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A Mn(II) salt and A+CN− under anaerobic conditions react to form 2‐D and 3‐D extended structured compounds of AmMnIIn(CN)m+2n stoichiometry. Here, the creation and characterization of this large family of compounds, for example AMnII3(CN)7, A2MnII3(CN)8, A2MnII5(CN)12, A3MnII5(CN)13, and A2MnII[MnII(CN)6], where A represents alkali and tetraalkylammonium cations, is reviewed. Cs2MnII[MnII(CN)6] has the typical Prussian blue face centered cubic unit cell. However, the other alkali salts are monoclinic or rhombohedral. This is in accord with smaller alkali cation radii creating void space that is minimized by increasing the van der Waals stabilization energy by reducing ∠Mn−N≡C, which, strengthens the magnetic coupling and increases the magnetic ordering temperatures. This is attributed to the non‐rigidity of the framework structure due the significant ionic character associated with the high‐spin MnII sites. For larger tetraalkylammonium cations, the high‐spin Mn sites lack sufficient electrostatic A+⋅⋅⋅NC stabilization and form unexpected 4‐ and 5‐coordinated Mn sites within a flexible, extended framework around the cation; hence, the size, shape, and charge of the cation dictate the unprecedented stoichio‐metry and unpredictable cation adaptive structures. Antiferromagnetic coupling between adjacent MnII sites leads to ferrimagnetic ordering, but in some cases antiferromagnetic coupling of ferrimagnetic layers are compensated and synthetic antiferromagnets are observed. The magnetic ordering temperatures for ferrimagnetic A2MnII[MnII(CN)6] with both octahedral high‐ and low‐spin MnII sites increase with decreasing ∠Mn−N≡C. The crystal structures for all of the extended structured materials were obtained by powder diffraction. [ABSTRACT FROM AUTHOR]

To identify the genesis of the differing magnetic behaviors for the ferro- (FO) and metamagnetic (MM) polymorphs of [FeCp*2][TCNQ] (Cp* = pentamethylcyclopentadienide; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) the low temperature (18 ± 1 K) structures of each polymorph were determined from high-resolution synchrotron powder diffraction data. Each polymorph possesses chains of alternating S = 1/2 [FeCp*2]˙+ cations and S = 1/2 [TCNQ]˙+, but with differing relative orientations. These as well as an additional paramagnetic polymorph do not thermally interconvert. In addition, the room and low (<70 ± 10 K) temperature structures of the MM polymorph, MMRT and MMLT, respectively, differ from that previously reported at 167 K (−106 °C) MM structure, and no evidence of either phase transition was previously noted even from the magnetic data. This transition temperature and enthalpy of this phase transition for MMRTMM was determined to be 226.5 ± 0.4 K (−46.7 ± 0.4 °C) and 0.68 ± 0.04 kJ mol−1 upon warming, respectively, from differential calorimetry studies (DSC). All three MM phases are triclinic (P1¯) with the room temperature phase having a doubled unit cell relative to the other two. The lower temperature phase transition involves a small rearrangement of the molecular ions and shift in lattice parameters. These three MM and FO polymorphs have been characterized and form extended 1-D chains with alternating S = 1/2 [FeCp*2]˙+ cations, and S = 1/2 [TCNQ]˙− anions, whereas the fifth, paramagnetic (P) polymorph possesses S = 0 π-[TCNQ]22− dimers. At 18 ± 1 K the intrachain Fe⋯Fe separations are 10.738(2) and 10.439(3) Å for the FO and MMLT polymorphs, respectively. The key structural differences between FO and MMLT at 18 ± 1 K are the 10% shorter interchain N⋯N and the 2.8% shorter intrachain Fe⋯Fe separation present for MMLT. Computational analysis of all nearest-neighbor spin couplings for the 18 K structures of FO and MMLT indicates that the intrachain [FeCp*2]˙+⋯[TCNQ]˙− spin couplings (H = −2Si·Sj) are the strongest (4.95 and 6.5 cm−1 for FO and MMLT, respectively), as previously hypothesized, and are ferromagnetic due to their S = 1/2 spins residing in orthogonal orbitals. The change in relative [TCNQ]˙−⋯[TCNQ]˙− orientations leads to a computed change from the ferromagnetic interaction (0.2 cm−1) for FO to an antiferromagnetic interaction (−0.1 cm−1) for MMLT in accord with its observed antiferromagnetic ground state. Hence, the magnetic ground state cannot be solely described by the dominant magnetic interactions. [ABSTRACT FROM AUTHOR]

