 50% acetonitrile and 1% formic acid were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) on an Orbitrap Fusion Lumos mass spectrometer. Protein Prospector database searches identified 51 peptides modified on tyrosine by diethoxyphosphate in SH-SY5Y cell lysate and 73 diethoxyphosphate-modified peptides in N2a cell lysate. Adducts appeared most frequently on the cytoskeleton proteins tubulin, actin, and vimentin. It was concluded that rabbit monoclonal 1C6 can be useful for studies that aim to understand the mechanism of neurotoxicity resulting from low-dose exposure to organophosphorus pesticides.Inkjet printing technique is susceptible to form coffer-ring patterns and inhomogeneous films owing to the evaporation and its accompanying hydrodynamics of microscale quantum dot droplet. Pioneer efforts are usually confined to two-dimensional flat substrates and inks with mixed solvents/additives. Herein we demonstrate that physically confined space offers an additional parameter in tailoring such processes of droplets and the following quantum-dot self-assembly deposition, without extra modification of quantum dots or solvent chemistry. Owing to the boundary of physically confined space, two three-phase border lines in both the bottom center (horizontal direction) and the barrier of the bank substrate (vertical direction) arise, inducing dual capillary flows and Marangoni backflows. The evaporation, fluid flow, and film-forming process in physically confined space are studied by introducing well-prepared single-solvent quantum dots inks. The systematical analysis offers valuable instructions including ink preparation, surface modification, and postprocessing evaporation technique for inkjet-printed patterning applications, especially for pixelated display, polychrome patterning, and sensor array.Late-stage functionalization of the periphery of oligophenylene dendrimers was efficiently achieved via site-selective C-H activation of a preconstructed, readily accessible dendron. By fourfold iridium-catalyzed C-H borylation followed by Suzuki-Miyaura cross-coupling, various arene units were introduced into the end points of the 1,3,5-phenylene-based hydrocarbon dendron. Coupling of the modified dendrons with a core unit, such as 2,6-dibromobenzoic acid derivatives, afforded the periphery-functionalized dendrimers that also have an endohedral functionality at the core position.Metal-semiconductor-metal plasmonic nanostructures enable both on-chip efficient manipulation and ultrafast photodetection of strongly confined modes by enhancing local electrostatic and optical fields. The latter is achieved by making use of nanostructured thin-film germanium (Ge) plasmonic-waveguide photodetectors. While their sizes and locations can be accurately controlled during the nanofabrication, the detector efficiencies are significantly reduced due to deposited Ge amorphous nature. We demonstrate that the efficiency of waveguide-integrated Ge plasmonic photodetectors can be increased significantly (more than 2 orders of magnitude) by spatially controlled laser-induced Ge crystallization. We investigate both free-space and waveguide-integrated Ge photodetectors subjected to 800 nm laser treatment, monitoring the degree of crystallization with Raman spectroscopy, and demonstrate the efficiency enhancement by detecting the telecom radiation. The demonstrated local postprocessing technique can be utilized in various nanophotonic devices for efficient and ultrafast on-chip radiation monitoring and detection, offering significantly improved detector characteristics without jeopardizing the performance of other components.The impact of liquid drops on a rigid surface is central in cleaning, cooling, and coating processes in both nature and industrial applications. However, it is not clear how details of pores, roughness, and texture on the solid surface influence the initial stages of the impact dynamics. Here, we experimentally study drops impacting at low velocities onto surfaces textured with asymmetric (tilted) ridges. We found that the difference between impact velocity and the capillary speed on a solid surface is a key factor of spreading asymmetry, where the capillary speed is determined by the friction at a moving three-phase contact line. The line-friction capillary number Caf = μfV0/σ (where μf,V0, and σ are the line friction, impact velocity, and surface tension, respectively) is defined as a measure of the importance of the topology of surface textures for the dynamics of droplet impact. We show that when Caf ≪ 1, the droplet impact is asymmetric; the contact line speed in the direction against the inclination of the ridges is set by line friction, whereas in the direction with inclination, the contact line is pinned at acute corners of the ridges. When Caf ≫ 1, the geometric details of nonsmooth surfaces play little role.Tessellations of kekulenes and cycloarenes are of considerable interest as nanomolecular belts in trapping and transportation of heavy metal ions and chloride ions, as they possess optimal electronic features and pore sizes. A class of cycloarenes called kekulenes have been the focus of several experimental and theoretical studies from the stand point of aromaticity, superaromaticity, chirality, and novel electrical and magnetic properties. In the present study, we investigate the entropies and topological characterization of different tessellations of kekulenes through topological computations of superaromatic structures