Noncentrosymmetric γ-Cs2I4O11 Obtained from IO4 Polyhedral Rearrangements in the Centrosymmetric ß-Phase.

We report the synthesis and optical properties of noncentrosymmetric (NCS) γ-Cs2I4O11 that was obtained through IO4 polyhedral rearrangements from centrosymmetric (CS) ß-Cs2I4O11. Trifluoroacetic acid (TFA) acts as a structure-directing agent and plays a key role in the synthesis. It is suggested that the function of TFA is to promote rearrangement reactions found in the organic synthesis of stereoisomers. γ-Cs2I4O11 crystallizes in the NCS monoclinic space group P21 (No. 4) and exhibits a strong second-harmonic-generation (SHG) response of 5.0 × KDP (KH2PO4) under 1064 nm laser radiation. Additional SHG experiments indicate that the material is type I phase matchable. First-principles calculations show that SHG intensity mainly comes from its d34, d21, and d23 SHG tensor components. The synthetic strategy of discovering γ-Cs2I4O11 provides a new way for designing novel NCS SHG materials.

Lanthanide thioborates, an emerging class of nonlinear optical materials, efficiently synthesized using the boron-chalcogen mixture method.

The Boron-Chalcogen Mixture method was used to obtain single crystals of the previously extremely difficult to synthesize lanthanide orthothioborates to investigate their structures and their structurally connected optical behavior, such as second harmonic generation. Using a combined halide and polychalcogenide flux, the BCM method yielded single crystals of LnBS3 (Ln = La, Ce, Pr, Nd), which are isostructural and crystallize in the non-centrosymmetric space group, Pna21. Second harmonic generation measurements confirmed the expectation that LaBS3 would exhibit a strong SHG response, measured at 1.5 × KDP.

Pharmacists' response during a pandemic: A survey on readiness to test during COVID-19.

BACKGROUND: Testing is a principle component to reopening society and bringing the coronavirus 2019 (COVID-19) pandemic to an end. Pharmacists have the ability to perform certain point-of-care tests under federal regulations. On April 8, 2020, the Office of the Assistant Secretary for Health issued new guidance authorizing licensed pharmacists to order and administer COVID-19 tests. OBJECTIVE: The primary objective of this study was to investigate the views of pharmacists about pharmacist-ordered and -administered COVID-19 testing. METHODS: A 13-item questionnaire was developed to survey pharmacists who currently hold an active license in Rhode Island. RESULTS: A total of 122 (13.8%) pharmacists consented and responded to at least 1 question of the survey. The results indicated that the primary concern of the pharmacists in regard to performing COVID-19 testing was spreading the infection to family members (71.3%). Becoming personally infected (59.8%) and not having access to appropriate personal protective equipment (PPE) (62.3%) were the second and third most common concerns of the pharmacists. Almost all of the pharmacists (99.9%) responded that they would be willing to take part in the testing process if they had appropriate PPE. A total of 46% of the pharmacists expressed concern regarding reimbursement for their company, whereas 56% of the pharmacists requested personal compensation for this service. CONCLUSION: Expanding the pool of health care providers who can perform testing is critical to achieving and sustaining proposed testing thresholds. Rhode Island pharmacists are willing to take part in performing COVID-19 testing provided appropriate PPE is available and services are reimbursed. Pharmacists are the most accessible and essential health care providers willing to take on critically important roles during the COVID-19 pandemic provided appropriate safety measures can be met.

Applying the index of watershed integrity to the Matanuska-Susitna basin.

The Matanuska-Susitna Borough is the fastest growing region in the State of Alaska and is impacted by a number of human activities. We conducted a multiscale assessment of the stressors facing the borough by developing and mapping the Index of Watershed Integrity (IWI) and Index of Catchment Integrity (the latter considers stressors in areas surrounding individual stream segments exclusive of upstream areas). The assessment coincided with the borough's stormwater management planning. We adapted the list of anthropogenic stressors used in the original conterminous United States IWI application to reflect the borough's geography, human activity, and data availability. This analysis also represents an early application of the NHDPlus High Resolution geospatial framework and the first use of the framework in an IWI study. We also explored how remediation of one important stressor, culverts, could impact watershed integrity at the catchment and watershed scales. Overall, we found that the integrity scores for the Matanuska-Susitna basin were high compared to the conterminous United States. Low integrity scores did occur in the rapidly developing Wasilla-Palmer core area. We also found that culvert remediation had a larger proportional impact in catchments with fewer stressors.

Hydrated Metal Ion Salts of the Weakly Coordinating Fluoroanions PF6-, TiF62-, B12F122-, Ga(C2F5)4-, B(3,5-C6H3(CF3)2)4-, and Al(OC(CF3)3)4-. In Search of the Weakest HOH···F Hydrogen Bonds.

