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Byline: Matthew Klimek (St John's University, Queens, New York); Matthew M. Lacroix, PharmD (St John's University College of Pharmacy and Health Professions, Department of Clinical Pharmacy Practice, Queens, New York, [...]

The Maine Prescription Monitoring Program (PMP) was created to prevent prescription drug misuse and diversion. The PMP collects data for all Schedule II, III and IV prescriptions dispensed by pharmacies licensed in Maine. This article presents a retrospective analysis of the PMP for prescribing trends and utilization patterns from state fiscal year 2006 to 2010. The sample included 11,542,850 Schedule prescriptions for 1,024,649 unduplicated patients in a 5-year database of the PMP. The number of controlled prescriptions steadily increased from 2.05 million in 2006 to 2.51 million in 2010. Opioid analgesics and stimulants were found to be the most commonly prescribed and fastest growing scheduled drug categories, respectively. Most individuals (82.9%) accessed their controlled drugs from one to two prescribers and pharmacies. Patients who utilized five prescribers and more used a greater number of pharmacies than those who utilized less than five prescribers ( p < 0.001). The dramatic increase in the number of controlled prescriptions shown in this study has important public health implications. [ABSTRACT FROM AUTHOR]

We report the synthesis and optical properties of noncentrosymmetric (NCS) γ - Cs 2 I 4 O 11 that was obtained through IO 4 polyhedral rearrangements from centrosymmetric (CS) β-Cs 2 I 4 O 11 . 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 - Cs 2 I 4 O 11 crystallizes in the NCS monoclinic space group P 2 1 (No. 4) and exhibits a strong second-harmonic-generation (SHG) response of 5.0 × KDP (KH 2 PO 4 ) 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 d 34 , d 21 , and d 23 SHG tensor components. The synthetic strategy of discovering γ - Cs 2 I 4 O 11 provides a new way for designing novel NCS SHG materials.

Room-temperature-attenuated total reflection-Fourier transform infrared (FTIR) spectra of the structurally characterized crystalline lithium salt Li 2 (H 2 O) 4 (B 12 F 12 ), which contains a cyclic S 4 symmetry (H 2 O) 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(OH bound ) bands, separated by 42 cm -1 , two distinguishable ν(OH free ) bands, separated by 13 cm -1 , and two distinguishable δ(HOH) bands, separated by 19 cm -1 , in the FTIR spectrum of Li 2 (H 2 O) 4 (B 12 F 12 ); (ii) B and E normal modes gave rise to two distinguishable ν(OD bound ) bands separated by 20 cm -1 in the FTIR spectrum of Li 2 (D 2 O) 4 (B 12 F 12 ); (iii) coupling between ν(OH bound ) and ν(OH free ) normal modes or between ν(OD bound ) and ν(OD free ) normal modes is weak, but finite, and resulted in shifts of 4-10 cm -1 for the respective bands in the spectra of Li 2 (H 2 O) 4 (B 12 F 12 ) vs Li 2 (HOD)(D 2 O) 3 (B 12 F 12 ) or in the spectra of Li 2 (D 2 O) 4 (B 12 F 12 ) vs Li 2 (HOD)(H 2 O) 3 (B 12 F 12 ); and (iv) a δ(DOD) band for an S 4 (D 2 O) 4 cluster, at ca. 1202 cm -1 , was observed for the first time. In addition, FTIR spectra of the lithium salt containing cyclic [(HOD)(H 2 O) 3 ] or [(HOD)(D 2 O) 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.

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(H 2 O) 4 (Al(OC(CF 3 ) 3 ) 4 ), Li(H 2 O)(B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ), Li(H 2 O) n (Ga(C 2 F 5 ) 4 ), Li(H 2 O)(PF 6 ), Li 2 (H 2 O) 2 (TiF 6 ), Li 2 (H 2 O) 4 (B 12 F 12 ), Na(H 2 O)(PF 6 ), Na 2 (H 2 O) 2 (B 12 F 12 ), K 2 (H 2 O) 2 (B 12 F 12 ), Rb 2 (H 2 O) 2 (B 12 F 12 ), Cs 2 (H 2 O)(B 12 F 12 ), and their partially or completely deuterated isotopologs and isotopomers. The O-D···F hydrogen bonds in Li(HOD)(H 2 O) 3 (Al(OC(CF 3 ) 3 ) 4 ) (ν(OD) = 2706 cm -1 ), Li(HOD)(B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ) (ν(OD) = 2705 cm -1 ), and Li(HOD)(H 2 O) n (Ga(C 2 F 5 ) 4 ) (ν(OD) = 2697 cm -1 ) rival HOD absorbed in polyvinylidene difluoride (ν(OD) = 2696 cm -1 ) and HOD···FCH 3 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 + , Mg 2+ , and Co 2+ hydrates of B 12 F 12 2- gave rise to two observable ν(OD) bands even though the two R (O···F) distances differ by only 0.010(4) Å (Mg 2+ ), 0.033(2) Å (Co 2+ ), 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)(H 2 O) 3 (Al(OC(CF 3 ) 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.

