Nanotube Structure of AsPS4-xSex (x = 0, 1).

Single-wall nanotubes of isostructural AsPS4-xSex (x = 0, 1) are grown from solid-state reaction of stoichiometric amounts of the elements. The structure of AsPS4 was determined using single-crystal X-ray diffraction and refined in space group P1¯. The infinite, single-walled AsPS4 nanotubes have an outer diameter of ≈1.1 nm and are built of corner-sharing PS4 tetrahedra and AsS3 trigonal pyramids. Each nanotube is nearly hexagonal, but the ≈3.4 Å distance between S atoms on adjacent nanotubes allows them to easily slide past one another, resulting in the loss of long-range order. Substituting S with Se disrupted the crystallization of the nanotubes, resulting in amorphous products that precluded the determination of the structure for AsPS3Se. 31P solid-state NMR spectroscopy indicated a single unique tetrahedral P environment in AsPS4 and five different P environments all with different degrees of Se substitution in AsPS3Se. Optical absorption spectroscopy revealed an energy band gap of 2.7 to 2.4 eV for AsPS4 and AsPS3Se, respectively. Individual AsPS4 microfibers showed a bulk conductivity of 3.2 × 10-6 S/cm and a negative photoconductivity effect under the illumination of light (3.06 eV) in ambient conditions. Thus, intrinsic conductivity originates from hopping through empty trap states along the length of the AsPS4 nanotubes.

Measuring Work-related Risk of Coronavirus Disease 2019 (COVID-19): Comparison of COVID-19 Incidence by Occupation and Industry-Wisconsin, September 2020 to May 2021.

BACKGROUND: Work-related exposures play an important role in severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) transmission, yet few studies have compared SARS-CoV-2 expsoure risk across occupations and industries. METHODS: During September 2020 to May 2021, the Wisconsin Department of Health Services collected occupation and industry data as part of routine coronavirus disease 2019 (COVID-19) case investigations. Adults aged 18-64 years with confirmed or probable COVID-19 in Wisconsin were assigned standardized occupation and industry codes. Cumulative incidence rates were weighted for non-response and calculated using full-time equivalent (FTE) workforce denominators from the 2020 American Community Survey. RESULTS: An estimated 11.6% of workers (347 013 of 2.98 million) in Wisconsin, ages 18-64 years, had COVID-19 from September 2020 to May 2021. The highest incidence by occupation (per 100 FTE) occurred among personal care and services workers (22.1), healthcare practitioners and support staff (20.7), and protective services workers (20.7). High-risk sub-groups included nursing assistants and personal care aides (28.8), childcare workers (25.8), food and beverage service workers (25.3), personal appearance workers (24.4), and law enforcement workers (24.1). By industry, incidence was highest in healthcare (18.6); the highest risk sub-sectors were nursing care facilities (30.5) and warehousing (28.5). CONCLUSIONS: This analysis represents one of the most complete examinations to date of COVID-19 incidence by occupation and industry. Our approach demonstrates the value of standardized occupational data collection by public health and may be a model for improved occupational surveillance elsewhere. Workers at higher risk of SARS-CoV-2 exposure may benefit from targeted workplace COVID-19 vaccination and mitigation efforts.

Lost time: COVID-19 indemnity claim reporting and results in the Wisconsin workers' compensation system from March 12 to December 31, 2020.

BACKGROUND: The COVID-19 pandemic introduced a new compensable infectious disease to workplaces. METHODS: This was a descriptive analysis of Wisconsin COVID workers' compensation (WC) claims between March 12 and December 31, 2020. The impact of the presumption law (March 12 to June 10, 2020) was also evaluated. RESULTS: Less than 1% of working-age residents with COVID-19 filed a claim. COVID-19 WC claim rates (per 100,000 FTE) were notably low for frontline industry sectors such as Retail Trade (n = 115), Manufacturing (n = 88), and Wholesale Trade (n = 31). Healthcare workers (764 claims per 100,000 FTE) comprised 73.2% of COVID-19 claims. Most claims (52.8%) were denied and the proportion of denied claims increased significantly after the presumption period for both first responders and other occupations. CONCLUSION: The presumption law made benefits accessible primarily to first responders. Further changes to WC systems are needed to offset the individual and collective costs of infectious diseases.

Characterization of global loss of imprinting in fetal overgrowth syndrome induced by assisted reproduction.

