Investigations on the EPR g factors and local structures for the orthorhombic and tetragonal Cu2+ centers in Pb[Zr0.54Ti0.46]O3.

The defect models of the orthorhombical and tetragonal Cu2+ centers in Pb[Zr0.54Ti0.46]O3 are attributed to Cu2+ ions occupying the sixfold coordinated octahedral Ti4+ site with and without charge compensation, respectively. The electron paramagnetic resonance (EPR) g factors gi (i = x, y, z) of the Cu2+ centers in Pb[Zr0.54Ti0.46]O3 are theoretically studied by using the perturbation formulas of a 3d9 ion under orthorhombically and tetragonally elongated octahedra. Based on the calculation, the impurity off-center displacements are about 0.253 and 0.162 Å for the orthorhombical and tetragonal Cu2+ centers, respectively. Meanwhile, the planar Cu2+-O2- bonds are found to experience the relative variation ΔR (≈0.102 Å) along the a- and b-axes for the orthorhombical Cu2+ center due to the Jahn-Teller (JT) effect. The theoretical EPR g factors based on the above local structures agree well with the observed values.

Prevalence of Mental, Behavioral, and Developmental Disorders Among Children and Adolescents with Diabetes, United States (2016-2019).

OBJECTIVE: To assess the association of diabetes and mental, behavioral, and developmental disorders in youth, we examined the magnitude of overlap between these disorders in children and adolescents. STUDY DESIGN: In this cross-sectional study, we calculated prevalence estimates using the 2016-2019 National Survey of Children's Health. Parents reported whether their child was currently diagnosed with diabetes or with any of the following mental, behavioral, or developmental disorders: attention-deficit/hyperactivity disorder, autism spectrum disorder, learning disability, intellectual disability, developmental delay, anxiety, depression, behavioral problems, Tourette syndrome, or speech/language disorder. We present crude prevalence estimates weighted to be representative of the US child population and adjusted prevalence ratios (aPRs) adjusted for age, sex, and race/ethnicity. RESULTS: Among children and adolescents (aged 2-17 years; n = 121 312), prevalence of mental, behavioral, and developmental disorders varied by diabetes status (diabetes: 39.9% [30.2-50.4]; no diabetes: 20.3% [19.8-20.8]). Compared with children and adolescents without diabetes, those with diabetes had a nearly 2-fold higher prevalence of mental, behavioral, and developmental disorders (aPR: 1.72 [1.31-2.27]); mental, emotional, and behavioral disorders (aPR: 1.90 [1.38-2.61]) and developmental, learning, and language disorders (aPR: 1.89 [1.35-2.66]). CONCLUSIONS: These results suggest that approximately 2 in 5 children and adolescents with diabetes have a mental, behavioral, or developmental disorder. Understanding potential causal pathways may ultimately lead to future preventative strategies for mental, behavioral, and developmental disorders and diabetes in children and adolescents.

Localized vibrational characteristics of biphenylene strips resulting in length-dependent Raman spectra.

The length dependence of the Raman spectra and vibrational properties of biphenylene strips are explored using density functional theory. The Raman intensity of two bands increases and decreases with length due to the enlarging and shrinking of the proportion of effective vibrating units. The red shift of vibrational modes is observed with the increase in length, owing to the various vibrational characteristics of the effective vibrating units. More importantly, a linear relationship between the energy gap and the wavenumber of the shifting Raman bands is obtained. The results allow us to interpret the length-dependence of the Raman spectra from the perspective of localized vibrational characteristics and suggest that Raman spectroscopy can be used as a convenient method to determine the energy gap of nanomaterials.

Atomic Scale Control of Spin Current Transmission at Interfaces.

Ferromagnet/heavy metal bilayers represent a central building block for spintronic devices where the magnetization of the ferromagnet can be controlled by spin currents generated in the heavy metal. The efficiency of spin current generation is paramount. Equally important is the efficient transfer of this spin current across the ferromagnet/heavy metal interface. Here, we show theoretically and experimentally that for Ta as heavy metal the interface only partially transmits the spin current while this effect is absent when Pt is used as heavy metal. This is due to magnetic moment reduction at the interface caused by 3d-5d hybridization effects. We show that this effect can be avoided by atomically thin interlayers. On the basis of our theoretical model we conclude that this is a general effect and occurs for all 5d metals with less than half-filled 5d shell.