with pores. We introduce the self-powered vertex degree-based topological indices and then derive the graph entropy measures for three different tessellations (zigzag, armchair, and rectangular) via various molecular descriptors that we derive here. Several applications to computing the molecular properties are pointed out. We demonstrate the existence of isentropic and yet nonisomorphic tessellations of kekulenes for the first time. The two tessellations are predicted to be quite close in energy with comparable energy gaps. Graph theory-based PPP methods with parameters derived from higher levels of theory are proposed to be promising tools for the predictions of relative stabilities of kekulene tessellations. We show that the developed techniques can be applied in the general context of artificial intelligence for the machine generation of nuclear magnetic resonance and electron spin resonance spectroscopic patterns as well as in robust computations of thermochemistry of a large combinatorial libraries of tessellations of kekulenes through the generation of bond-equivalence classes.The first light-driven method for the α-trifluoromethoxylation of ketones is reported. Enol carbonates react with N-trifluoromethoxy-4-cyano-pyridinium, using the photoredox catalyst 4-CzIPN under 456 nm irradiation, affording the α-trifluoromethoxy ketones in ≤50% isolated yield and complete chemoselectivity. As shown by 29 examples, the reaction is general and proceeds very rapidly under batch (1 h) and flow conditions (2 min). Diverse product manipulations demonstrate the synthetic potential of the disclosed method in accessing elusive trifluoromethoxylated bioactive ingredients.Carbon dots (CDs), as emerging luminescent nanomaterials, possess excellent but complex properties, and thus, they have attracted immense attention for their applications. Further practical application of CDs has been hindered by their limited photostability and photoluminescence intermittency. In this study, we demonstrated that an antioxidant (Trolox) can dramatically enhance the photostability and minimize the photoblinking of CDs without affecting their native spectral characteristics. Significant photoluminescence enhancement and stabilization were observed with the addition of Trolox in ensemble level. Meanwhile, strikingly stable emissions from individual CDs have been observed in the presence of Trolox in single-particle-level experiments. Our observations revealed that the charged state of CDs can be effectively recovered to a neutral state by Trolox via electron transfer. These results prove that the combination of antioxidants and CDs is a powerful means to improve their fluorescence robustness, which is crucial for applications that demand long-lived, nonblinking emission.Staphylococci bind to the blood protein von Willebrand Factor (vWF), thereby causing endovascular infections. Whether and how this interaction occurs with the medically important pathogen Staphylococcus epidermidis is unknown. Using single-molecule experiments, we demonstrate that the S. epidermidis protein Aap binds vWF via an ultrastrong force, ∼3 nN, the strongest noncovalent biological bond ever reported, and we show that this interaction is activated by tensile loading, suggesting a catch-bond behavior. Aap-vWF binding involves exclusively the A1 domain of vWF but requires both the A and B domains of Aap, as revealed by inhibition assays using specific monoclonal antibodies. Collectively, our results point to a mechanism where force-induced unfolding of the B repeats activates the A domain of Aap, shifting it from a weak- to a strong-binding state, which then engages into an ultrastrong interaction with vWF A1. This shear-dependent function of Aap offers promise for innovative antistaphylococcal therapies.Diastereomers have historically been ignored when building kinetic mechanisms for combustion. Low-temperature oxidation kinetics, which continues to gain interest in both combustion and atmospheric communities, may be affected by the inclusion of diastereomers in radical chain-branching pathways. In this work, key intermediates and transition states lacking stereochemical specification in an existing diethyl ether low-temperature oxidation mechanism were replaced with their diastereomeric counterparts. Rate coefficients for reactions involving diastereomers were computed with ab initio transition state theory master equation calculations. The presence of diastereomers increased rate coefficients by factors of 1.2-1.6 across various temperatures and pressures. Ignition delay simulations incorporating these revised rate coefficients indicate that the diastereomers enhanced the overall reactivity of the mechanism by almost 15% and increased the peak ketohydroperoxide concentration by 30% in the negative temperature coefficient region at combustion-relevant pressures. These results provide an illustrative indication of the important role of stereomeric effects in oxidation kinetics.Palladium catalyzes a domino Heck arylation and alkylation of nonconjugated cyclodienes to produce trans isomers of disubstituted cyclohexenes in exceptionally high enantiomeric ratios, reaching 1001 to 2001 in many cases. Importantly, the interactions of the two CF bonds of Josiphos and the sodium ion of malonates facilitates stereoselective allylic attack through DFT calculations and experiments. This is a new type of attractive noncovalent interactions found in organometallic catalysis.The