Embryos generated with the use of assisted reproductive technologies (ART) can develop overgrowth syndromes. In ruminants, the condition is referred to as large offspring syndrome (LOS) and exhibits variable phenotypic abnormalities including overgrowth, enlarged tongue, and abdominal wall defects. These characteristics recapitulate those observed in the human loss-of-imprinting (LOI) overgrowth syndrome Beckwith-Wiedemann (BWS). We have recently shown LOI at the KCNQ1 locus in LOS, the most common epimutation in BWS. Although the first case of ART-induced LOS was reported in 1995, studies have not yet determined the extent of LOI in this condition. Here, we determined allele-specific expression of imprinted genes previously identified in human and/or mouse in day ∼105 Bos taurus indicus × Bos taurus taurus F1 hybrid control and LOS fetuses using RNAseq. Our analysis allowed us to determine the monoallelic expression of 20 genes in tissues of control fetuses. LOS fetuses displayed variable LOI compared with controls. Biallelic expression of imprinted genes in LOS was associated with tissue-specific hypomethylation of the normally methylated parental allele. In addition, a positive correlation was observed between body weight and the number of biallelically expressed imprinted genes in LOS fetuses. Furthermore, not only was there loss of allele-specific expression of imprinted genes in LOS, but also differential transcript amounts of these genes between control and overgrown fetuses. In summary, we characterized previously unidentified imprinted genes in bovines and identified misregulation of imprinting at multiple loci in LOS. We concluded that LOS is a multilocus LOI syndrome, as is BWS.

Long COVID Among Wisconsin Workers in the Workers' Compensation System: Associations With Sociodemographics, Vaccination, and Predominant Variant Period From March 1, 2020 to July 31, 2022.

OBJECTIVE: This analysis aimed to determine the likelihood of developing long COVID among Wisconsin workers while adjusting for sociodemographics, COVID-19 vaccination, industry, and occupation. METHODS: This retrospective analysis determined the odds ratios of developing long COVID among Wisconsin workers who were compensated for COVID-19 lost time during March 1, 2020 to July 31, 2022. RESULTS: A total of 234 workers (11.7%) were determined to have long COVID. Factors associated with long COVID were age ≥40 years, non-White race, infection occurrence during the initial and Omicron variant dominant periods, and the absence of COVID-19 vaccination. Workers in manufacturing and public administration were more likely to develop long COVID compared with those in health care and social assistance. CONCLUSIONS: Long COVID disproportionately affects some worker groups. This calls for more worker protection and preventative care to mitigate its impact.

Work and Life in the Balance: COVID-19 Mortality by Usual Occupation and Industry in Wisconsin.

INTRODUCTION: Work is central to the discourse surrounding the pandemic. Going to work during the COVID-19 pandemic put individuals at risk for both disease and death. This study assesses COVID-19 mortality by industry and occupation for working-age adults in Wisconsin and applies a health equity lens to understand COVID-19, demographics, work, and mortality in the state. METHODS: We used vital records data to evaluate COVID-19 mortality in Wisconsin. We assessed the demographics of working-age decedents using chi-square tests and logistic regression. We also classified decedents by usual occupation with Standard Occupational Classification (2018) and North American Industry Classification System (2017) codes to calculate mortality rates. We then calculated proportional mortality ratios to evaluate if mortality rates from COVID-19 in industry or occupation groups were significantly higher than the overall (ie, average) mortality rate from COVID-19 among all working-age Wisconsin adults. RESULTS: Both Asian/Pacific Islander and Hispanic individuals in Wisconsin had elevated likelihoods of dying from COVID-19. Lower levels of education also were associated with a higher likelihood of COVID-19-attributable death. Additionally, we found several occupations and industries that had elevated mortality rates from COVID-19. Proportional mortality ratios showed higher than expected mortality for several occupations including Protective Service; Office and Administrative Support; Farming, Fishing, and Forestry; and Installation, Maintenance, and Repair. Moreover, several industries had elevated proportional mortality ratios, including Agriculture, Forestry, Fishing, and Hunting; Finance and Insurance; Transportation and Warehousing; and Public Administration. DISCUSSION: The lessons of the pandemic are important for public health and worker safety. Understanding who bears disparate risks allows us to prepare, communicate, and mitigate risk.

COVID-19 Outbreaks Linked to Workplaces, 23 US Jurisdictions, August-October 2021.

OBJECTIVES: Early in the COVID-19 pandemic, several outbreaks were linked with facilities employing essential workers, such as long-term care facilities and meat and poultry processing facilities. However, timely national data on which workplace settings were experiencing COVID-19 outbreaks were unavailable through routine surveillance systems. We estimated the number of US workplace outbreaks of COVID-19 and identified the types of workplace settings in which they occurred during August-October 2021. METHODS: The Centers for Disease Control and Prevention collected data from health departments on workplace COVID-19 outbreaks from August through October 2021: the number of workplace outbreaks, by workplace setting, and the total number of cases among workers linked to these outbreaks. Health departments also reported the number of workplaces they assisted for outbreak response, COVID-19 testing, vaccine distribution, or consultation on mitigation strategies. RESULTS: Twenty-three health departments reported a total of 12 660 workplace COVID-19 outbreaks. Among the 12 470 workplace types that were documented, 35.9% (n = 4474) of outbreaks occurred in health care settings, 33.4% (n = 4170) in educational settings, and 30.7% (n = 3826) in other work settings, including non-food manufacturing, correctional facilities, social services, retail trade, and food and beverage stores. Eleven health departments that reported 3859 workplace outbreaks provided information about workplace assistance: 3090 (80.1%) instances of assistance involved consultation on COVID-19 mitigation strategies, 1912 (49.5%) involved outbreak response, 436 (11.3%) involved COVID-19 testing, and 185 (4.8%) involved COVID-19 vaccine distribution. CONCLUSIONS: These findings underscore the continued impact of COVID-19 among workers, the potential for work-related transmission, and the need to apply layered prevention strategies recommended by public health officials.

