Connection between Tamoxifen versus. Toremifene in oily hard working liver development and lipid users inside cancer of the breast.
Propionate and Butyrate Made by Belly Microbiota after Probiotic Using supplements Attenuate Respiratory Metastasis associated with Cancer malignancy Cells throughout Rats.
Background The size-specific dose estimate (SSDE) is a patient-focused CT dose metric. However, published size-dependent conversion factors (fsize) used to calculate SSDE were determined primarily by using phantoms; only eight to 15 patient data sets were used, all at 120 kV. Purpose To determine the effect of different tube potentials on the water-equivalent diameter (WED) and SSDE for patient CT scans of the head, chest, and abdomen. Materials and Methods This retrospective study used 250 noncontrast CT scans acquired between March 2013 and June 2017. Bony structures were segmented, and their CT numbers were modified to reflect bone attenuation at 70, 90, 110, 130, and 150 kV. Soft-tissue CT numbers were unchanged because of negligible energy dependence. fsize was measured in anthropomorphic phantoms for each tube potential and fit to an exponential function. WED and SSDE were determined for each patient at all tube potentials, regression analysis was performed relative to the WED and SSDE at 120 kV, and mean differences relative to 120 kV were calculated. Results In 250 patients (median age, 21.5 years; interquartile range, 44 years; 130 women), WED for all tube potentials was linearly related to the WED at 120 kV in all body regions (R2 = 0.995-1.000). The effect of tube potential on WED was negligible for torso examinations (Cohen d less then 0.05). In the head, a medium effect size was observed at 70 kV; however, the mean absolute difference in WED was small (-0.49 cm ± 0.08 [standard deviation]; P less then .001). For commonly used combinations of tube potential and patient size, the mean differences in SSDE at alternative tube potentials relative to SSDE at 120 kV were less than 5%. Conclusion At noncontrast CT, published size-dependent conversion factors accurately determined size-specific dose estimates on 250 patient scans at five tube potentials other than 120 kV. © RSNA, 2022 Online supplemental material is available for this article. See also the editorial by Boone in this issue.MRI plays an important role as a secondary test or problem-solving modality in the evaluation of adnexal lesions depicted at US. MRI has increased specificity compared with US, decreasing the number of false-positive diagnoses for malignancy and thereby avoiding unnecessary or over-extensive surgery in patients with benign lesions or borderline tumors, while women with possible malignancies can be expeditiously referred for oncologic surgical evaluation. The Ovarian-Adnexal Reporting and Data System (O-RADS) MRI Committee is an international collaborative effort formed under the direction of the American College of Radiology and includes a diverse group of experts on adnexal imaging and management who developed the O-RADS MRI risk stratification system. This scoring system assigns a probability of malignancy based on the MRI features of an adnexal lesion and provides information to facilitate optimal patient management. The widespread implementation of a codified reporting system will lead to improved interpretation agreement and standardized communication between radiologists and referring physicians. In addition, it will allow for high-quality multi-institutional collaborations-an important unmet need that has hampered the performance of high-quality research in this area in the past. This article provides guidelines on using the O-RADS MRI risk stratification system in clinical practice, as well as in the educational and research settings.Background Urinary continence after radical prostatectomy (RP) is an important determinant of patient quality of life. Anatomic measures at prostate MRI have been previously associated with continence outcomes, but their predictive ability and interrater agreement are unclear in comprehensive clinical models. Purpose To evaluate the predictive ability and interrater agreement of MRI-based anatomic measurements of post-RP continence when combined with clinical multivariable models. Materials and Methods In this retrospective cohort study, continence outcomes were evaluated in men who underwent RP from August 2015 to October 2019. Preoperative MRI-based anatomic measures were obtained retrospectively by four abdominal radiologists. Before participation, these radiologists completed measure-specific training. Logistic regression models were developed with clinical variables alone, MRI variables alone, and combined variables for predicting continence at 3, 6, and 12 months after RP; some patient data were missing). Conclusion Preoperative MRI-measured coronal membranous urethra length was an independent predictor of urinary continence after prostatectomy. © RSNA, 2022 Online supplemental material is available for this article.It is unclear whether synesthesia is one condition or many, and this has implications for whether theories should postulate a single cause or multiple independent causes. Study 1 analyses data from a large sample of self-referred synesthetes (N = 2,925), who answered a questionnaire about N = 164 potential types of synesthesia. Clustering and factor analysis methods identified around seven coherent groupings of synesthesia, as well as showing that some common types of synesthesia do not fall into any grouping at all (mirror-touch, hearing-motion, tickertape). There was a residual positive correlation between clusters (they tend to associate rather than compete). Moreover, we observed a "snowball effect" whereby the chances of having a given cluster of synesthesia go up in proportion to the number of other clusters a person has (again suggesting non-independence). Clusters tended to be distinguished by shared concurrent experiences rather than shared triggering stimuli (inducers). We speculate that modulatory feedback pathways from the concurrent to inducers may play a key role in the emergence of synesthesia. Study 2 assessed the external validity of these clusters by showing that they predict performance on other measures known to be linked to synesthesia.In the Dutch nursing context, work remains in strengthening the voice of nurses serving as frontline health care providers and board members alike. Conceptual clarity of Public Opinion Leadership (POL) in nursing practice is needed to provide attributes, antecedents and consequences for nurses and nurse leaders so they can contribute in the public debate and policy making