Objective To assess sales of anti-cancer medicines in the 2017 World Health Organization's WHO Model list of essential medicines in China, Indonesia, Kazakhstan, Malaysia, Philippines and Thailand from 2007 (2008 for Kazakhstan and Malaysia) to 2017. Methods We extracted sales volume data for 39 anti-cancer medicines from the IQVIA database. We divided the total quantity sold by the reference defined daily dose to estimate the total number of defined daily doses sold, per country per year, for three types of anti-cancer therapies (traditional chemotherapy, targeted therapy and endocrine therapy). We adjusted these data by the number of new cancer cases in each country for each year. Findings We observed an increase in sales across all types of anti-cancer therapies in all countries. The largest number of defined daily doses of traditional chemotherapy per new cancer case was sold in Thailand; however, the largest relative increase per new cancer case occurred in Indonesia (9.48-fold). The largest absolute and relative increases in sales of defined daily doses of targeted therapies per new cancer case occurred in Kazakhstan. Malaysia sold the largest number of adjusted defined daily doses of endocrine therapies in 2017, while China and Indonesia more than doubled their adjusted sales volumes between 2007 and 2017. Conclusion The use of sales data can fill an important knowledge gap in the use of anti-cancer medicines, particularly during periods of insurance coverage expansion. Combined with other data, sales volume data can help to monitor efforts to improve equitable access to essential medicines. [ABSTRACT FROM AUTHOR]

We report a new polymorph of acridine, C13H9N, denoted form IX, obtained as thin needles by slow evaporation of a toluene solution. The structure was solved and refined from powder X-ray data. The structures of five unsolvated forms were previously known, but this is only the second with one molecule in the asymmetric unit. The melting point [differential scanning calorimetry (DSC) onset] and heat of fusion are 108.8 (3) °C and 19.2 (4) kJ mol−1, respectively. [ABSTRACT FROM AUTHOR]

The reaction of MnII(O2CMe)2 and NaCN or LiCN in water forms a light green insoluble material. Structural solution and Rietveld refinement of high‐resolution synchrotron powder diffraction data for this unprecedented, complicated compound of previously unknown composition revealed a new alkali‐free ordered structural motif with [MnII4(μ3‐OH)4]4+ cubes and octahedral [MnII(CN)6]4− ions interconnected in 3D by MnII‐N≡C‐MnII linkages. The composition is {[MnII(OH2)3][MnII(OH2)]3}(μ3‐OH)4][MnII(μ‐CN)2(CN)4]⋅H2O=[MnII4(μ3‐OH)4(OH2)6][MnII(μ‐CN)2(CN)4]⋅H2O, which is further simplified to [Mn4(OH)4][Mn(CN)6](OH2)7 (1). 1 has four high‐spin (S=5/2) MnII sites that are antiferromagnetically coupled within the cube and are antiferromagnetically coupled to six low‐spin (S=1/2) octahedral [MnII(CN)6]4− ions. Above 40 K the magnetic susceptibility, χ(T), can be fitted to the Curie–Weiss expression, χ ∝(T−θ)−1, with θ=−13.4 K, indicative of significant antiferromagnetic coupling and 1 orders as an antiferromagnet at Tc=7.8 K. Structural solution and Rietveld refinement of high‐resolution diffraction data for an unprecedented, complicated compound of previously unknown composition revealed a new alkali‐free ordered structural motif with [MnII4(μ3‐OH)4]4+ cubes and octahedral [MnII(CN)6]4− ions interconnected in 3D. [ABSTRACT FROM AUTHOR]