FTIR spectra of microcrystalline samples of 11 metal ion salt hydrates of a variety of weakly coordinating fluoroanions are reported. The compounds studied were Li(H2O)4(Al(OC(CF3)3)4), Li(H2O)(B(3,5-C6H3(CF3)2)4), Li(H2O)n(Ga(C2F5)4), Li(H2O)(PF6), Li2(H2O)2(TiF6), Li2(H2O)4(B12F12), Na(H2O)(PF6), Na2(H2O)2(B12F12), K2(H2O)2(B12F12), Rb2(H2O)2(B12F12), Cs2(H2O)(B12F12), and their partially or completely deuterated isotopologs and isotopomers. The O-D···F hydrogen bonds in Li(HOD)(H2O)3(Al(OC(CF3)3)4) (ν(OD) = 2706 cm-1), Li(HOD)(B(3,5-C6H3(CF3)2)4) (ν(OD) = 2705 cm-1), and Li(HOD)(H2O)n(Ga(C2F5)4) (ν(OD) = 2697 cm-1) rival HOD absorbed in polyvinylidene difluoride (ν(OD) = 2696 cm-1) and HOD···FCH3 in a frozen Ar matrix (ν(OD) = 2685 cm-1) for the weakest hydrogen bonds between a water molecule and an F atom in any compound. As weak as they are, minor differences in O-H···F hydrogen bonds in the same fluoroanion salt can be distinguished spectroscopically. Uncoupled HOD molecules in asymmetric F···HOD···F' hydrogen bonding environments in Rb+, Cs+, Mg2+, and Co2+ hydrates of B12F122- gave rise to two observable ν(OD) bands even though the two R(O···F) distances differ by only 0.010(4) Å (Mg2+), 0.033(2) Å (Co2+), 0.074(4) Å (Rb+), and 0.106(6) Å (Cs+). A plot of ν(OD) for hydrates with a single uncoupled HOD molecule per metal ion (e.g., Li(HOD)(H2O)3(Al(OC(CF3)3)4)) vs R(O···F) distance from single-crystal X-ray or neutron diffraction structures was prepared. The ν(OD) values range from 2305 to 2706 cm-1 and the R(O···F) distances range from 2.58 to 3.17 Å. The plot consists of 53 {ν(OD), R(O···F)} data points, 23 of which are new and have ν(OD) > 2600 cm-1, in contrast to a 1994 ν(OD) vs R(O···F) plot with 28 data points, none of which had ν(OD) > 2600 cm-1. There is a clear and significant difference between the new ν(OD) vs R(O···F) plot and a literature ν(OD) vs R(O···O) plot for hydrates containing O-D···O hydrogen bonds. For a given ν(OD) stretching frequency, the exponential regression curves show that R(O···F) is typically 0.1-0.2 Å shorter than R(O···O), in harmony with the lower basicity and smaller size of F atoms vs O atoms.

Room-Temperature FTIR Spectra of the Cyclic S4 (H2O)4 Cluster in Crystalline Li2(H2O)4(B12F12): Observation of B and E ν(OH) Bands and Coupling of Strong O-H···O and Weak O-H···F Vibrations.

Room-temperature-attenuated total reflection-Fourier transform infrared (FTIR) spectra of the structurally characterized crystalline lithium salt Li2(H2O)4(B12F12), which contains a cyclic S4 symmetry (H2O)4 cluster, and several partially or completely deuterated isotopologs, suggest the following conclusions: (i) B and E normal modes gave rise to two distinguishable ν(OHbound) bands, separated by 42 cm-1, two distinguishable ν(OHfree) bands, separated by 13 cm-1, and two distinguishable δ(HOH) bands, separated by 19 cm-1, in the FTIR spectrum of Li2(H2O)4(B12F12); (ii) B and E normal modes gave rise to two distinguishable ν(ODbound) bands separated by 20 cm-1 in the FTIR spectrum of Li2(D2O)4(B12F12); (iii) coupling between ν(OHbound) and ν(OHfree) normal modes or between ν(ODbound) and ν(ODfree) normal modes is weak, but finite, and resulted in shifts of 4-10 cm-1 for the respective bands in the spectra of Li2(H2O)4(B12F12) vs Li2(HOD)(D2O)3(B12F12) or in the spectra of Li2(D2O)4(B12F12) vs Li2(HOD)(H2O)3(B12F12); and (iv) a δ(DOD) band for an S4 (D2O)4 cluster, at ca. 1202 cm-1, was observed for the first time. In addition, FTIR spectra of the lithium salt containing cyclic [(HOD)(H2O)3] or [(HOD)(D2O)3] clusters are the first examples in which bands that are unambiguously assigned to both HO-D···O and DO-H···O hydrogen bonds in the same sample have been observed for a water tetramer.

Manifestations of Weak O-H···F Hydrogen Bonding in M(H2O) n(B12F12) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg-Ba, Co, Ni, Zn).