processes. Using Rodgers' method of evolutionary concept analysis and the key words "POL," "lobbying" and "public affairs," we searched PubMed (including MEDLINE), CINAHL, PsycINFO and Cochrane Library for articles written in English, published between January 1999 and May 2020, which resulted in a final selection of seven studies. link= https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html In addition, transcripts of an expert panel discussion regarding POL were analyzed. Attributes of POL are credibility, accessibility, altruism, dynamic networking and sense of systemness. Antecedents are a clinical background, authentic authority, policy and political awareness and strategic skills. The main consequences of POL entail influencing those who are involved in policy making processes, a new generation of public opinion leaders, and the raising of bottom-up political leaders. POL is a relatively new concept for nursing, with increasing interest given the need to ensure quality of care by increasing the use of evidence in clinical practice. POL in nursing practice is defined as the action of influencing public debate regarding policy making processes by maintaining dynamic (social) networks, having a high sense of systemness, and being (clinically) credible, altruistic and accessible to peers and a wide variety of stakeholders.As the Biden administration took office last January, with the pandemic peaking at more than 130,000 COVID-19 hospitalizations in the United States, there were high hopes for a new plan of "sticking to the science" and expectations that public health policies, communication, and trust would return to levels not seen for many years. That didn't happen. Why?The globally circulating severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) variant of concern Omicron (B.1.1.529) has a large number of mutations, especially in the spike protein, indicating that recognition by neutralizing antibodies may be compromised. We tested Wuhan (Wuhan-Hu-1 reference strain), Beta (B.1.351), Delta (B.1.617.2), or Omicron pseudoviruses with sera of 51 participants who received two or three doses of the messenger RNA (mRNA)-based COVID-19 vaccine BNT162b2. After two doses, Omicron-neutralizing titers were reduced >22-fold compared with Wuhan-neutralizing titers. One month after the third vaccine dose, Omicron-neutralizing titers were increased 23-fold relative to their levels after two doses and were similar to levels of Wuhan-neutralizing titers after two doses. The requirement of a third vaccine dose to effectively neutralize Omicron was confirmed with sera from a subset of participants using live SARS-CoV-2. These data suggest that three doses of the mRNA vaccine BNT162b2 may protect against Omicron-mediated COVID-19.A damaging inflammatory response is implicated in the pathogenesis of severe coronavirus disease 2019 (COVID-19), but mechanisms contributing to this response are unclear. In two prospective cohorts, early non-neutralizing, afucosylated immunoglobulin G (IgG) antibodies specific to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) were associated with progression from mild to more severe COVID-19. https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html To study the biology of afucosylated IgG immune complexes, we developed an in vivo model that revealed that human IgG-Fc-gamma receptor (FcγR) interactions could regulate inflammation in the lung. Afucosylated IgG immune complexes isolated from patients with COVID-19 induced inflammatory cytokine production and robust infiltration of the lung by immune cells. In contrast to the antibody structures that were associated with disease progression, antibodies that were elicited by messenger RNA SARS-CoV-2 vaccines were highly fucosylated and enriched in sialylation, both modifications that reduce the inflammatory potential of IgG. Vaccine-elicited IgG did not promote an inflammatory lung response. These results show that human IgG-FcγR interactions regulate inflammation in the lung and define distinct lung activities mediated by the IgG that are associated with protection against, or progression to, severe COVID-19.
According to DSM-5, catatonia and delirium are mutually exclusive clinical syndromes. The investigators explored the co-occurrence of delirium and catatonia (i.e., catatonic delirium) and the clinical significance of this syndrome with a sample of neurological patients.
This prospective study with consecutive sampling included patients diagnosed with delirium at the National Institute of Neurology and Neurosurgery of Mexico. DSM-5 criteria for delirium, the Confusion Assessment Method, and the Delirium Rating Scale-Revised-98 were used to select and characterize patients. Catatonia was assessed using the Bush-Francis Catatonia Rating Scale and DSM-5 diagnostic criteria. Logistic regression analysis was performed to identify etiological factors associated with catatonic delirium.
A total of 264 patients with delirium were included, 61 (23%) of whom fulfilled the criteria for catatonia and delirium simultaneously. Brain tumors, subarachnoid hemorrhage, acute hydrocephalus, and ischemic stroke were associated with delirium without catatonic signs. Catatonic delirium was observed among patients with encephalitis, epilepsy, brain neoplasms, and brain tuberculosis. After multivariate analysis, the association between catatonic delirium and encephalitis (both viral and anti-
-methyl-d-aspartate receptor [NMDAR]) was confirmed.
Delirium is a common complication of neurological diseases, and it can coexist with catatonia. The recognition of catatonic delirium has clinical significance in terms of etiology, as it was significantly associated with viral and anti-NMDAR encephalitis.
Delirium is a common complication of neurological diseases, and it can coexist with catatonia. The recognition of catatonic delirium has clinical significance in terms of etiology, as it was significantly associated with viral and anti-NMDAR encephalitis.
Symptoms of mental disorders are common, are underrecognized, and contribute to worse outcomes after traumatic brain injury (TBI). Post-TBI, prevalence of anxiety disorders and prevalence of posttraumatic stress disorder (PTSD) are comparable with that of depression, but evidence-based treatment guidelines are lacking. The investigators examined psychotropic medication use and psychotherapy patterns among individuals diagnosed with anxiety disorders and PTSD post-TBI.
Administrative claims data were used to compare the prevalence and patterns of pharmacotherapy and psychotherapy utilization among individuals diagnosed with an anxiety disorder or PTSD post-TBI.