Review of Sponge City implementation in China: performance and policy.

Urban flooding is a major problem for large cities around the world. Rapid urbanization in China has tremendously increased, resulting in more frequent incidences of urban flooding. In 2013, China launched a program of 30 pilot sponge cities (SPCs) to establish integrated urban stormwater management. However, today, after several years of implementation, some sponge cities still experience flooding. This study provides answers and solutions to these problems, by evaluating the overall performance of SPC in China from a systematic perspective considering the variable climatic conditions. This paper also highlights the limitations associated with implementing the current SPC. The adoption of overseas models, before adhering them to Chinese catchment properties, has generated significant uncertainty for simulation outputs and material provision challenges at various stages of the implementation process. Furthermore, hydrological connectivity between neighboring catchments has been neglected in most SPC projects. Developing local models based on local conditions and needs would address these issues and open new research windows for exploring more effective stormwater management initiatives. That includes the advancement of cost-effective evaluation studies, modern optimum efficiency design studies, and the analysis of groundwater contamination due to high infiltration rates and so on.

Design, Synthesis, and Biological Evaluation of 5,6,7,8-Tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidines as Microtubule Targeting Agents.

A series of eleven 4-substituted 5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidines were designed and synthesized and their biological activities were evaluated. Synthesis involved the Gewald reaction to synthesize ethyl 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate ring, and SNAr reactions. Compound 4 was 1.6- and ~7-fold more potent than the lead compound 1 in cell proliferation and microtubule depolymerization assays, respectively. Compounds 4, 5 and 7 showed the most potent antiproliferative effects (IC50 values < 40 nM), while compounds 6, 8, 10, 12 and 13 had lower antiproliferative potencies (IC50 values of 53-125 nM). Additionally, compounds 4-8, 10 and 12-13 circumvented Pgp and ßIII-tubulin mediated drug resistance, mechanisms that diminish the clinical efficacy of paclitaxel (PTX). In the NCI-60 cell line panel, compound 4 exhibited an average GI50 of ~10 nM in the 40 most sensitive cell lines. Compound 4 demonstrated statistically significant antitumor effects in a murine MDA-MB-435 xenograft model.

Discovery of 6-substituted thieno[2,3-d]pyrimidine analogs as dual inhibitors of glycinamide ribonucleotide formyltransferase and 5-aminoimidazole-4-carboxamide ribonucleotide formyltransferase in de novo purine nucleotide biosynthesis in folate receptor expressing human tumors.

We discovered 6-substituted thieno[2,3-d]pyrimidine compounds (3-9) with 3-4 bridge carbons and side-chain thiophene or furan rings for dual targeting one-carbon (C1) metabolism in folate receptor- (FR) expressing cancers. Synthesis involved nine steps starting from the bromo-aryl carboxylate. From patterns of growth inhibition toward Chinese hamster ovary cells expressing FRα or FRß, the proton-coupled folate transporter or reduced folate carrier, specificity for uptake by FRs was confirmed. Anti-proliferative activities were demonstrated toward FRα-expressing KB tumor cells and NCI-IGROV1 ovarian cancer cells. Inhibition of de novo purine biosynthesis at both 5-aminoimidazole-4-carboxamide ribonucleotide formyltransferase and glycinamide ribonucleotide formyltransferase (GARFTase) was confirmed by metabolite rescue, metabolomics and enzyme assays. X-ray crystallographic structures were obtained with compounds 3-5 and human GARFTase. Our studies identify first-in-class C1 inhibitors with selective uptake by FRs and dual inhibition of enzyme targets in de novo purine biosynthesis, resulting in anti-tumor activity. This series affords an exciting new platform for selective multi-targeted anti-tumor agents.

Enabling chiral separations in discovery chemistry with open-access chiral supercritical fluid chromatography.