Reaction of [Ru 2 (O 2 CMe) 4 ]Cl and Na[Co III Pc(CN) 2 ] (H 2 Pc = phthalocyanine) forms [Ru 2 (O 2 CMe) 4 ][Co III Pc(CN) 2 ] with the targeted linear structure possessing linear ⋯Ru–N C–Co⋯ linkages. The magnetic properties of [Ru 2 (O 2 CMe) 4 ][Co III Pc(CN) 2 ] can be fit to a zero field splitting model with D /k B = 95 K (66 cm −1 ). Attempts to prepare the Cr(III) analogue were unsuccessful due to cyanide abstraction by the ruthenium site. [ABSTRACT FROM AUTHOR]

Objectives: There is global concern that antimicrobial resistance is a major threat to healthcare. Antimicrobial use is a primary driver of resistance but little information exists about the variation in antimicrobial use in individual hospitals in England over time or comparative use between hospitals. The objective of this study was to collate, analyse and report issue data from pharmacy records of 158 National Health Service (NHS) acute hospitals.Methods: This was a cohort study of inpatient antibacterial use in acute hospitals in England analysed over 5 years through a data warehouse from IMS Health, a leading provider of information, services and technology for the healthcare industry. Around 98% of NHS hospitals were included in a country with a population of 50 million residents.Results: There was a dramatic change in the usage of different groups of antibacterials between 2009 and 2013 with a marked reduction in the use of first-generation cephalosporins by 24.7% and second-generation cephalosporins by 41%, but little change in the use of third-generation cephalosporins (+5.7%) and fluoroquinolones (+1.6%). In contrast, use of co-amoxiclav, carbapenems and piperacillin/tazobactam increased by 60.1%, 61.4% and 94.8%, respectively. There was wide variation in the total and relative amounts of antibacterials used between individual hospitals.Conclusions: Longitudinal analysis of antibacterial use demonstrated remarkable changes in NHS hospitals, probably reflecting governmental and professional guidance to mitigate the risk of Clostridium difficile infection. The wide variation in usage between individual hospitals suggests potential for quality improvement and benchmarking. Quality measures of optimal hospital antimicrobial prescribing need urgent development and validation to support antimicrobial stewardship initiatives. [ABSTRACT FROM AUTHOR]

Objectives: To examine the impact of the characteristics of doctors and patients on the use of low cost generic formulations in Brazil in 2012. Setting: This study examined 17,627 consultations in which a medicine known to have an unbranded generic formulation available was prescribed. These consultations were generated by a sample of 723 doctors working in both public and private sectors in 2012. Results: 74% of doctors prescribed both branded and unbranded formulations. Only 8/723 doctors never prescribed a generic of any sort. Doctors were found to prescribe less expensive formulations of medicines to those patients with co-morbid conditions and those needing treatment with higher priced medicines. Increasing patient age was significantly associated with less expensive formulations. Conclusion: This study indicates that Brazil is a relatively mature generic market with most doctors prescribing a generic formulation. Doctors prescribe formulations that are relatively less expensive where the absolute price of the medicine is higher and where the patient is older or being treated for more than one diagnosis. This suggests that the economic burden of treatment may be being taken into account. [ABSTRACT FROM AUTHOR]