Among 207,354 adults with TBI, prevalence of anxiety disorders was 20.5%, and prevalence of PTSD was 0.6% post-TBI. Receipt of pharmacotherapy pre- and post-TBI (anxiety pre-TBI=58.4%, post-TBI=76.2%; PTSD pre-TBI=53.7%, post-TBI=75.2%) was considerably more common than receipt of psychotherapy (anxiety pre-TBI=5.8%, post-TBI=19.1%; PTSD pre-TBI=1therapy engagement suggests that barriers and facilitators to psychotherapy utilization post-TBI should be examined in future studies.Parvalbumin (PV) interneurons are present in multiple brain regions and produce complex influences on brain functioning. An increasing number of research findings indicate that the function of these interneurons is more complex than solely to inhibit pyramidal neurons in the cortex. They generate feedback and feedforward inhibition of cortical neurons, and they are critically involved in the generation of neuronal network oscillation. These oscillations, generated by various brain regions, are linked to perceptions, thought processes, and cognitive functions, all of which, in turn, influence human emotions and behavior. Both animal and human studies consistently have found that meditation practice results in enhancement in the effects of alpha-, theta-, and gamma-frequency oscillations, which may correspond to positive changes in cognition, emotion, conscious awareness, and, subsequently, behavior. Although the study of meditation has moved into mainstream neuroscience research, the link between PV interneurons and any role they might play in meditative states remains elusive. This article is focused primarily on gamma-frequency oscillation, which is generated by PV interneurons, to develop insight and perspective into the role of PV interneurons in meditation. This article also points to new and emerging directions that address whether this role of PV interneurons in meditation extends to a beneficial, and potentially therapeutic, role in the treatment of common psychiatric disorders, including schizophrenia.
Increased impulsivity is a hallmark trait of some neuropsychiatric illnesses, including addiction, traumatic brain injury, and externalizing disorders. The authors hypothesized that altered cerebral white matter microstructure may also underwrite normal individual variability in impulsive behaviors and tested this among healthy individuals.
Impulsivity and diffusion tensor imaging (DTI) data were collected from 74 healthy adults (32 women; mean age=36.6 years [SD=13.6]). Impulsivity was evaluated using the Barratt Impulsiveness Scale-11, which provides a total score and scores for three subdomains attentional, motor, and nonplanning impulsiveness. DTI was processed using the Enhancing Neuro Imaging Genetics Through Meta Analysis-DTI analysis pipeline to measure whole-brain and regional white matter fractional anisotropy (FA) values in 24 tracts.
Whole-brain total average FA was inversely correlated with motor impulsiveness (r=-0.32, p=0.007) and positively correlated with nonplanning impulsiveness (r=0.29, p=0.02); these correlations were significant after correction for multiple comparisons. Additional significant correlations were observed for motor impulsiveness and regional FA values for the corticospinal tract (r=-0.29, p=0.01) and for nonplanning impulsiveness and regional FA values for the superior fronto-occipital fasciculus (r=0.32, p=0.008).
These results provide initial evidence that the motor and nonplanning subdomains of impulsive behavior are linked to specific white matter microstructural connectivity, supporting the notion that impulsivity is in part a network-based construct involving white matter microstructural integrity among otherwise healthy populations.
These results provide initial evidence that the motor and nonplanning subdomains of impulsive behavior are linked to specific white matter microstructural connectivity, supporting the notion that impulsivity is in part a network-based construct involving white matter microstructural integrity among otherwise healthy populations.
The authors investigated for presence of cognitive impairment after occurrence of bilateral lesions of the genu of the internal capsule (GIC). Clinical and neuropsychological features of unilateral GIC lesions have previously been studied, but the cognitive profile of bilateral lesions of the GIC has not been fully explored.
An investigation was conducted of neurocognitive deficits and computerized tomography MRI findings among 4,200 stroke patients with bilateral GIC involvement who were admitted to the hospital between January 2010 and October 2018.
Eight patients with bilateral lesions of the capsular genu were identified and their data analyzed. Overall, behavioral and cognitive dysfunction were characterized by impairment of frontal, memory, and executive functions. Attention and abstraction were present among all eight patients (100%); apathy, abulia, and executive dysfunctions, among seven (87.5%); global mental dysfunction and planning deficits, among six (75.0%); short-term verbal memory deficits and language dysfunctions, among five (62.5%); long-term verbal memory deficits, among four (50.0%); and spatial memory deficits, reading, writing, counting dysfunctions, and anarthria, among two (25.0%). Four of the patients (50.0%) without a history of cognitive disorder showed severe mental deterioration compatible with the clinical picture of dementia. A clinical picture of dementia was still present in these patients 6 months after stroke.
Bilateral lesions of the capsular genu appearing either simultaneously or at different times were significantly associated with executive dysfunctions.
Bilateral lesions of the capsular genu appearing either simultaneously or at different times were significantly associated with executive dysfunctions.
The investigators examined the factors predictive of novel oppositional defiant disorder in the 6-12 months following traumatic brain injury (TBI).
Children ages 5-14 years old who experienced a TBI were recruited from consecutive admissions to five hospitals. Participants were evaluated soon after injury (baseline) for preinjury characteristics, including psychiatric disorders, adaptive function, family function, psychosocial adversity, family psychiatric history, socioeconomic status, and injury severity, to develop a biopsychosocial predictive model for development of novel oppositional defiant disorder. MRI analyses were conducted to examine potential brain lesions. Psychiatric outcome, including that of novel oppositional defiant disorder, was assessed 12 months after injury.