Eight M(H 2 O) n (Z) salt hydrates were characterized by single-crystal X-ray diffraction (Z 2- = B 12 F 12 2- ): 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(H 2 O) n 2+ cations and Z 2- 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 ν asym (OH/OD) and ν sym (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) = ν asym (OX) - ν sym (OX)). The isomorphic hexahydrates ( R3̅) have two fac-(H 2 O) 3 sets of H 2 O ligands and nearly octahedral coordination spheres. They exhibited four resolvable ν(OH) bands, one ν asym (OH)/ν sym (OH) pair for H 2 O ligands with longer O(H)···F distances and one ν asym (OH)/ν sym (OH) pair for H 2 O ligands with shorter O(H)···F distances. The ν(OH) bands for the three H 2 O 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 H 2 O 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 Mg 2+ > Co 2+ > Ni 2+ > Zn 2+ , essentially the same progression as the p K a 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(H 2 O) 5,8 (Z), Sr(H 2 O) n,m (Z), and Ca(H 2 O) 4,6 (Z). Finally, the H 2 O/D 2 O exchange reaction Co(D 2 O) 6 (Z) → Co(H 2 O) 6 (Z) was ca. 50% complete in 1 h at 50 °C in N 2 /17 Torr H 2 O( g).

Structures of the alkali-metal hydrates Li 2 (H 2 O) 4 Z, LiK(H 2 O) 4 Z, Na 2 (H 2 O) 3 Z, and Rb 2 (H 2 O) 2 Z, unit cell parameters for Rb 2 Z and Rb 2 (H 2 O) 2 Z, and the density functional theory (DFT)-optimized structures of K 2 Z, K 2 (H 2 O) 2 Z, Rb 2 Z, Rb 2 (H 2 O) 2 Z, Cs 2 Z, and Cs 2 (H 2 O)Z are reported (Z 2- = B 12 F 12 2- ) and compared with previously reported X-ray structures of Na 2 (H 2 O) 0,4 Z, K 2 (H 2 O) 0,2,4 Z, and Cs 2 (H 2 O)Z. Unusually rapid room-temperature hydration/dehydration cycles of several M 2 Z/M 2 (H 2 O) n Z salt hydrate pairs, which were studied by isothermal gravimetry, are also reported. Finely ground samples of K 2 Z, Rb 2 Z, and Cs 2 Z, which are not microporous, exhibited latent porosity by undergoing hydration at 24-25 °C in the presence of 18 Torr of H 2 O(g) to K 2 (H 2 O) 2 Z, Rb 2 (H 2 O) 2 Z, and Cs 2 (H 2 O)Z in 18, 40, and 16 min, respectively. These hydrates were dehydrated at 24-25 °C in dry N 2 to the original anhydrous M 2 Z compounds in 61, 25, and 76 min, respectively (the exact times varied from sample to sample depending on the particle size). The hydrate Na 2 (H 2 O) 2 Z also exhibited latent porosity by undergoing multiple 90 min cycles of hydration to Na 2 (H 2 O) 3 Z and dehydration back to Na 2 (H 2 O) 2 Z at 23 °C. For the K 2 Z, Rb 2 Z, and Cs 2 Z transformations, the maximum rate of hydration (rh max ) decreased, and the absolute value of the maximum rate of dehydration (rd max ) increased, as T increased. For K 2 Z ↔ K 2 (H 2 O) 2 Z hydration/dehydration cycles with the same sample, the ratio rh max /rd max decreased 26 times over 8.6 °C, from 3.7 at 23.4 °C to 0.14 at 32.0 °C. For Rb 2 Z ↔ Rb 2 (H 2 O) 2 Z cycles, rh max /rd max decreased from 0.88 at 23 °C to 0.23 at 27 °C. For Cs 2 Z ↔ Cs 2 (H 2 O)Z cycles, rh max /rd max decreased 20 times over 8 °C, from 6.7 at 24 °C to 0.34 at 32 °C. In addition, the reversible substitution of D 2 O for H 2 O in fully hydrated Rb 2 (H 2 O) 2 Z in the presence of N 2 /16 Torr of D 2 O(g) was complete in only 60 min at 23 °C.