conformational analysis of a 2,4-bis(4-dialkylamino-2-amido)phenyl squaraine dye revealed the presence of two rotational isomers at room temperature. Combination of spectroscopic and computational techniques showed that the rotational barrier is influenced by hydrogen bonds between the amido substituents and the oxygen atoms at the quadratic core. Even small amounts of trifluoroacetic acid interfered with the intramolecular hydrogen bond formation and accelerated the interconversion of the conformers.Herein, we present a new strategy for the development of efficient heavy-atom free singlet oxygen photosensitizers based on rigid borafluorene scaffolds. Physicochemical properties of borafluorene complexes can be easily tuned through the choice of ligand, thus allowing exploration of numerous organoboron structures as potent 1O2 sensitizers. The singlet oxygen generation quantum yields of studied complexes vary in the range of 0.55-0.78. Theoretical calculations reveal that the introduction of the borafluorene moiety is crucial for the stabilization of a singlet charge transfer state, while intersystem crossing to a local triplet state is facilitated by orthogonal donor-acceptor molecular architecture. Our study shows that quantitative oxidation of selected organic substrates can be achieved in 20-120 min of irradiation with only 0.05 mol % loading of a photocatalyst.Electron microscopy, scanning probe, and optical super-resolution imaging techniques with nanometric resolution are now routinely available but cannot capture the characteristically fast (MHz-GHz frequency) movements of micro-/nano-objects. Meanwhile, optical interferometric techniques can detect high-frequency picometric displacements but only with diffraction-limited lateral resolution. Here, we introduce a motion visualization technique, based on the spectrally resolved detection of secondary electron emission from moving objects, that combines picometric displacement sensitivity with the nanometric spatial (positional/imaging) resolution of electron microscopy. The sensitivity of the technique is quantitatively validated against the thermodynamically defined amplitude of a nanocantilever's Brownian motion. It is further demonstrated in visualizing externally driven modes of cantilever, nanomechanical photonic metamaterial, and MEMS device structures. With a noise floor reaching ∼1 pm/Hz1/2, it can provide for the study of oscillatory movements with subatomic amplitudes, presenting new opportunities for the interrogation of motion in functional structures across the materials, bio- and nanosciences.Na-ion and K-ion batteries are promising alternatives for large-scale energy storage due to their abundance and low cost. Intercalation of these large ions could cause irreversible structural deformation and partial to complete amorphization in the crystalline electrodes. A lack of understanding of the dynamic changes in the amorphous nanostructure during battery operation is the bottleneck for further developments. Here, we report the utilization of in-operando digital image correlation and XRD techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium ion intercalation. In-operando XRD demonstrates amorphization in the electrode's nanostructure during the first charge and discharge cycle. Additionally, ex situ HR-TEM further confirms the amorphization after potassium-ion intercalation. An in situ strain analysis detects reversible deformations associated with redox reactions in the amorphous phases. Our approach offers new insights into the mechanism of ion intercalation in the amorphous nanostructure which are highly potent for the development of next-generation batteries.A practicable strategy to a reversible mechanochromic material featuring interconversion of classical/frustrated Brönsted pairs has been established. We report the mechanochromic property of 2,6-bis(4-biphenyl)isonicotinic acid (1), which features a frustrated Brönsted pair in the crystalline form and a classical Brönsted pair after grinding. A large mechanochromic shift was found from 428 to 505 nm. In addition, compound 1 also exhibits acidochromic behavior, which further proves that the formation of an acid-base interaction is responsible for the mechanochromic phenomenon.The synthesis of calix[4]- and -[6]arene derivatives P6(H)22+·(Cl-)2, V4(H)24+·(Cl-)2·(I-)2, and V6(H)24+·(Cl-)2·(I-)2 bearing N-linked pyridinium (P) and viologen (V) units at the upper rim is described here. A rare example of an anionic conformational template is reported for p-pyridiniumcalix[6]arene P6(H)22+, which adopts a 1,3,5-alternate conformation in the presence of chloride anions. Derivatives P6(H)22+·(Cl-)2, V6(H)24+·(Cl-)2·(I-)2, and V4(H)24+·(Cl-)2·(I-)2 show a negative solvatochromism, while their UV-vis acid-base titration evidenced that upon addition of a base, new bands appear at 487, 583, and 686 nm, respectively, due to the formation of betainic monodeprotonated species P6(H)1+, V6(H)13+, and V4(H)13+. These new bands were attributable to the intramolecular charge-transfer (CT) transition from the phenoxide to the pyridinium or viologen moiety and were responsive to the presence of cations. In fact, the band at 487 nm of P6(H)1+ was quenched in the presence of a hard Li+ cation, and the color of its acetonitrile solution was changed from pink to colorless upon addition of LiI. Consequently, this derivative can be considered as a useful host for the recognition and sensing of lithium cations.We report a