Although 177 children were recruited for the study, 120 children without preinjury oppositional defiant disorder, conduct disorder, or disruptive behavior disorder not otherwise specified (DBD NOS) returned for the 12-month assessment. link2 Of these 120 children, seven (5.8%) exhibited novel oppositional defiant disorder, and none developed conduct disorder or DBD NOS in the 6-12 months postinjury. Novel oppositional defiant disorder was significantly associated with lower socioeconomic status, higher psychosocial adversity, and lower preinjury adaptive functioning.
These results demonstrate that novel oppositional defiant disorder following TBI selectively and negatively affects an identifiable group of children. Both proximal (preinjury adaptive function) and distal (socioeconomic status and psychosocial adversity) psychosocial variables significantly increase risk for this outcome.
These results demonstrate that novel oppositional defiant disorder following TBI selectively and negatively affects an identifiable group of children. Both proximal (preinjury adaptive function) and distal (socioeconomic status and psychosocial adversity) psychosocial variables significantly increase risk for this outcome.We report a new reversible lysine conjugation that features a novel diazaborine product and much slowed dissociation kinetics in comparison to the previously known iminoboronate chemistry. Incorporating the diazaborine-forming warhead RMR1 to a peptide ligand gives potent and long-acting reversible covalent inhibitors of the staphylococcal sortase. The efficacy of sortase inhibition is demonstrated via biochemical and cell-based assays. A comparative study of RMR1 and an iminoboronate-forming warhead highlights the significance and potential of modulating bond dissociation kinetics in achieving long-acting reversible covalent inhibitors.Organic photovoltaics (OPV) is an emerging solar cell technology that offers vast advantages such as low-cost manufacturing, transparency, and solution processability. However, because the performance of OPV devices is still disappointing compared to their inorganic counterparts, better understanding of how controlling the molecular-level morphology can impact performance is needed. link3 To this end, one has to overcome significant challenges that stem from the complexity and heterogeneity of the underlying electronic structure and molecular morphology. In this Letter, we address this challenge in the context of the DBP/C70 OPV system by employing a modular workflow that combines recent advances in electronic structure, molecular dynamics, and rate theory. We show how the wide range of interfacial pairs can be classified into four types of interfacial donor-acceptor geometries and find that the least populated interfacial geometry gives rise to the fastest charge transfer (CT) rates.An earth-abundant and inexpensive Mn(I)-catalyzed alkylation of 2-pyridone with maleimide has been reported for the first time, in contrast to previously reported Diels-Alder products. Notably, an unexpected rearrangement has been discovered in the presence of acetic acid, which also provides a unique class of compounds bearing three different N-heterocycles with an all-carbon quaternary center. Furthermore, single crystal X-ray and HRMS revealed a five-membered manganacycle intermediate. This methodology tolerates a wide variety of functional groups delivering the alkylated products in moderate to excellent yields.A general phase-transfer-catalyzed asymmetric (n+1) (n = 4 or 5) annulation reaction, featuring the direct coupling of simple oxindoles with alkyl dihalides that are allylic/benzylic and non-allylic/benzylic, has been developed to provide previously inaccessible cyclopentane- and cyclohexane-fused spirooxindole scaffolds with high yields and enantioselectivities (88-95% ee). Along with a broad scope and mild conditions, the new protocol also enables a two-step and gram-scale synthesis of the core of the drug ubrogepant.Considerable efforts have been devoted to developing oxygen evolution reaction (OER) catalysts based on transition metal oxides. Polyoxometalates (POMs) can be regarded as model compounds of transition metal oxides, and cobalt-containing POMs (Co-POMs) have received significant interest as candidates. Nanocomposites based on Co-POMs have been reported to show high OER activities due to synergistic effects among the components; however, the role of each component is unclear due to its complex structure. Herein, we utilize porous ionic crystals (PICs) based on Co-POMs, which enable a composition-structure-function relationship to be established to understand the origin of the synergistic catalysis. Specifically, a Keggin-type POM [α-CoW12O40]6- and a Cr complex [Cr3O(OOCCH2CN)6(H2O)3]+ are implemented as PIC building blocks for the OER under nonbasic conditions. The potentially OER-active but highly soluble [α-CoW12O40]6- was successfully anchored in the crystalline PIC matrix via Coulomb interactions and hydrogen bonding induced by polar cyano groups of the Cr complex. The PIC exhibits efficient and sustained OER catalytic activity, while each building block is inactive. The Tafel slope of the linear sweep voltammetry curve and the relatively large kinetic isotope effect value suggest that elementary steps closely related to the OER rate involve single-electron and proton transfer reactions. Electrochemical and spectroscopic studies clearly show that the synergistic catalysis originates from the charge transfer from the Cr complex to [α-CoW12O40]6-; the increased electron density of [α-CoW12O40]6- may increase its basicity and accelerate proton abstraction as well as enhance electron transfer to stabilize the reaction intermediates adsorbed on [α-CoW12O40]6-.Understanding the mechanism that connects heat transport with crystal structures and order/disorder phenomena is crucial to develop materials with ultralow thermal conductivity (κ), for thermoelectric and thermal barrier applications, and requires the study of highly pure materials. We synthesized the n-type sulfide CuPbBi5S9 with an ultralow κ value of 0.6-0.4 W m-1 K-1 in the temperature range 300-700 K. In contrast to prior studies, we show that this synthetic sulfide does not exhibit the ordered gladite mineral structure but instead forms a copper-deficient disordered aikinite structure with