Work from this paper details a novel walk-up open-access (OA) approach to enable chiral analytical method development and preparative separation of enantiomers in early discovery chemistry using supercritical fluid chromatography (SFC). We have demonstrated the success of this OA approach using immobilized chiral stationary phases (CSPs). After screening a diverse set of racemic drug candidates, we have concluded that a simplified OA chiral SFC platform can successfully purify approximately 60% of the analysed racemates. This streamlined OA workflow enables medicinal chemists with limited expertise in chiral method development to successfully and rapidly purify enantiomers for their projects using Waters UPC2 and Prep100-SFC instrumentation.

Determination of Pb, Cr, Cd, and As in Aluminum-Plastic Packaging Materials via Inductively Coupled Plasma-Mass Spectrometry with Microwave Digestion.

Microwave digestion was performed to study the pretreatment methods of aluminum-plastic packaging materials (APPMs). Five different digestion reagent combinations and proportions were thoroughly considered. Digestion results indicated that the most suitable reagent combination was sulfuric and nitric acids with the optimal proportion of 1∶7 after the orthogonal experiment. Moreover, the possible reasons of the experimental phenomenon were analyzed. The contents of Pb, Cr, Cd, and As in APPMs were subsequently determined via inductively coupled plasma-mass spectrometry (ICP-MS). The satisfactory linearity of calibration curves was obtained with the linear correlation coefficients above 0.999 5, and the instrument detection limits of Pb, Cr, Cd, and As for the current method were 0.215, 0.067, 0.006 and 0.020 ng·mL-1, respectively. Furthermore, the recoveries of standard addition ranged from 83.8% to 111.6%, and the relative standard deviations ranged from 0.5% to 7.4%. Two independent parallel determination results of Pb, Cr, Cd, and As in APPMs were approaching, and the student's t-test (confidence level, α=0.05) showed that the determination results had no significant differences. In conclusion, the present method exhibited fine linearity, low detection limit, high recovery, and good precision, which can accurately be utilized to analyze Pb, Cr, Cd, and As elements in APPMs or other similar materials.

Impact of the COVID-19 Pandemic on Medical Expenditures Among Medicare Fee-for-Service Beneficiaries Aged ≥67 Years With Diabetes.

OBJECTIVE: To compare total and out-of-pocket (OOP) medical expenditures between pre-COVID-19 (March 2019 to February 2020) and COVID-19 (March 2020 to February 2022) periods among Medicare beneficiaries with diabetes. RESEARCH DESIGN AND METHODS: Data were from 100% Medicare fee-for-service claims. Diabetes was identified using ICD-10 codes. We calculated quarterly total and OOP medical expenditures at the population and per capita level in total and by service type. Per capita expenditures were calculated by dividing the population expenditure by the number of beneficiaries with diabetes in the same quarter. Changes in expenditures were calculated as the differences in the same quarters between the prepandemic and pandemic years. RESULTS: Population total expenditure fell to $33.6 billion in the 1st quarter of the pandemic from $41.7 billion in the same prepandemic quarter; it then bounced back to $36.8 billion by the 4th quarter of the 2nd pandemic year. The per capita total expenditure fell to $5,356 in the 1st quarter of the pandemic from $6,500 in the same prepandemic quarter. It then increased to $6,096 by the 4th quarter of the 2nd pandemic year, surpassing the same quarter in the prepandemic year ($5,982). Both population and per capita OOP expenditures during the pandemic period were lower than the prepandemic period. Changes in per capita expenditure between the pre-COVID-19 and COVID-19 periods by service type varied. CONCLUSIONS: COVID-19 had a significant impact on both total and per capita medical expenditures among Medicare beneficiaries with diabetes. The COVID-19 pandemic was associated with lower OOP expenditures.

The relationship between appearance anxiety and depression among students in a medical university in China: a serial multiple mediation model.