Polysulfide chalcogels with ion-exchange properties and highly efficient mercury vapor sorption.

We report the synthesis of metal-chalcogenide aerogels from Pt(2+) and polysulfide clusters ([S(x)](2-), x = 3-6). The cross-linking reaction of these ionic building blocks in formamide solution results in spontaneous gelation and eventually forms a monolithic dark brown gel. The wet gel is transformed into a highly porous aerogel by solvent exchanging and subsequent supercritical drying with CO(2). The resulting platinum polysulfide aerogels possess a highly porous and amorphous structure with an intact polysulfide backbone. These chalcogels feature an anionic network that is charged balanced with potassium cations, and hosts highly accessible S-S bonding sites, which allows for reversible cation exchange and mercury vapor capture that is superior to any known material.

Molecular germanium selenophosphate salts: phase-change properties and strong second harmonic generation.

A new series of germanium chalcophosphates with the formula A(4)GeP(4)Q(12) (A = K, Rb, Cs; Q = S, Se) have been synthesized. The selenium compounds are isostructural and crystallize in the polar orthorhombic space group Pca2(1). The sulfur analogues are isostructural to one another but crystallize in the centrosymmetric monoclinic space group C2/c. All structures contain the new molecular anion [GeP(4)Q(12)](4-); however, the difference between the sulfides and selenides arises from the change in crystal packing. Each discrete molecule is comprised of two ethane-like P(2)Q(6) units that chelate to a central tetrahedral Ge(4+) ion in a bidentate fashion. The selenides were synthesized pure by stoichiometric reaction of the starting materials, whereas the sulfides contained second phases. The band gaps of the molecular salts are independent of the alkali metal counterions and have a value of 2.0 eV for the selenides and 3.0-3.1 eV for the sulfides. All A(4)GeP(4)Se(12) compounds melt congruently, and the potassium analogue can be quenched to give a glassy phase that retains its short-range order as shown by Raman spectroscopy and powder X-ray diffraction. Interestingly, K(4)GeP(4)Se(12) is a phase-change material that reversibly converts between glassy and crystalline states and passes through a metastable crystalline state upon heating just before crystallizing into its slow-cooled form. Initial second harmonic generation (SHG) experiments showed crystalline K(4)GeP(4)Se(12) outperforms the other alkali metal analogues and exhibits the strongest second harmonic generation response among reported quaternary chalcophosphates, ~30 times that of AgGaSe(2) at 730 nm. A more thorough investigation of the nonlinear optical (NLO) properties was performed across a range of wavelengths that is almost triple that of previous reports (λ = 1200-2700 nm) and highlights the importance of broadband measurements. Glassy K(4)GeP(4)Se(12) also exhibits a measurable SHG response with no poling.

Germanium selenophosphates: the incommensurately modulated 1/∞[Ge(4-x)P(x)Se12(4-)] and the molecular [Ge2P2Se14]6-.

The new germanium selenophosphates K(4)Ge(4-x)P(x)Se(12) (1) and Rb(6)Ge(2)P(2)Se(14) (2) are reported. The former is a one-dimensional metastable compound synthesized using the polychalcogenide flux method that crystallizes in the monoclinic space group P2(1)/c with lattice parameters a = 6.7388(7) Å, b = 13.489(1) Å, c = 6.3904(6) Å, and ß = 91.025(8)°. At a glance, a mixed Ge(4+)/P(5+) tetrahedral site and disordered Se position are found among the corner sharing tetrahedra that make up the polymeric anion. After careful examination, the structure was found to be incommensurately modulated and a single q-vector of q = 0.4442(6)a* + 0.3407(6)c* was determined after annealing single crystals below their decomposition point for 30d. The latter compound contains the new discrete molecular anion [Ge(2)P(2)Se(14)](6-) and crystallizes in P1 with lattice parameters a = 7.2463(8) Å, b = 9.707(1)Å, c = 11.987(1)Å, α = 79.516(9)°, ß = 89.524(9)°, and γ = 68.281(9)°. Both compounds are semiconductors with band gaps of 1 and 2 being 1.9 eV and 2.2 eV, respectively.