partial Pb replacement by Bi, according to the chemical formula Cu1/3□2/3Pb1/3Bi5/3S3. By combining experiments and lattice dynamics calculations, we elucidated that the ultralow κ value of this compound is due to very low energy optical modes associated with Pb and Bi ions and, to a smaller extent, Cu. This vibrational complexity at low energy hints at substantial anharmonic effects that contribute to enhance phonon scattering. Importantly, we show that this aikinite-type sulfide, despite being a poor semiconductor, is a potential matrix for designing novel, efficient n-type thermoelectric compounds with ultralow κ values. A drastic improvement in the carrier concentration and thermoelectric figure of merit have been obtained upon Cl for S and Bi for Pb substitution. The Cu1-x□xPb1-xBi1+xS3 series provides a new, interesting structural prototype for engineering n-type thermoelectric sulfides by controlling disorder and optimizing doping.In this paper, the application of differentiating catalysis in the [4 + 2]-cycloaddition between 2-alkyl-3-formylheteroarenes and α,β-unsaturated aldehydes is described. Within the developed approach, the same aminocatalyst is employed for the independent activation of both starting materials, differentiating their properties via LUMO-lowering and HOMO-rising principles. By the combination of dearomative dienamine activation with iminium ion chemistry high enantio- and diastereoselectivity of the doubly asymmetric process was accomplished. Selected transformations of products were also demonstrated.The dimerization of transactive response DNA-binding protein of 43 kDa (TDP-43) is crucial for the RNA metabolism, and the higher-order aggregation of TDP-43 would induce several neurodegenerative diseases. The dimerization and aggregation of TDP-43 are regulated by the phosphorylation on its N-terminal domain (NTD). Understanding the regulation mechanism of TDP-43 NTD dimerization is crucial for the preventing of harmful aggregation and the associated diseases. In this study, the dimerization processes of wild-type (WT), phosphorylated S48 (pS48), and phosphomimic S48E mutation (S48E) of TDP-43 NTD are characterized by the enhanced sampling technology. Our results show that the phosphorylation not only shift the conformation population of bound and unbound state of TDP-43 NTD, but also would regulate the dimerization processes, including increase the binding free-energy barrier. The phosphomimic mutation would also shift the conformational space of TDP-43 NTD dimer to the unbound structures; however, the thermodynamic and kinetic properties of the dimerization processes between the phosphorylated and phosphomimic mutant systems are distinct, which reminds us to carefully study the phosphorylation regulation by using the phosphomimic mutations.A photochemical approach for the preparation of α-keto-N-acyl sulfoximines from NH sulfoximines and gem-difluoroalkenes has been developed. In the presence of NBS, the reactions proceed in air without the need of a photocatalyst or additional oxidant. Results of mechanistic studies suggest that the two oxygens in the products stem from water and dioxygen.A highly modular 1,4-difunctionalization of 1,3-dienes with bromodifluoroacetamides and sulfinates/amines through a photoinduced palladium-catalyzed radical relay process is described herein. This developed protocol offers a facile and general route to access a variety of value-added CF2-incorporated alkenes in moderate to good yields. The versatility and flexibility of this approach have been well illustrated by readily accessible starting materials, synthetic convenience, and wide functional group compatibility.Mechano-bactericidal surfaces deliver lethal effects to contacting bacteria. Until now, cell death has been attributed to the mechanical stress imparted to the bacterial cell envelope by the surface nanostructures; however, the process of bacterial death encountering nanostructured surfaces has not been fully illuminated. Here, we perform an in-depth investigation of the mechano-bactericidal action of black silicon (bSi) surfaces toward Gram-negative bacteria Pseudomonas aeruginosa. We discover that the mechanical injury is not sufficient to kill the bacteria immediately due to the survival of the inner plasma membrane. Instead, such sublethal mechanical injury leads to apoptosis-like death (ALD) in affected bacteria. In addition, when the mechanical stress is removed, the self-accumulated reactive oxygen species (ROS) incur poststress ALD in damaged cells in a nonstressed environment, revealing that the mechano-bactericidal actions have sustained physiological effects on the bacterium. This work creates a new facet and can introduce many new regulation tools to this field.Complex van der Waals heterostructures from layered molecular stacks are promising optoelectronic materials offering the means to efficient, modular charge separation and collection layers. The effect of stacking in the electrodynamics of such hybrid organic-inorganic two-dimensional materials remains largely unexplored, whereby molecular scale engineering could lead to advanced optical phenomena. For instance, tunable Fano engineering could make possible on-demand transparent conducting layers or photoactive elements, and passive cooling. We employ an adapted Gersten-Nitzan model and real time time-dependent density functional tight-binding to study the optoelectronics of self-assembled monolayers on graphene nanoribbons. We find Fano resonances that cause electromagnetic induced opacity and transparency and reveal an additional incoherent process leading to interlayer exciton formation with a characteristic charge transfer rate. These results showcase hybrid van der Waals heterostructures as paradigmatic 2D optoelectronic stacks, featuring tunable Fano optics and unconventional charge transfer channels.Dynamic covalent bonds are useful tools in a wide range of applications. Although various reversible chemical reactions have been studied for this purpose, the requirement for harsh conditions, such as high temperature and low or high pH, to activate generally stable covalent bonds limits their potential applications involving biomolecules or household utilization. Here, we report the design, synthesis, characterization, and dynamic covalent bonding properties of 1,2-disubstituted 