Adamantane-like Clusters Of The Zinc-group Elements

Three new types of chalcogenate-bridged adamantane-like clusters of the zinc-group elements have been studied in detail: those with alkylthiolates as bridging ligands, formulated as (({dollar}\mu{dollar}-{dollar}\rm SAlk)\sb6(MX)\sb4\rbrack\sp{lcub}2-{rcub}{dollar} (Alk = Me, Et, 1-Pr, 2-Pr, 1-Bu, 2-Bu, c-{dollar}\rm C\sb6H\sb{lcub}11{rcub}{dollar}(Cy), or CH{dollar}\sb2{dollar}Ph (Bz); M = Zn, Cd, or Hg; X = Cl, Br, or I); those with phosphines as terminal ligands, formulated as (({dollar}\mu{dollar}-ER){dollar}\sb6{dollar}(CdPPh{dollar}\sb3)\sb{lcub}4-n{rcub}{dollar}(Cd){dollar}\sb{lcub}n{rcub}\rbrack \sp{lcub}2+{rcub}{dollar} (E = S or Se; R = 1-Pr, 2-Pr, 1-{dollar}\rm C\sb5H\sb{lcub}11{rcub}{dollar} (1-Pe), Cy, or Ph; n = 0, 1, or 2); and those with halides as bridging ligands, formulated as (({dollar}\mu{dollar}-ER){dollar}\sb{lcub}6-m{rcub}(\mu{dollar}-X){dollar}\sb{lcub}m{rcub}{dollar}(MX){dollar}\sb4\rbrack\sp{lcub}2-{rcub}{dollar} (E = S or Se; R = Et, 1-Pr, 2-Pr, 1-Bu, Cy, of Ph; m = 0, 1, or 2; X = Cl, Br, or I; M = Cd or Hg). In total, seventy-one new clusters have been isolated analytically pure; more than one hundred species have been characterized in solution by multinuclear magnetic resonance; and three representative crystal structures have been obtained by X-ray analysis (carried out by others).;In general, for the adamantane-like species, the metal chemical shift, {dollar}\delta\sb{lcub}\rm Cd{rcub}{dollar} or {dollar}\delta\sb{lcub}\rm Hg{rcub}{dollar}, varies with R in the order primary alkyl {dollar}\u3e{dollar} secondary alkyl {dollar}\u3e{dollar} phenyl, with X in the order Cl {dollar}\u3e{dollar} Br {dollar}\u3e{dollar} I, and with temperature in the order reduced T {dollar}\u3e{dollar} ambient T. In a study of the mixed-metal clusters, (({dollar}\mu{dollar}-SAlk){dollar}\sb6{dollar}(MX){dollar}\sb{lcub}4-n{rcub}{dollar}(M{dollar}\sp\prime{dollar}X){dollar}\sb{lcub}n{rcub}{dollar}) {dollar}\sp{lcub}2-{rcub}{dollar}, (M/M{dollar}\sp\prime{dollar} = Cd/Zn, Cd/Hg, or Hg/Zn), {dollar}\delta\sb{lcub}\rm Cd{rcub}{dollar} varies with n in the order 0 {dollar}\u3e{dollar} 1 {dollar}\u3e{dollar} 2 {dollar}\u3e{dollar} 3 in Cd{dollar}\sb{lcub}4-n{rcub}{dollar}Zn{dollar}\sb{lcub}n{rcub}{dollar} or Cd{dollar}\sb{lcub}4-n{rcub}{dollar}Hg{dollar}\sb{lcub}n{rcub}{dollar} mixtures, while {dollar}\delta\sb{lcub}\rm Hg{rcub}{dollar} varies with n in the order {dollar}0\ \ 1\ \u3e\ 2\ \u3e\ 3{dollar} in Hg{dollar}\sb{lcub}4-n{rcub}{dollar}Zn{dollar}\sb{lcub}n{rcub}{dollar} mixture. For the mixed-halide clusters, (({dollar}\mu{dollar}-SPr{dollar}\sp{lcub}\rm i{rcub})\sb6{dollar}(CdX){dollar}\sb{lcub}4-n{rcub}{dollar}(CdX{dollar}\sp\prime)\sb{lcub}n{rcub}{dollar}) {dollar}\sp{lcub}2-{rcub}{dollar} (X/X{dollar}\sp\prime{dollar} = I/Br, I/Cl, or Br/Cl), it has been shown that when X is heavier than X{dollar}\sp\prime,\ \delta\sb{lcub}\rm Cd{rcub}{dollar} varies with n in the order {dollar}0\ \u3c\ 1\ \u3c\ 2\ \u3c\ 3{dollar} for CdX site, and in the order {dollar}1\ \u3c\ 2\ \u3c\ 3\ \u3c\ 4{dollar} for CdX{dollar}\sp\prime{dollar} site. In (({dollar}\mu{dollar}-{dollar}\rm ER)\sb6(Cd\sb{lcub}A{rcub}PPh\sb3)\sb{lcub}4-n{rcub}(Cd\sb{lcub}B{rcub})\sb{lcub}n{rcub}\rbrack \sp{lcub}2+{rcub},\ \delta\sb{lcub}Cd{rcub}{dollar} varies with n in the order {dollar}0\ \u3c\ 1\ \u3c\ 2{dollar} for Cd{dollar}\sb{lcub}\rm A{rcub}{dollar} or Cd{dollar}\sb{lcub}\rm B{rcub}{dollar}. Importantly, for Cd{dollar}\sb{lcub}\rm B{rcub}{dollar}, the PPh{dollar}\sb3{dollar}-free site, the terminal position can be occupied by OClO{dollar}\sb3\sp-{dollar} giving tetrahedral coordination geometry about the Cd. In (({dollar}\mu{dollar}-ER){dollar}\sb{lcub}6-m{rcub}(\mu{dollar}-X{dollar}\sb{lcub}m{rcub}{dollar}(MX{dollar}\sb4{dollar}) {dollar}\sp{lcub}2-{rcub}{dollar}, halides participate in bridging. When m = 2, the two bridging halides prefer to form a trans-({dollar}\mu{dollar}-X){dollar}\sb2{dollar} structure. These results provide model data for studies on metallothioneins and other biological systems with metal-cysteine sites

