Cooling, nucleation, and phase growth are ubiquitous processes in nature. Effective control of nucleation and phase growth is of significance to yield refined microstructures with enhanced performance for materials. Recent studies reveal that ultrafine grained (UFG)/nanocrystalline metals exhibit extraordinary properties. However, conventional microstructure refinement methods, such as fast cooling and inoculation, have reached certain fundamental limits. It has been considered impossible to fabricate bulk UFG/nanocrystalline metals via slow cooling. Here, we report a new discovery that nanoparticles can refine metal grains to ultrafine/nanoscale by instilling a continuous nucleation and growth control mechanism during slow cooling. The bulk UFG/nanocrystalline metal with nanoparticles also reveals an unprecedented thermal stability. This method overcomes the grain refinement limits and may be extended to any other processes that involve cooling, nucleation, and phase growth for widespread applications.

Background To evaluate whether blood markers of lead, cadmium, and mercury can improve prediction for cardiovascular disease (CVD) mortality when added individually, jointly, or as an integrative index/Environmental Risk Score (ERS), in a model with established risk factors. Methods and Results Our study sample comprised 16 028 adults aged ≥40 years who were enrolled in the National Health and Nutrition Examination Survey 1999-2012 and followed up through December 31, 2015. The study sample was randomly split into training for the ERS construction (n=8043) and testing for the evaluation of prediction performance (n=7985). ERS was computed using elastic-net penalized Cox's model based on the selected metal predictors predicting CVD mortality. During median follow-up of 7.2 years, 517 died from CVD. In the training set, linear terms of cadmium and mercury, squared terms of lead and mercury, and all 3 pairwise interactions were selected by elastic-net for ERS construction. In the testing set, the C-statistic increased from 0.845 when only established CVD risk factors were in the model to 0.854 when the ERS was additionally added to the model. Addition of all linear, squared, and pairwise interaction terms of blood metals to the Cox's models improved C-statistic from 0.845 to 0.857. The improvement remained significant when it was assessed by net reclassification improvement and integrated discrimination improvement. Conclusions Our findings suggest that blood markers of toxic metals can improve CVD risk prediction over the established risk factors and highlight their potential utility for CVD risk assessment, prevention, and precision health.

Experimental and epidemiological studies have linked metals with women's reproductive aging, but the mechanisms are not well understood. Disrupted ovarian folliculogenesis and diminished ovarian reserve could be a pathway through which metals impact reproductive hormones and outcomes.

We investigated the associations between blood concentrations of lead and cadmium with stroke mortality, and potential effect modification by obesity. Our study analyzed data from 23,437 individuals aged 40 and above, using the National Health and Nutrition Examination Survey (NHANES 1999-2016) linked to the National Death Index. During a median follow-up period of 8.3 years, 336 stroke-related deaths were reported. After adjusting for potential confounders, we found that higher baseline concentrations of lead and cadmium were significantly associated with increased stroke mortality. Specifically, the hazard ratios (HRs) per doubling of metal concentrations were 1.16 (95% CI: 1.11, 1.20) for lead and 1.31 (95% CI: 1.26, 1.36) for cadmium. Stratified analysis showed that stronger associations were observed among participants who were normal weight or overweight, relative to those who were obese. In conclusion, our study demonstrates that elevated blood concentrations of lead and cadmium are significantly associated with an increased risk of stroke mortality, especially among individuals who are normal weight or overweight.

Environmental exposure to metals may play a role in the pathogenesis of diabetes; however, evidence from human studies is limited. We prospectively evaluated the associations of 20 urinary metal concentrations and their mixtures with incident diabetes in the Study of Women's Health Across the Nation, a multisite, multiethnic cohort study of midlife women.

Exposure to metals may contribute to the development of metabolic syndrome (MetS); however, evidence from midlife women who are at greater risk of cardiometabolic disease is limited. We assessed the associations of 15 urinary metal concentrations with incident MetS in a prospective cohort of midlife women in the United States. The study population included 947 White, Black, Chinese and Japanese women, aged 45-56 years, free of MetS at baseline (1999-2000), who participated in the Study of Women's Health Across the Nation Multi-Pollutant Study. Fifteen metals were detected in almost all participants urine samples using inductively coupled plasma mass spectrometry at the baseline. Incident MetS was identified annually through 2017 as having at least three of the following five components: high blood pressure, impaired fasting glucose, abdominal obesity, high triglycerides, and poor high-density lipoprotein cholesterol. We used the Cox proportional hazards models to investigate the associations between individual metals and MetS incidence. The adjusted hazard ratios (HR) (95% CI) for MetS in associations with each doubling of urinary metal concentration were 1.14 (1.08, 1.23) for arsenic, 1.14 (1.01, 1.29) for cobalt, and 1.20 (1.06, 1.37) for zinc. We further evaluated the associations between metal mixtures and MetS using the elastic net penalized Cox model and summarized the results into the environmental risk score (ERS). Arsenic, barium, cobalt, copper, nickel, antimony, thallium, and zinc had positive weights, and cadmium, cesium, mercury, molybdenum, lead, and tin had negative weights in the construction of the ERS. The adjusted HR of MetS comparing 75th vs. 25th percentiles of the ERS was 1.45 (1.13, 1.87). These findings support the view that arsenic, cobalt, zinc, as well as metal mixtures, might influence the risks of incident MetS in midlife women.