1,2-dihydro-1,2,4,5-tetrazine-3,6-dione (TETRAD). Hetero-Diels-Alder reactions of TETRAD with furan derivatives and their retro-reactions proceeded rapidly at room temperature under neutral conditions, enabling a chemically induced sol-gel transition system.Combining solid phase microextraction (SPME) and mass spectrometry (MS) analysis has become increasingly important to many bioanalytical, environmental, and forensic applications due to its simplicity, rapid analysis, and capability of reducing matrix effects for complex samples. To further promote the adoption of SPME-MS based analysis and expand its application scope calls for efficient and convenient interfaces that couple the SPME sample handling with the efficient analyte ionization for MS. Here, we report a novel interface that integrates both the desorption and the ionization steps in one device based on the capillary vibrating sharp-edge spray ionization (cVSSI) method. We demonstrated that the cVSSI is capable of nebulizing liquid samples in a pulled-tip glass capillary with a battery powered function generator. The cVSSI device allows the insertion of a SPME probe into the spray capillary for desorption and then direct nebulization of the desorption solvent in situ. With the integrated interface, we have demonstrated rapid MS analysis of drug compounds from serum samples. Quantitative determination of various drug compounds including metoprolol, pindolol, acebutolol, oxprenolol, capecitabine, and irinotecan was achieved with good linearity (R2 = 0.97-0.99) and limit of detection ranging from 0.25 to 0.59 ng/mL without using a high voltage source. Only 3.5 μL of desorption solvent and 3 min desorption time were needed for the present method. Overall, we demonstrated a portable SPME-MS interface featuring high sensitivity, short analysis time, small footprint, and low cost, which makes it an attractive method for many applications requiring sample cleanup including drug compound monitoring, environmental sample analysis, and forensic sample analysis.Filamin C (FLN c) is a novel allergen in shellfish. In this study, FLN c from Scylla paramamosain was divided into three regions for recombinant expression based on the number of domains and amino acids. Using dot blot and basophil activation tests, the allergic predominant region of FLN c was determined to be 336-531 amino acid positions (named FLN c-M). It was confirmed that by X-ray diffraction, the crystal structure of FLN c-M with immunoglobulin-like folding at a resolution of 1.7 Å was obtained. The monomer was a barrel structure composed of 16 β-strands and 2 α-helices. Three conformational epitopes were predicted, six linear epitopes were verified by serological test, and they were positioned on the crystal structure of FLN c-M. For the first time, the crystal structure of the allergic predominant region of FLN c was determined, and it provided an accurate template for the localization of IgE epitopes.Degradation of the mechanical properties of α-titanium, which is used to manufacture parts of jet engines, due to high-temperature oxidation is detrimental for the engine components. Therefore, to overcome this problem there are ongoing endeavors to develop novel oxidation-resistant titanium alloys and improve the properties of the existing ones. In an effort to understand the effect of alloying on oxidation of the α-Ti(0001) surface and to identify descriptors for rational design of oxidation-resistant alloys, in this work, using density functional theory-based calculations, we studied oxygen sorption and surface to subsurface diffusion on pure and alloyed α-Ti(0001) surfaces. Zr, Hf, Nb, and Mo from the d block and Al, Ga, Si, and Ge from the p block were used as alloying elements. We find that the alloying elements prefer to segregate on the surface compared to the subsurface layers. Our calculations show that the diffusion barrier correlates with the difference in the electronegativity between the alloying element and Ti. Elements which are more electropositive than Ti are found to hinder the oxygen dissolution in Ti and vice versa. We propose that the electronegativity difference can act as a good descriptor for choosing alloying elements. Our results are in reasonably good agreement with experimental reports on the growth of oxide layers on these alloyed Ti surfaces.A rationalization for the chirality transfer mechanism in the supramolecular host-guest assemblies of an achiral Zn(II) porphyrin dimer (host) and a series of chiral diamines and diamino esters (substrates) via cyclic dimer formation has been reported for the first time. Stepwise formations of 22 host-guest cyclic dimers and 12 host-guest monomeric complexes have been observed via intermolecular assembling and disassembling processes. A large bisignate CD couplet was observed for the cyclic dimer, whereas the monomeric complexes exhibited negligible CD intensity. Crystallographic characterizations demonstrate that the strong intermolecular H bonding in cyclic dimers is responsible for their stability over the linear chain, which thereby display high-intensity bisignate CD couplets. In order to minimize the steric crowding within the host-guest assembly, the cyclic dimer switches its helicity toward the conformer having less steric hindrance. The cyclic scaffold is oriented according to the pre-existing chirality of the substrate in both the solid and solution phases the substrates having R chirality display a negative CD couplet, whereas the substrates with S chirality display a positive couplet. Opposite signs for the CD couplets between R and S substrates suggest that the stereographic projection at the chiral centers solely dictates the overall helicity of the cyclic dimer. DFT studies further support the experimental observations.Size-based separation of particles in microfluidic devices can be achieved using arrays of micro- or nanoscale posts using a technique known as deterministic lateral displacement (DLD). To date, DLD arrays have been limited to parallelogram or rotated-square arrangements of posts, with various post shapes having been explored in these two principal arrangements. This work examines a new DLD geometry based on patterning obtainable through self-assembly of single-layer nanospheres, which we call hexagonally arranged triangle (HAT) geometry. Finite element simulations are used to