HyperINR: A Fast and Predictive Hypernetwork for Implicit Neural Representations via Knowledge Distillation

Implicit Neural Representations (INRs) have recently exhibited immense potential in the field of scientific visualization for both data generation and visualization tasks. However, these representations often consist of large multi-layer perceptrons (MLPs), necessitating millions of operations for a single forward pass, consequently hindering interactive visual exploration. While reducing the size of the MLPs and employing efficient parametric encoding schemes can alleviate this issue, it compromises generalizability for unseen parameters, rendering it unsuitable for tasks such as temporal super-resolution. In this paper, we introduce HyperINR, a novel hypernetwork architecture capable of directly predicting the weights for a compact INR. By harnessing an ensemble of multiresolution hash encoding units in unison, the resulting INR attains state-of-the-art inference performance (up to 100x higher inference bandwidth) and can support interactive photo-realistic volume visualization. Additionally, by incorporating knowledge distillation, exceptional data and visualization generation quality is achieved, making our method valuable for real-time parameter exploration. We validate the effectiveness of the HyperINR architecture through a comprehensive ablation study. We showcase the versatility of HyperINR across three distinct scientific domains: novel view synthesis, temporal super-resolution of volume data, and volume rendering with dynamic global shadows. By simultaneously achieving efficiency and generalizability, HyperINR paves the way for applying INR in a wider array of scientific visualization applications

AMD-DBSCAN: An Adaptive Multi-density DBSCAN for datasets of extremely variable density

DBSCAN has been widely used in density-based clustering algorithms. However, with the increasing demand for Multi-density clustering, previous traditional DSBCAN can not have good clustering results on Multi-density datasets. In order to address this problem, an adaptive Multi-density DBSCAN algorithm (AMD-DBSCAN) is proposed in this paper. An improved parameter adaptation method is proposed in AMD-DBSCAN to search for multiple parameter pairs (i.e., Eps and MinPts), which are the key parameters to determine the clustering results and performance, therefore allowing the model to be applied to Multi-density datasets. Moreover, only one hyperparameter is required for AMD-DBSCAN to avoid the complicated repetitive initialization operations. Furthermore, the variance of the number of neighbors (VNN) is proposed to measure the difference in density between each cluster. The experimental results show that our AMD-DBSCAN reduces execution time by an average of 75% due to lower algorithm complexity compared with the traditional adaptive algorithm. In addition, AMD-DBSCAN improves accuracy by 24.7% on average over the state-of-the-art design on Multi-density datasets of extremely variable density, while having no performance loss in Single-density scenarios. Our code and datasets are available at https://github.com/AlexandreWANG915/AMD-DBSCAN.Comment: Accepted at DSAA202