The sintering of supported metal nanoparticles is a major route to the deactivation of industrial heterogeneous catalysts, which largely increase the cost and decrease the productivity. Here, we discover that supported palladium/gold/platinum nanoparticles distributed at the interface of oxide supports and nitrogen-doped carbon shells would undergo an unexpected nitrogen-doped carbon atomization process against the sintering at high temperatures, during which the nanoparticles can be transformed into more active atomic species. The in situ transmission electron microscopy images reveal the abundant nitrogen defects in carbon shells provide atomic diffusion sites for the mobile atomistic palladium species detached from the palladium nanoparticles. More important, the catalytic activity of sintered and deactivated palladium catalyst can be recovered by this unique N-doped carbon atomization process. Our findings open up a window to preparation of sintering-resistant single atoms catalysts and regeneration of deactivated industrial catalysts.

While laser-printed metals do not tend to match the mechanical properties and thermal stability of conventionally-processed metals, incorporating and dispersing nanoparticles in them should enhance their performance. However, this remains difficult to do during laser additive manufacturing. Here, we show that aluminum reinforced by nanoparticles can be deposited layer-by-layer via laser melting of nanocomposite powders, which enhance the laser absorption by almost one order of magnitude compared to pure aluminum powders. The laser printed nanocomposite delivers a yield strength of up to 1000 MPa, plasticity over 10%, and Young's modulus of approximately 200 GPa, offering one of the highest specific Young's modulus and specific yield strengths among structural metals, as well as an improved specific strength and thermal stability up to 400 °C compared to other aluminum-based materials. The improved performance is attributed to a high density of well-dispersed nanoparticles, strong interfacial bonding between nanoparticles and Al matrix, and ultrafine grain sizes.

Exposure to carcinogenic metals, such as trivalent arsenic [As(III)] and hexavalent chromium [Cr(VI)], through drinking water is a major global public health problem and is associated with various cancers. However, the mechanism of their carcinogenicity remains unclear. In this study, we used azoxymethane/dextran sodium sulfate (AOM/DSS)-induced mouse colitis-associated colorectal cancer model to investigate their tumorigenesis. Our results demonstrate that exposure to As(III) or Cr(VI), alone or in combination, together with AOM/DSS pretreatment has a promotion effect, increasing the colorectal tumor incidence, multiplicity, size, and grade, as well as cell inflammatory response. Two-dimensional differential gel electrophoresis coupled with mass spectrometry revealed that As(III) or Cr(VI) treatment alone significantly changed the density of proteins. The expression of β-catenin and phospho-GSK was increased by treatment of carcinogenic metals alone. Concomitantly, the expression of NADPH oxidase1 (NOX1) and the level of 8-OHdG were also increased by treatment of carcinogenic metals alone. Antioxidant enzymes, such as superoxide dismutase (SOD) and catalase, were decreased. Similarly, in an in vitro system, exposure of CRL-1807 to carcinogenic metals increased reactive oxygen species (ROS) generation, the expression of β-catenin, phospho-GSK, and NOX1. Inhibition of ROS generation by addition of SOD or catalase inhibited β-catenin expression and activity. Our study provides a new animal model to study the carcinogenicity of As(III) and Cr(VI) and suggests that As(III) and Cr(VI) promote colorectal cancer tumorigenesis, at least partly, through ROS-mediated Wnt/β-catenin signaling pathway.

As common coinage metals, silver and silver compounds have very rich application in the organic catalytic reaction. Immobilization of silver compounds on heterogeneous media is the most common way used in industrial catalytic reactions. In this work, we designed and synthesized a new heterogeneous porous silver catalyst, with in situ-formed Ag-S rods as connecting nodes and thiosemicarbazide-functionalized linear ligands, used in both σ- and π-catalytic transformations. Strong Ag-S bonds bypassed the loss of noble silver elements and inhibited the formation of nonporous silver particles which always led to the decrease of yields in homogenous reactions. Furthermore, various derivatives of propargylamines and phenylacetylenes were applied as both σ and π-active substrates with moderate to good yields.

The abrupt occurrence of twinning when Mg is deformed leads to a highly anisotropic response, making it too unreliable for structural use and too unpredictable for observation. Here, we describe an in-situ transmission electron microscopy experiment on Mg crystals with strategically designed geometries for visualization of a long-proposed but unverified twinning mechanism. Combining with atomistic simulations and topological analysis, we conclude that twin nucleation occurs through a pure-shuffle mechanism that requires prismatic-basal transformations. Also, we verified a crystal geometry dependent twin growth mechanism, that is the early-stage growth associated with instability of plasticity flow, which can be dominated either by slower movement of prismatic-basal boundary steps, or by faster glide-shuffle along the twinning plane. The fundamental understanding of twinning provides a pathway to understand deformation from a scientific standpoint and the microstructure design principles to engineer metals with enhanced behavior from a technological standpoint.

The biosynthesis of metal nanoparticles from precious metals has been of wide concern. Their antibacterial activity is a main bottleneck restricting the bacterial activity and reduction performance. Here, bio-electrochemical systems were used to harvest electroactive biofilms (EABs), where bacteria were naturally protected by extracellular polymeric substances to keep activity. The biofilm was further encapsulated with polydopamine (PDA) as additional shield. Silver nanoparticles (AgNPs) were biosynthesized on EABs, whose electroactivity could be fully recovered after Ag+ reduction. The PDA increased bacterial viability by 90%-105%, confirmed as an effective protection against antibacterial activity of Ag+/AgNPs. The biosynthetic process changed the component and function of the microbial community, shifting from bacterial Fe reduction to archaeal methanogenesis. These results demonstrated that the electrochemical acclimation of EABs and encapsulation with PDA were effective protective measures during the biosynthesis of AgNPs. These approaches have a bright future in the green synthesis of nanomaterials, biotoxic wastewater treatment, and sustainable bio-catalysis.