straightforward synthetic strategy for the preparation of trihydroxypiperidine azasugars decorated with lipophilic chains at both the nitrogen and the adjacent carbon as potential inhibitors of the lysosomal enzyme glucocerebrosidase (GCase), which is involved in Gaucher disease. The procedure relies on the preparation of C-erythrosyl N-alkylated nitrones 10 through reaction of aldehyde 8 and primary amines 13 followed by oxidation of the imines formed in situ with the methyltrioxorhenium catalyst and urea hydrogen peroxide. The addition of octylMgBr to nitrone 10e provided access to both epimeric hydroxylamines 21 and 22 with opposite configuration at the newly created stereocenter in a stereodivergent and completely stereoselective way, depending on the absence or presence of BF3·Et2O. Final reductive amination and acetonide deprotection provided compounds 14 and 15 from low-cost d-mannose in remarkable 43 and 32% overall yields, respectively, over eight steps. The C-2 R-configured bis-alkylated trihydroxypiperidine 15 was the best ligand for GCase (IC50 = 15 μM), in agreement with MD simulations that allowed us to identify the chair conformation corresponding to the best binding affinity.Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with MnIII tris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2 was generated at the MnV/IV potential with hydroxide, but a more anodic potential was required to evolve O2 with only water. With a synthetic MnV(O) complex of 1, a second-order rate constant, k2(OH-), of 7.4 × 103 M-1 s-1 was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with a k2(H2O) value of 4.4 × 10-3 M-1 s-1. This large reactivity difference of MnV(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a MnIV-peroxo species was identified with various spectroscopic methods, including UV-vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex. Density functional theory calculations suggested that the nucleophilic attack of hydroxide on MnV(O) and also WNA to 1e--oxidized MnV(O) are feasibly involved in the catalytic cycles but that direct WNA to MnV(O) is not likely to be the main O-O bond formation pathway in the electrocatalytic water oxidation by 1.We developed a general method for the selective photochemical homo- and heterodimerization of cinnamic acid derivatives with the use of commercially available 1,8-dihydroxynaphthalene as a covalent template. A variety of symmetrical and unsymmetrical β-truxinic acids were obtained in high yields and as single diastereomers. The use of a template not only provides the alignment of the two olefins with suitable proximity ( less then 4.2 Å) but also allows the heterodimerization of two different cinnamic acids, leading to unsymmetrical β-truxinic acid products.The use of combinations of aroma compounds is common in many food and cosmetic applications. To investigate the binding behavior between high-amylose maize starch and binary aroma combinations of decanal and thymol, starch-aroma inclusion complexes (ICs) were prepared by a one-step or two-step method with different concentrations and orders of addition. The thymol molecule induced the starch chain to form a larger helical cavity and was more likely to form hydrogen bonds with solvents. The encapsulation efficiency and loading efficiency of starch-thymol ICs were always higher than those of starch-decanal ICs, independent of the aroma concentration and addition order in binary aroma ICs. However, starch-decanal ICs prepared in the presence of thymol encapsulated more decanal than in the absence of thymol. The V6I-type crystals formed by starch-decanal ICs and the V6III-type crystals formed by starch-thymol ICs were both present in binary aroma ICs, resulting in a less-ordered structure and lower thermal transition temperatures. In summary, the complexation between binary aroma compounds and starch exhibited both cooperative and competitive binding behaviors. The synergistic effects between decanal and thymol provide guidance in enhancing the aroma encapsulation in starch carriers.Manganese (Mn) is a biologically important and redox-active metal that may exert a poorly recognized control on carbon (C) cycling in terrestrial ecosystems. Manganese influences ecosystem C dynamics by mediating biochemical pathways that include photosynthesis, serving as a reactive intermediate in the breakdown of organic molecules, and binding and/or oxidizing organic molecules through organo-mineral associations. However, the potential for Mn to influence ecosystem C storage remains unresolved. Although substantial research has demonstrated the ability of Fe- and Al-oxides to stabilize organic matter, there is a scarcity of similar information regarding Mn-oxides. Furthermore, Mn-mediated reactions regulate important litter decomposition pathways, but these processes are poorly constrained across diverse ecosystems. Here, we discuss the ecological roles of Mn in terrestrial environments and synthesize existing knowledge on the multiple pathways by which biogeochemical Mn and C cycling intersect. We demonstrate that Mn has a high potential to degrade organic molecules through abiotic and microbially mediated oxidation and to stabilize organic molecules, at least temporarily, through organo-mineral associations. We outline research priorities needed to advance understanding of Mn-C interactions, highlighting knowledge gaps that may address key uncertainties in soil C predictions.
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