Transient receptor potential channel 1 deficiency impairs host defense and proinflammatory responses to bacterial infection by regulating protein kinase Cα signaling

Transient receptor potential channel 1 (TRPC1) is a nonselective cation channel that is required for Ca2+ homeostasis necessary for cellular functions. However, whether TRPC1 is involved in infectious disease remains unknown. Here, we report a novel function for TRPC1 in host defense against Gram-negative bacteria. TRPC1-/- mice exhibited decreased survival, severe lung injury, and systemic bacterial dissemination upon infection. Furthermore, silencing of TRPC1 showed decreased Ca2+ entry, reduced proinflammatory cytokines, and lowered bacterial clearance. Importantly, TRPC1 functioned as an endogenous Ca2+ entry channel critical for proinflammatory cytokine production in both alveolar macrophages and epithelial cells. We further identified that bacterium-mediated activation of TRPC1 was dependent on Toll-like receptor 4 (TLR4), which induced endoplasmic reticulum (ER) store depletion. After activation of phospholipase Cγ (PLC-γ), TRPC1 mediated Ca2+ entry and triggered protein kinase Cα (PKC-α) activity to facilitate nuclear translocation of NF-kB/Jun N-terminal protein kinase (JNK) and augment the proinflammatory response, leading to tissue damage and eventually mortality. These findings reveal that TRPC1 is required for host defense against bacterial infections through the TLR4-TRPC1-PKCγ signaling circuit.Fil: Zhou, Xikun. University Of North Dakota; Estados Unidos. West China Hospital Of Sichuan University; ChinaFil: Ye, Yan. University Of North Dakota; Estados UnidosFil: Sun, Yuyang. University Of North Dakota; Estados UnidosFil: Li, Xuefeng. West China Hospital Of Sichuan University; China. University Of North Dakota; Estados UnidosFil: Wang, Wenxue. University Of North Dakota; Estados UnidosFil: Privratsky, Breanna. University Of North Dakota; Estados UnidosFil: Tan, Shirui. University Of North Dakota; Estados UnidosFil: Zhou, Zongguang. West China Hospital Of Sichuan University; ChinaFil: Huang, Canhua. West China Hospital Of Sichuan University; ChinaFil: Wei, Yu-Quan. West China Hospital Of Sichuan University; ChinaFil: Birnbaumer, Lutz. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. National Institute Of Environmental Health Sciences; Estados UnidosFil: Singh, Brij B.. University Of North Dakota; Estados UnidosFil: Wu, Min. University Of North Dakota; Estados Unido

High extinction risk in large foraminifera during past and future mass extinctions.

There is a strong relationship between metazoan body size and extinction risk. However, the size selectivity and underlying mechanisms in foraminifera, a common marine protozoa, remain controversial. Here, we found that foraminifera exhibit size-dependent extinction selectivity, favoring larger groups (>7.4 log10 cubic micrometer) over smaller ones. Foraminifera showed significant size selectivity in the Guadalupian-Lopingian, Permian-Triassic, and Cretaceous-Paleogene extinctions where the proportion of large genera exceeded 50%. Conversely, in extinctions where the proportion of large genera was <45%, foraminifera displayed no selectivity. As most of these extinctions coincided with oceanic anoxic events, we conducted simulations to assess the effects of ocean deoxygenation on foraminifera. Our results indicate that under suboxic conditions, oxygen fails to diffuse into the cell center of large foraminifera. Consequently, we propose a hypothesis to explain size distribution-related selectivity and Lilliput effect in animals relying on diffusion for oxygen during past and future ocean deoxygenation, i.e., oxygen diffusion distance in body

Biosynthesis of ganglioside mimics in Campylobacter jejuni OH4384. Identification of the glycosyltransferase genes, enzymatic synthesis of model compounds, and characterization of nanomole amounts by 600-mhz (1)h and (13)c NMR analysis.