characterize the DLD separation properties of the HAT geometry. The relationship between the array angle, the gap spacing, and the critical diameter for separation is derived for the HAT geometry and expressed in a similar mathematical form as conventional parallelogram and rotated-square DLD arrays. At array angles less then 7°, HAT structures demonstrate smaller particle sorting capability (smaller critical diameter-to-gap spacing ratio) compared to published experimental results for parallelogram-type DLD arrays with circular posts. Experimental validation of DLD separation confirms the separation ability of the HAT array geometry. It is envisioned that this work will provide the first step toward future implementation of nanoscale DLD arrays fabricated by low-cost, bottom-up self-assembly approaches.The α- and β-modifications of barium metaborate are important functional materials used in optoelectronic devices. A new theoretically predicted modification of BaB2O4 has been synthesized under conditions of 3 GPa and 900 °C, using the DIA-type apparatus. The new high-pressure modification, γ-BaB2O4, crystallizes in a centrosymmetrical group of monoclinic syngony (P21/n (#14), a = 4.6392(4) Å, b = 10.2532(14) Å, c = 7.066(1) Å, β = 91.363(10)°, Z = 4). A distinctive feature of the γ-BaB2O4 structure is the presence of edge-sharing tetrahedra [B2O6] which form infinite double chains ∞[B4O4O8/2] stretching along the a axis. The number of known structural types with the [B2O6] group is limited. Phase γ-BaB2O4 has the shortest distance between boron atoms of shared tetrahedra among all currently known compounds. The [B2O6] group angles are 95.5° and 105.5°. Thermodynamic stability and electronic properties of the γ-BaB2O4 modification were studied. The width of the band gap, calculated using the HSE06 functional, is 7.045 eV which implies transparency in the deep-UV region. Experimental and numerical methods which demonstrate a good match were used to the study the Raman spectra of γ-BaB2O4 and β-BaB2O4 modifications. In the Raman spectra of γ-BaB2O4, the most intense band at a frequency of 853 cm-1 was found to correspond to the symmetric bending mode of the B-O-B-O ring in edge-sharing tetrahedra.The application of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) imaging to quantitative analyses is restricted by the variability of MS intensity of the analytes in nonreproducible matrix crystals of tissues. To overcome this challenge, a fluorescence-assisted spraying method was developed for a constant matrix amount employing an MS-detectable fluorescent reagent, rhodamine 6G (R6G), which was sprayed with the matrix. To form a homogeneous matrix crystal on the tissue section, a matrix solution, 1,5-diaminonaphthalene (10 mg/mL), containing R6G (40 μg/mL) and O-dinitrobenzene (O-DNB, 10 mg/mL) was sprayed until the desired constant fluorescence intensity was achieved. Compared with that obtained via conventional cycle-number-fixed spraying [relative standard deviation (RSD) = 31.1%], the reproducibility of the relative MS intensity of the analyte [ferulic acid (FA), RSD = 3.1%] to R6G was significantly improved by the fluorescence-assisted matrix spraying. This result indicated that R6G could be employed as an index of the matrix amount and an MS normalizing standard. The proposed matrix spraying successfully quantified nifedipine (0.5-40 pmol/mm2 in the positive mode, R2 = 0.965) and FA (0.5-75 pmol/mm2 in the negative mode, R2 = 0.9972) in the kidney section of a rat. Employing the quantitative MALDI-MS imaging assay, FA, which accumulated in the kidney of the rat after 50 mg/kg was orally administered, was visually determined to be 3.5, 3.0, and 0.2 μmol/g tissue at 15, 30, and 60 min, respectively.For several decades, surface grafted polyethylene glycol (PEG) has been a go-to strategy for preserving the synthetic identity of liposomes in physiological milieu and preventing clearance by immune cells. However, the limited clinical translation of PEGylated liposomes is mainly due to the protein corona formation and the subsequent modification of liposomes' synthetic identity, which affects their interactions with immune cells and blood residency. Here we exploit the electric charge of DNA to generate unPEGylated liposome/DNA complexes that, upon exposure to human plasma, gets covered with an opsonin-deficient protein corona. The final product of the synthetic process is a biomimetic nanoparticle type covered by a proteonucleotidic corona, or "proteoDNAsome", which maintains its synthetic identity in vivo and is able to slip past the immune system more efficiently than PEGylated liposomes. Accumulation of proteoDNAsomes in the spleen and the liver was lower than that of PEGylated systems. link2 Our work highlights the importance of generating stable biomolecular coronas in the development of stealth unPEGylated particles, thus providing a connection between the biological behavior of particles in vivo and their synthetic identity.The harm caused by small rubber particles generated from tire abrasion to the atmosphere is receiving a continuing concern. For developing environmental-friendly tire tread materials with high wear resistance, building the strong interface between nano-fillers and rubber matrix is the primary challenge. Herein, ionic liquid (IL, 1-allyl-3-methylimidazole chloride) was used to modify graphene oxide (GO) by π-cation interaction and hydrogen bonding between IL and GO. Furthermore, an IL-GO/natural rubber (NR) masterbatch possessing fine dispersion of GO was prepared by the emulsion compounding method, and thereafter, a further compound with solution polymerized styrene butadiene rubber (SSBR) was fabricated for the tread rubber composite. Results showed that the double bond in the IL enhanced the cross-linking reaction during the vulcanization of rubber composites occurred at high temperature, leading to an elevated interfacial interaction between the IL-modified GO and the rubber macromolecules. Compared with silicon dioxide (SiO2)-filled NR/SSBR composites, the cross-link density, 300% modulus, and tear strength of the IL-GO/SiO2/NR/SSBR composites were increased by 10.2, 42.6, and 20.2%, respectively. Importantly, the wear resistance of the IL-GO/SiO2/NR/SSBR composites was improved by 17.3%, ascribing to the strong interface between IL-GO and rubber macromolecules.Mass