Background: Appearance anxiety and depression have become common and global public health problems worldwide, especially among adolescents. However, few studies have revealed the mechanisms between them. This study aimed to explore the multiple mediating roles of interpersonal sensitivity and social support between appearance anxiety and depression among medical college students. Methods: With 13 invalid samples excluded, 724 college students participated in our survey and completed questionnaires. The average age of 724 samples was 19.8 ± 2.02 including freshman to senior year and graduate school and above; 31.9% of the participants were male and 68.1% were female. SPSS 25.0 and Hayes' PROCESS macro were used for statistical description, correlation analysis and built multiple mediation models. Results: Appearance anxiety can not only directly affect depression, but also indirectly affect depression through three significant mediating pathways: (1) IS (B = 0.106, 95% CI [0.082-0.132]), which accounted for 49.77% of the total effect, (2) SS (B = 0.018, 95% CI [0.008-0.031]), which accounted for 8.45% of the total effect, and (3) IS and SS (B = 0.008, 95% CI [0.003-0.014]), which accounted for 3.76% of the total effect. And the total mediating effect was 61.97%. Limitations: It is a cross-sectional research method and the causal relationship is unclear. Conclusions: This study found that lower interpersonal sensitivity and higher social support can effectively reduce depression caused by appearance anxiety among college students. The schools and relevant departments should take measures to reduce the interpersonal sensitivity of college students and establish reliable social support, so as to reduce the occurrence of depression.

Tuning the Crystallization Mechanism by Composition Vacancy in Phase Change Materials.

Interface-influenced crystallization is crucial to understanding the nucleation- and growth-dominated crystallization mechanisms in phase-change materials (PCMs), but little is known. Here, we find that composition vacancy can reduce the interface energy by decreasing the coordinate number (CN) at the interface. Compared to growth-dominated GeTe, nucleation-dominated Ge2Sb2Te5 (GST) exhibits composition vacancies in the (111) interface to saturate or stabilize the Te-terminated plane. Together, the experimental and computational results provide evidence that GST prefers (111) with reduced CN. Furthermore, the (8 - n) bonding rule, rather than CN6, in the nuclei of both GeTe and GST results in lower interface energy, allowing crystallization to be observed at the simulation time in general PCMs. In comparison to GeTe, the reduced CN in the GST nuclei further decreases the interface energy, promoting faster nucleation. Our findings provide an approach to designing ultrafast phase-change memory through vacancy-stabilized interfaces.

Changes in health care utilization among Medicare beneficiaries with diabetes two years into the COVID-19 pandemic.

IMPORTANCE: The coronavirus 2019 (COVID-19) pandemic abruptly impacted health care service delivery and utilization. However, the impact on older adults with diabetes in the United States is unclear. OBJECTIVE: To estimate changes in health care utilization among older adults with diabetes during the initial 2 years of the COVID-19 pandemic compared to the 2 years before, and to examine the variation in utilization changes by demographic and socioeconomic characteristics. DESIGN SETTING AND PARTICIPANTS: In this study, we analyzed changes in utilization, measured by the average use of health care services per 1,000 persons with diabetes, using medical claims for Medicare fee-for-service beneficiaries aged 67 years and above. Utilization changes by setting (acute inpatient, emergency room [ER], hospital outpatient, physician office, and ambulatory surgery center [ASC]) and by media (telehealth and in-person) were examined for 22 months of the pandemic (03/2020-12/2021) compared with pre-pandemic period (03/2018-12/2019). We also estimated utilization changes by beneficiaries' age group, sex, race/ethnicity, and residential urbanicity. RESULTS: The study sample consisted of approximately 6 million beneficiaries with diabetes each month. In the first 2 years of the pandemic, the average use of health care services by setting was 5-17% lower than the pre-pandemic level for all types of services. Phase 1 (03/2020-05/2020) had the largest decrease in utilization: physician office visits changed by -51.2% (95% CI, -55.0% to -47.5%), ASC procedures by -45.1% (95% CI, -49.8% to -40.4%), ER visits by -36.9% (95% CI, -39.0% to -34.7%), acute inpatient stays by -31.5% (95% CI, -33.6% to -29.3%), and hospital outpatient visits by -27% (95% CI, -29.3% to -24.8%). The reduction in utilization varied by sociodemographic subgroup. During the pandemic, the use of telehealth visits increased by 511.1% (95% CI, 502.2% to 520.0%) compared to the pre-pandemic period. The increase was smaller among rural residents. CONCLUSIONS AND RELEVANCE: Medicare beneficiaries with diabetes experienced a reduction in the use of health care services during the COVID-19 pandemic, some of which persisted through two years into the pandemic. Telehealth visits increased, but not enough to overcome decreases in in-person visits. Understanding these patterns may help to optimize the use of health care resources for diabetes management in the post-pandemic era and during future emergencies.