We have applied two strategies for the cloning of four genes responsible for the biosynthesis of the GT1a ganglioside mimic in the lipooligosaccharide (LOS) of a bacterial pathogen,Campylobacter jejuni OH4384, which has been associated with Guillain-Barre syndrome. We first cloned a gene encoding an α-2,3-sialyltransferase (cst-I) using an activity screening strategy. We then used nucleotide sequence information from the recently completed sequence from C. jejuni NCTC 11168 to amplify a region involved in LOS biosynthesis from C. jejuni OH4384. The LOS biosynthesis locus from C. jejuni OH4384 is 11.47 kilobase pairs and encodes 13 partial or complete open reading frames, while the corresponding locus in C. jejuni NCTC 11168 spans 13.49 kilobase pairs and contains 15 open reading frames, indicating a different organization between these two strains. Potential glycosyltransferase genes were cloned individually, expressed in Escherichia coli, and assayed using synthetic fluorescent oligosaccharides as acceptors. We identified genes encoding a β-1,4-N-acetylgalactosaminyl-transferase (cgtA), a β-1,3-galactosyltransferase (cgtB), and a bifunctional sialyltransferase (cst-II), which transfers sialic acid to O-3 of galactose and to O-8 of a sialic acid that is linked α-2,3- to a galactose. The linkage specificity of each identified glycosyltransferase was confirmed by NMR analysis at 600 MHz on nanomole amounts of model compounds synthesized in vitro. Using a gradient inverse broadband nano-NMR probe, sequence information could be obtained by detection of3J(C,H) correlations across the glycosidic bond. The role of cgtA and cst-II in the synthesis of the GT1a mimic in C. jejuni OH4384 were confirmed by comparing their sequence and activity with corresponding homologues in two relatedC. jejuni strains that express shorter ganglioside mimics in their LOS

The Impact of Callous-Unemotional Traits and Externalizing Tendencies on Neural Responsivity to Reward and Punishment in Healthy Adolescents

Both externalizing behavior and callous-unemotional (CU) traits in youth are precursors to later criminal offending in adulthood. It is posited that disruptions in reward and punishment processes may engender problematic behavior, such that CU traits and externalizing behavior may be linked to a dominant reward response style (e.g., heightened responsivity to rewards) and deficient punishment-processing. However, prior research has generated mixed findings and work examining both the sole and joint contribution of CU traits and externalizing problems related to functional brain alterations is lacking. In this pilot functional magnetic resonance imaging study, we measured externalizing behavior and CU traits in a community sample of adolescents (n = 29) and examined their impacts on brain activity associated with anticipation and receipt of reward and punishment using the Modified Monetary Incentive Delay task. We found that CU traits were associated with greater activation of the ventral striatum (VST) during reward anticipation. However, this effect became non-significant after controlling for externalizing behavior, indicating substantial overlap between the CU and externalizing measures in explaining VST activation when anticipating reward. In addition, externalizing behavior (but not CU) was significantly negatively associated with amygdala activation during punishment receipt, even after controlling for CU traits. The present findings extend previous evidence of hyper-responsivity to reward and hyporesponsivity to punishment in relation to psychopathic traits and antisocial behavior to non-clinical, non-incarcerated youths

An effective route to the additive manufacturing of a mechanically gradient supramolecular polymer nanocomposite structure

3D Printing techniques are additive methods of fabricating parts directly from computer-aided designs. Whilst the clearest benefit is the realisation of geometrical freedom, multi-material printing allows the introduction of compositional variation and highly tailored product functionality. The paper reports a proof-of-concept additive manufacturing study to deposit a supramolecular polymer and a complementary organic filler to form composites with gradient composition to enable spatial distribution of mechanical properties and functionality by tuning the number of supramolecular interactions. We use a dual-feed extrusion 3D printing process, with feed stocks based on the supramolecular polymer and its organic composite, delivered at ratios predetermined. This allows for production of a graded specimen with varying filler concentration that dictates the mechanical properties. The printed specimen was inspected under dynamic load in a tensile test using digital image correlation to produce full-field deformation maps, which showed clear differences in deformation in regions with varying compositions, corresponding to the designed-in variations. This approach affords a novel method for printing material with graded mechanical properties which are not currently commercially available or easily accessible, however, the method can potentially be directly translated to the generation of biomaterial-based composites featuring gradients of mechanical properties