Purpose: Poly(ADP-ribose) polymerase-1 (PARP-1) is a nuclear enzyme important in DNA repair. PARP-1 activation at points of DNA strand break results in poly(ADP-ribose) polymer formation, opening the DNA structure, and allowing access of other repair enzymes. CEP-9722 inhibits PARP-1 and PARP-2 and is designed to potentiate DNA-damaging chemotherapies. Methods: This dose-escalating phase 1 study assessed the safety, maximum tolerated dose (MTD), and pharmacokinetics/pharmacodynamics of CEP-9722 plus temozolomide in adults with solid tumors. Tumor response was also assessed. Participants received a 14-day cycle of CEP-9722 (days 1 and 3-5 or days 1-5), followed by 28-day cycles of CEP-9722 plus temozolomide 150 mg/m on days 1-5. The initial CEP-9722 dose (cohort 1) was 150 mg/day; dose escalation followed a modified Fibonnaci sequence. Results: Twenty-six patients received CEP-9722 150-1,000 mg/day combined with temozolomide. Dose-limiting toxicities of asthenia and persistent weight loss at 1,000 mg/day resulted in 750 mg/day being defined as the MTD and recommended dose for further study. Overall, 24 (92 %) patients had treatment-related adverse events (TRAEs), mostly grade 1 or 2, with nausea, vomiting, and diarrhea having the strongest relation to CEP-9722. Four patients had grade 3 TRAEs (asthenia, myositis, diarrhea, and fatigue). Systemic exposure generally increased with dosage, with high inter- and intra-patient variability at all doses. Pharmacodynamic assessment confirmed PARP inhibition although no dose response was apparent. One patient with melanoma achieved a partial response (1,000 mg/day). Conclusions: CEP-9722 was adequately tolerated with temozolomide; the MTD was 750 mg/day. Only limited clinical activity was observed. [ABSTRACT FROM AUTHOR]

Polar oxides are technically of great interest but difficult to prepare. Our recent discoveries predicted that polar oxides can be synthesized in the corundum-derivative A2BB'O6 family with unusually small cations at the A-site and a d0 electron configuration ion at B'-site. When magnetic transition-metal ions are incorporated more interesting polar magnetic oxides can form. In this work we experimentally verified this prediction and prepared LiNbO3 (LN)-type polar magnetic Zn2FeTaO6 via high pressure and temperature synthesis. The crystal structure analysis indicates highly distorted ZnO6 and (Fe/ Ta)O6 octahedra, and an estimated spontaneous polarization (Ps) of ∼50 pC/cm2 along the oaxis was obtained from point charge model calculations. Zn2Fe3+Ta5+O6 has a lower magnetic transition temperature (TN ∼ 22 K) than the Mn2FeTaO6 analogue but is less conductive. The dielectric and polarization measurements indicate a potentially switchable component. [ABSTRACT FROM AUTHOR]

Abstract: Vaccines offer the most cost-effective solution to prevent both communicable and non-communicable disease in poor countries. Published studies suggest that vaccine research is seeing declining success. This study updates the latest analyses on success rates in vaccine research, and examines the potential causes of decline and their ongoing impact. Success rates are shown to decline, the observed probability of market entry being just 1.8%, almost a fourfold decline over 5 years, but in the context of a very different product portfolio from that seen in earlier studies. DNA vaccines see high Phase I failures as expected, and therapeutic vaccines have lower success rates than prophylactic vaccines. The changing scientific challenge, lack of investment and lack of co-operation are highlighted as potential causes of the decline. Many issues have now been resolved, but co-operation between academia, regulators and industry remains a significant challenge, requiring links across new disciplines and technologies. [Copyright &y& Elsevier]

Li[TCNE] (TCNE = tetracyanoethylene) magnetically orders as a weak ferromagnet (canted antiferromagnet) below 21.0 ± 0.1 K, as observed from the bifurcation of the field-cooled and zero-field-cooled magnetizations, as well as remnant magnetization. The structure, determined ab initio from synchrotron X-ray powder diffraction data, consists of a planar μ4-[TCNE]•- bound to four tetrahedral Li+ ions. The structure consists of two interpenetrating diamondoid sublattices, with closest interlattice distances of 3.43 and 3.48 Å. At 5 K this magnetic state is characterized by a coercivity of ~30 Oe, a remnant magnetization of 10 emu·Oe/mol, and a canting angle of 0.5°. [ABSTRACT FROM AUTHOR]