spectrometry (MS)-based quantitative proteomic methods have become some of the major tools for protein biomarker discovery and validation. The recently developed parallel reaction monitoring-parallel accumulation-serial fragmentation (prm-PASEF) approach on a Bruker timsTOF Pro mass spectrometer allows the addition of ion mobility as a new dimension to LC-MS-based proteomics and increases proteome coverage at a reduced analysis time. In this study, a prm-PASEF approach was used for the multiplexed absolute quantitation of proteins in human plasma using isotope-labeled peptide standards for 125 plasma proteins, over a broad (104-106) dynamic range. Optimization of LC and MS parameters, such as accumulation time and collision energy, resulted in improved sensitivity for more than half of the targets (73 out of 125 peptides) by increasing the signal-to-noise ratio by a factor of up to 10. Overall, 41 peptides showed up to a 2-fold increase in sensitivity, 25 peptides showed up to a 5-fold increase in sensitivity, and 7 peptides showed up to a 10-fold increase in sensitivity. Implementation of the prm-PASEF method allowed absolute protein quantitation (down to 1.13 fmol) in human plasma samples. A comparison of the concentration values of plasma proteins determined by MRM on a QTRAP instrument and by prm-PASEF on a timsTOF Pro revealed an excellent correlation (R2 = 0.97) with a slope of close to 1 (0.99), demonstrating that prm-PASEF is well suited for "absolute" quantitative proteomics.Rapid, ultrasensitive, and selective quantification of circulating microRNA (miRNA) biomarkers in body fluids is increasingly deployed in early cancer diagnosis, prognosis, and therapy monitoring. While nanoparticle tags enable detection of nucleic acid or protein biomarkers with digital resolution and subfemtomolar detection limits without enzymatic amplification, the response time of these assays is typically dominated by diffusion-limited transport of the analytes or nanotags to the biosensor surface. Here, we present a magnetic activate capture and digital counting (mAC+DC) approach that utilizes magneto-plasmonic nanoparticles (MPNPs) to accelerate single-molecule sensing, demonstrated by miRNA detection via toehold-mediated strand displacement. Spiky Fe3O4@Au MPNPs with immobilized target-specific probes are "activated" by binding with miRNA targets, followed by magnetically driven transport through the bulk fluid toward nanoparticle capture probes on a photonic crystal (PC). By spectrally matching the localized surface plasmon resonance of the MPNPs to the PC-guided resonance, each captured MPNP locally quenches the PC reflection efficiency, thus enabling captured MPNPs to be individually visualized with high contrast for counting. We demonstrate quantification of the miR-375 cancer biomarker directly from unprocessed human serum with a 1 min response time, a detection limit of 61.9 aM, a broad dynamic range (100 aM to 10 pM), and a single-base mismatch selectivity. The approach is well-suited for minimally invasive biomarker quantification, enabling potential applications in point-of-care testing with short sample-to-answer time.Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr3 to a ⟨110⟩ oriented FAn+2PbnBr3n+2 structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate n phase in the FAn+2PbnBr3n+2 structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented mono-halide/cation perovskite. Proton transfer reaction-mass spectroscopy carried out to precisely quantify the decomposition product reveals that the organic solvent in the film is a key contributor to the structural transformation and, therefore, the chromism in the ⟨110⟩ structure. These intermediate n phases (2 ≤ n ≤ ∞) stabilize in metastable states in the FAn+2PbnBr3n+2 system, which is accessible via strain or optical or thermal input. The structure reversibility in the ⟨110⟩ perovskite allowed us to demonstrate a class of photochromic sensors capable of self-adaptation to lighting.Organic color centers (OCCs) are atomic defects that can be synthetically created in single-walled carbon nanotube hosts to enable the emission of shortwave infrared single photons at room temperature. link3 However, all known chemistries developed thus far to generate these quantum defects produce a variety of bonding configurations, posing a formidable challenge to the synthesis of identical, uniformly emitting color centers. https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html'>https://www.selleckchem.com/products/pci-32765.html Herein, we show that laser irradiation of the nanotube host can locally reconfigure the chemical bonding of aryl OCCs on (6,5) nanotubes to significantly reduce their spectral inhomogeneity. After irradiation the defect emission narrows in distribution by ∼26% to yield a single photoluminescence peak. We use hyperspectral photoluminescence imaging to follow this structural transformation on the single nanotube level. Density functional theory calculations corroborate our experimental observations, suggesting that the OCCs convert from kinetic structures to the more thermodynamically stable configuration. This approach may enable localized tuning and creation of identical OCCs for emerging applications in bioimaging, molecular sensing, and quantum information sciences.Two-dimensional (2D) materials and their in-plane and out-of-plane (i.e., van der Waals, vdW) heterostructures are promising building blocks for next-generation electronic and optoelectronic devices. Since the performance of the devices is strongly dependent on the crystalline quality of the materials and the interface characteristics of the heterostructures, a fast and nondestructive method for distinguishing and characterizing various 2D building blocks is desirable to promote the device integrations. In this work, based on the color space information on 2D materials' optical microscopy images, an artificial neural network-based deep learning algorithm is developed and applied to identify eight kinds of 2D materials with accuracy well above 90% and a mean value of 96%. More importantly, this data-driven method enables two interesting functionalities (1) resolving the interface distribution of chemical vapor deposition (CVD) grown in-plane and vdW heterostructures and (2) identifying defect concentrations of CVD-grown 2D semiconductors.