Income-related inequalities in diagnosed diabetes prevalence among US adults, 2001-2018.

AIMS: The overall prevalence of diabetes has increased over the past two decades in the United States, disproportionately affecting low-income populations. We aimed to examine the trends in income-related inequalities in diabetes prevalence and to identify the contributions of determining factors. METHODS: We estimated income-related inequalities in diagnosed diabetes during 2001-2018 among US adults aged 18 years or older using data from the National Health Interview Survey (NHIS). The concentration index was used to measure income-related inequalities in diabetes and was decomposed into contributing factors. We then examined temporal changes in diabetes inequality and contributors to those changes over time. RESULTS: Results showed that income-related inequalities in diabetes, unfavorable to low-income groups, persisted throughout the study period. The income-related inequalities in diabetes decreased during 2001-2011 and then increased during 2011-2018. Decomposition analysis revealed that income, obesity, physical activity levels, and race/ethnicity were important contributors to inequalities in diabetes at almost all time points. Moreover, changes regarding age and income were identified as the main factors explaining changes in diabetes inequalities over time. CONCLUSIONS: Diabetes was more prevalent in low-income populations. Our study contributes to understanding income-related diabetes inequalities and could help facilitate program development to prevent type 2 diabetes and address modifiable factors to reduce diabetes inequalities.

Nanoscale Phase Change Material Array by Sub-Resolution Assist Feature for Storage Class Memory Application.

High density phase change memory array requires both minimized critical dimension (CD) and maximized process window for the phase change material layer. High in-wafer uniformity of the nanoscale patterning of chalcogenides material is challenging given the optical proximity effect (OPE) in the lithography process and the micro-loading effect in the etching process. In this study, we demonstrate an approach to fabricate high density phase change material arrays with half-pitch down to around 70 nm by the co-optimization of lithography and plasma etching process. The focused-energy matrix was performed to improve the pattern process window of phase change material on a 12-inch wafer. A variety of patternings from an isolated line to a dense pitch line were investigated using immersion lithography system. The collapse of the edge line is observed due to the OPE induced shrinkage in linewidth, which is deteriorative as the patterning density increases. The sub-resolution assist feature (SRAF) was placed to increase the width of the lines at both edges of each patterning by taking advantage of the optical interference between the main features and the assistant features. The survival of the line at the edges is confirmed with around a 70 nm half-pitch feature in various arrays. A uniform etching profile across the pitch line pattern of phase change material was demonstrated in which the micro-loading effect and the plasma etching damage were significantly suppressed by co-optimizing the etching parameters. The results pave the way to achieve high density device arrays with improved uniformity and reliability for mass storage applications.

Plasmon Driven Nanocrystal Transformation by Aluminum Nano-Islands with an Alumina Layer.

The plasmonic photothermal effects of metal nanostructures have recently become a new priority of studies in the field of nano-optics. Controllable plasmonic nanostructures with a wide range of responses are crucial for effective photothermal effects and their applications. In this work, self-assembled aluminum nano-islands (Al NIs) with a thin alumina layer are designed as a plasmonic photothermal structure to achieve nanocrystal transformation via multi-wavelength excitation. The plasmonic photothermal effects can be controlled by the thickness of the Al2O3 and the intensity and wavelength of the laser illumination. In addition, Al NIs with an alumina layer have good photothermal conversion efficiency even in low temperature environments, and the efficiency will not decline significantly after storage in air for 3 months. Such an inexpensive Al/Al2O3 structure with a multi-wavelength response provides an efficient platform for rapid nanocrystal transformation and a potential application for the wide-band absorption of solar energy.