Arsenic-containing chalcophosphate molecular anions.

We report five new discrete molecular arsenic-based chalcophosphates, K(7)As(3)(P(2)Se(6))(4) (1), K(6)As(2)(P(2)Se(6))(3) (2), Cs(6)As(2)(P(2)Se(6))(3) (3), and Cs(5)As(P(2)Q(6))(2) [Q = Se (4a) and S (4b)]. Each of the compounds contains unique complex anions comprised of common building blocks that have condensed to produce these anions. Phosphorus forms well-known [P(2)Q(6)](4-) moieties in all of the compounds that are bridged by arsenic trigonal pyramids in 1 and 2 and distorted octahedra in 3, 4a, and 4b. Although 2 and 3 have the same molecular formula, the structural difference between the two salts is attributed to the size of the alkali metal. The influence of flux basicity also seems to play a role in the formation of the molecular anion in 4a and 4b, which has been observed with other trivalent main-group elements at the octahedral position but only with the highly basic cesium alkali metal as the counterion. All structures were determined by single-crystal X-ray diffraction and are discussed along with phase-purity powder X-ray diffraction, thermal analyses, electronic absorption, and Raman spectroscopy.

Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS4)(PS5)2]6- and [In(PS4)2(PS5)]6-.

The first discrete anionic indium thiophosphate complexes are reported. The structures of K(6)[In(PS(4))(1.5)(PS(5))(1.5)] (1), Rb(6)[In(PS(4))(PS(5))(2)] (2), and Cs(6)[In(PS(4))(1.5)(PS(5))(1.5)] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS(4)](3-) and the new [PS(5)](3-) ion. The conformation and bonding of the unsymmetric chelate ligand [PS(5)](3-) to indium give rise to different anions of the general formula [In(PS(4))(1+x)(PS(5))(2-x)](6-) (x = 0, 0.5). The anionic moiety in K(6)[In(PS(4))(1.5)(PS(5))(1.5)] (1) consists of cocrystallizing lambda-[In(PS(4))(2)(PS(5))](6-) and Lambdalambdadelta-[In(PS(4))(PS(5))(2)](6-) anions in a ratio of 1:1 (and their enantiomers). In Rb(6)[In(PS(4))(PS(5))(2)] (2), no cocrystallizatzion of anions was observed, and only the Lambdalambdalambda-[In(PS(4))(PS(5))(2)](6-) anion (and its enantiomer) is present. Cs(6)[In(PS(4))(1.5)(PS(5))(1.5)] (3) shows the same disorder between [PS(4)](3-) and [PS(5)](3-) ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Lambdadeltadelta-[In(PS(4))(PS(5))(2)](6-) anion cocrystallizing with delta-[In(PS(4))(2)(PS(5))](6-). Additionally, ordered Rb(6)[In(PS(4))(PS(5))(2)] (2) was characterized by (31)P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.

Soft-hard acid-base interactions: probing coordination preferences of sulfur and selenium in mixed chalcophosphates in the family APbPS(4-x)Se(x) (A = K, Rb, Cs; x = 0-4).

The synthesis and structures of the three new compounds, KPbPS(1.84)Se(2.16) (1), RbPbPS(1.56)Se(2.43) (2), and CsPbPS(3.46)Se(0.54) (3), are reported. The solid state structures of 1-3 consist of two-dimensional layers of [PbP(S/Se)(4)] separated by alkali metal ions. The structure of 1 was solved in the orthorhombic space group Pna2(1). Compounds 2 and 3 possess the CsSmGeS(4) structure type, crystallizing in the orthorhombic space group P2(1)2(1)2(1). All compounds were refined as racemic twins. All chalcogen sites around the tetrahedrally coordinated P atoms show mixed S/Se occupancy; however, there is a preference for Se binding to Pb ions and S binding to alkali ions. A (31)P magic angle spinning NMR study on 1 suggests that, in mixed seleno-/thiophosphates, all of the anions [PS(x)Se(4-x)](3-) (x = 0, 1, 2, 3, 4) are present. The different amount of sulfur and selenium present in KPbPS(1.84)Se(2.16) (1), RbPbPS(1.56)Se(2.43) (2), and CsPbPS(3.46)Se(0.54) (3) is reflected in the solid state absorption spectra from which bandgaps of 2.2 eV were determined for 1 and 2, and a blue-shift to 2.5 eV was observed because of the higher sulfur-content in 3. Thermogravimetric analysis experiments indicated that, upon heating, compound 1 decomposes forming PbSe and sulfur together with other unidentified products. A Raman spectrum of compound 1 showed more bands than are usually observed in seleno- or thiophosphate salts and is another indicator of the mixed seleno-/thiophosphate anions found in 1.