Eight M(H2O) n(Z) salt hydrates were characterized by single-crystal X-ray diffraction (Z2- = B12F122-): M = Ca, Sr, n = 7; M = Mg, Co, Ni, Zn, n = 6; M = Ba, n = 4, 5. Weak O-H···F hydrogen bonding between the M(H2O) n2+ cations and Z2- resulted in room-temperature Fourier transform infrared (FTIR) spectra having sharp ν(OH) bands, with full widths at half max of 10-30 cm-1, which are much more narrow than ν(OH) bands in room temperature FTIR spectra of most salt hydrates. Clearly resolved νasym(OH/OD) and νsym(OH/OD) bands with Δν(OH) as small as 17 cm-1 and Δν(OD) as small as 11 cm-1 were observed (Δν(OX) = νasym(OX) - νsym(OX)). The isomorphic hexahydrates ( R3̅) have two fac-(H2O)3 sets of H2O ligands and nearly octahedral coordination spheres. They exhibited four resolvable ν(OH) bands, one νasym(OH)/νsym(OH) pair for H2O ligands with longer O(H)···F distances and one νasym(OH)/νsym(OH) pair for H2O ligands with shorter O(H)···F distances. The ν(OH) bands for the three H2O molecules with shorter, slightly stronger O(H)···F hydrogen bonds were broader, more intense, and red-shifted by ca. 25 cm-1 relative to the bands for the three other H2O molecules, the first time that such small differences in relatively weak O(H)···F hydrogen bonds in the same crystalline hexahydrate have resulted in observable IR spectroscopic differences at room temperature. For the first time room temperature ν(OH) values for salt hexahydrates showed the monotonic progression Mg2+ > Co2+ > Ni2+ > Zn2+, essentially the same progression as the p Ka values for these metal ions in aqueous solution. A further manifestation of the weak O-H···F hydrogen bonding in these hydrates is the latent porosity exhibited by Ba(H2O)5,8(Z), Sr(H2O) n,m(Z), and Ca(H2O)4,6(Z). Finally, the H2O/D2O exchange reaction Co(D2O)6(Z) → Co(H2O)6(Z) was ca. 50% complete in 1 h at 50 °C in N2/17 Torr H2O( g).

Latent Porosity in Alkali-Metal M2B12F12 Salts: Structures and Rapid Room-Temperature Hydration/Dehydration Cycles.

Structures of the alkali-metal hydrates Li2(H2O)4Z, LiK(H2O)4Z, Na2(H2O)3Z, and Rb2(H2O)2Z, unit cell parameters for Rb2Z and Rb2(H2O)2Z, and the density functional theory (DFT)-optimized structures of K2Z, K2(H2O)2Z, Rb2Z, Rb2(H2O)2Z, Cs2Z, and Cs2(H2O)Z are reported (Z2- = B12F122-) and compared with previously reported X-ray structures of Na2(H2O)0,4Z, K2(H2O)0,2,4Z, and Cs2(H2O)Z. Unusually rapid room-temperature hydration/dehydration cycles of several M2Z/M2(H2O)nZ salt hydrate pairs, which were studied by isothermal gravimetry, are also reported. Finely ground samples of K2Z, Rb2Z, and Cs2Z, which are not microporous, exhibited latent porosity by undergoing hydration at 24-25 °C in the presence of 18 Torr of H2O(g) to K2(H2O)2Z, Rb2(H2O)2Z, and Cs2(H2O)Z in 18, 40, and 16 min, respectively. These hydrates were dehydrated at 24-25 °C in dry N2 to the original anhydrous M2Z compounds in 61, 25, and 76 min, respectively (the exact times varied from sample to sample depending on the particle size). The hydrate Na2(H2O)2Z also exhibited latent porosity by undergoing multiple 90 min cycles of hydration to Na2(H2O)3Z and dehydration back to Na2(H2O)2Z at 23 °C. For the K2Z, Rb2Z, and Cs2Z transformations, the maximum rate of hydration (rhmax) decreased, and the absolute value of the maximum rate of dehydration (rdmax) increased, as T increased. For K2Z ↔ K2(H2O)2Z hydration/dehydration cycles with the same sample, the ratio rhmax/rdmax decreased 26 times over 8.6 °C, from 3.7 at 23.4 °C to 0.14 at 32.0 °C. For Rb2Z ↔ Rb2(H2O)2Z cycles, rhmax/rdmax decreased from 0.88 at 23 °C to 0.23 at 27 °C. For Cs2Z ↔ Cs2(H2O)Z cycles, rhmax/rdmax decreased 20 times over 8 °C, from 6.7 at 24 °C to 0.34 at 32 °C. In addition, the reversible substitution of D2O for H2O in fully hydrated Rb2(H2O)2Z in the presence of N2/16 Torr of D2O(g) was complete in only 60 min at 23 °C.

Report of the 2016-17 Academic Affairs Standing Committee: Entrustable Professional Activities Implementation Roadmap.

The purpose of this report is to: 1) Identify linkages across the EPA statements, Center for the Advancement of Pharmacy Education 2013 Educational Outcomes (CAPE 2013) and the Joint Commission of Pharmacy Practitioners' Pharmacist Patient Care Process (PPCP); 2) Provide ways EPA statements can be used to communicate core skills that are part of the entry-level pharmacist identity; 3) Suggest a potential roadmap for AACP members on how to implement EPA statements.