Surface plasmon assisted preparation of X1-type Y2SiO5:Eu3+-Au luminescent crystals.

Rare-earth doped yttrium orthosilicate (Y2SiO5) crystals have many important applications due to their unique optical and luminescence properties. However, the indispensable high temperature treatment and long period reaction tend to greatly reduce the preparation efficiency. Here, the plasmonic photothermal effect of Au nanoparticles has been properly applied to realize in situ transformation from a composite structure NaYF4:Eu3+@SiO2@Au into a single monoclinic X1-type Y2SiO5:Eu3+-Au particle. It is worth mentioning that the X1-type Y2SiO5-Au particle can be well obtained within about 10 seconds when the thickness of the SiO2 shell is about 15 nm, which is unattainable with conventional approaches. Moreover, the particle turns out to possess good crystallinity, controllable morphology, and significantly improved luminescence performance. This study not only provides a brand-new path for the preparation of yttrium silicate crystals but also further extends the application of surface plasmons in the field of catalytic luminescent materials.

Impacts of Built Environment on Risk of Women's Lung Cancer: A Case Study of China.

Built environment factors such as air pollution are associated with the risk of respiratory disease, but few studies have carried out profound investigation. We aimed to evaluate the association between the built environment and Chinese women's lung cancer incidence data from the China Cancer Registry Annual Report 2017, which covered 345,711,600 people and 449 qualified cancer registries in mainland China. The air quality indicator (PM2.5) and other built environment data are obtained from the China Statistical Yearbook and other official approved materials. An exploratory regression tool is applied by using Chinese women's lung cancer incidence data (Segi population) as the dependent variable, PM2.5 index and other built environment factors as the independent variables. An apparent clustering region with a high incidence of women's lung cancer was discovered, including regions surrounding Bohai bay and the three Chinese northeastern provinces, Heilongjiang, Liaoning and Inner Mongolia. Besides air quality, built environment factors were found to have a weak but clear impact on lung cancer incidence. Land-use intensity and the greening coverage ratio were positive, and the urbanization rate and population density were negatively correlated with lung cancer incidence. The role of green spaces in Chinese women's lung cancer incidence has not been proven.

Plasmonic Effect of Ag/Au Composite Structures on the Material Transition.

Noble metal nanostructures can produce the surface plasmon resonance under appropriate photoexcitation, which can be used to promote or facilitate chemical reactions, as well as photocatalytic materials, due to their strong plasmon resonance in the visible light region. In the current work, Ag/Au nanoislands (NIs) and Ag NIs/Au film composite systems were designed, and their thermocatalysis performance was investigated using luminescence of Eu3+ as a probe. Compared with Ag NIs, the catalytic efficiency and stability of surface plasmons of Ag/Au NIs and Ag NIs/Au film composite systems were greatly improved. It was found that the metal NIs can also generate strong localized heat at low temperature environment, enabling the transition of NaYF4:Eu3+ to Y2O3: Eu3+, and anti-oxidation was realized by depositing gold on the surface of silver, resulting in the relative stability of the constructed complex.

Plasmon driven nanocrystal transformation in low temperature environments.

The preparation and modification of crystal structures in cryogenic environments with conventional methods is challenging, but it is essential for the development of composite materials, energy savings, and future human space exploration. Plasmon induced hot carriers and local thermal effects help to overcome the challenges of chemical reactions under extreme conditions, for which molecular reactions have attracted considerable research attention. In this work, the plasmon thermal effect enables fast and efficient nanocrystal transformation in cryogenic environments, which was previously unattainable with conventional heating methods. The transformation of NaYF4 nanocrystals on gold nanoparticle island films can be achieved even in a low temperature environment of 11 K. Compared with the structure with gold nanoparticles adhered to NaYF4 nanocrystals directly, the structure of gold nanoparticle island films with an Al2O3 layer offered better heat trapping properties, which allows the complete transformation to take place of NaYF4 nanocrystals into Y2O3 nanocrystals in low temperature environments. This work explores the potential of applying the photothermal effect of a plasmon to induce rapid transformation of nanocrystals in extreme environments and provides insight into the process of crystal transformation and growth.