Abstract: The structures of FeIICl2bipy and FeII(NCS)2bipy (bipy=2,2′-bipyridine) have been determined with the use of synchrotron powder diffraction data. FeIICl2bipy has a pentacoordinate square pyramidal Fe(II) and forms a centrosymmetric dimer with asymmetric bridging Fe–Cl–Fe bonds. FeII(NCS)2bipy has an octahedral Fe(II) and forms an extended zigzag 1-D chain structure consistent with its previously reported magnetic properties. The magnetic data of FeIICl2bipy is best fit by a S =2 dinuclear model with weak intradimer ferromagnetic coupling (J/k B =2.05K; H =−2J ij S i·S j) and weaker interdimer antiferromagnetic coupling. [Copyright &y& Elsevier]

The mechanism of Ni substitution into the oxide semiconductor InTaO4 has been studied through a combination of structural and spectroscopic techniques, providing insights into its previously reported photo activity. Magnetic susceptibility and X-ray absorption near-edge spectroscopy (XANES) measurements demonstrate that nickel is divalent within the host lattice. The combined refinement of synchrotron X-ray and neutron powder diffraction data indicates that the product of Ni doping has the stoichiometry of (In1-xNi2x/3Tax/3)TaO4 with a solubility limit of x ≈ 0.18, corresponding to 12% Ni on the In site. Single-phase samples were only obtained at synthesis temperatures of 1150 °C or higher due to the sluggish reaction mechanism that is hypothesized to result from small free energy differences between (In1-xNi2x/3Tax/3)TaO4 compounds with different x values. Undoped InTaO4 is shown to have an indirect band gap of 3.96 eV, with direct optical transitions becoming allowed at photon energies in excess of 5.1 eV. Very small band-gap reductions (less than 0.2 eV) result from Ni doping, and the origin of the yellow color of (In1-xNi2x/3Tax/3)TaO4 compounds instead results from a weak 3A2g → 3T1g internal d → d transition not associated with the conduction or valence band that is common to oxide compounds with Ni2+ in an octahedral environment. [ABSTRACT FROM AUTHOR]

Cell survival following DNA damage depends on activating checkpoints to arrest proliferation. Most cancer cells have dysregulated G1 checkpoints making them dependent on their S and G2 checkpoints, which are activated by ATR/Chk1 signalling. Thus, inhibiting ATR or Chk1 should selectively sensitise cancer cells to DNA damage. Genetic inactivation of ATR and Chk1 abrogates cell cycle arrest and enhances cytotoxicity following exposure to DNA-damaging agents. Similar effects were seen with small-molecule Chk1 inhibitors in preclinical studies, and clinical trial data are starting to emerge. Recently, potent ATR inhibitors have been identified that also sensitise cancer cells in vitro. ATR and Chk1 inhibitors might also cause ‘synthetic lethality’ in tumour cells defective in defined DNA repair pathways. [ABSTRACT FROM AUTHOR]

Abstract: To meet Kyoto Protocol obligations, New Zealand is required to estimate forest carbon stock change over the first commitment period (2008–2012). New Zealand has three subcategories of forest, namely: Natural forest; Pre-1990 forest; and Post-1989 forest. The Post-1989 forest carbon inventory undertaken in 2008 used discrete return airborne LiDAR and ground-based measurements of 0.06ha circular plots located on a 4-km×4-km grid. The national carbon stock estimate was based on a double sampling scheme consisting of 246 plots from which both ground and LiDAR data were obtained, supplemented with 46 additional plots assessed using only LiDAR. This paper describes the relationships established between carbon stocks estimated using ground-based measurements and LiDAR metrics. A regression model explaining 74% of the variation in total carbon was developed using LiDAR 30th percentile height (P30ht) and canopy cover (%Cover). The regression estimator improved the precision of the national carbon stock estimate in 2008 by 6% compared to the ground-based estimate. This inventory indicates that it is possible to reduce the cost of obtaining carbon stock estimates to a specified level of precision using a combination of ground-based and LiDAR measurements in a double sampling approach. The theoretical maximum improvement in precision expected in 2012, when additional LiDAR data are expected to be available, is 50–55%. [Copyright &y& Elsevier]

Abstract: Reaction of [Ru2(O2CMe)4]Cl and K2[Ni(CN)4] forms [Ru2(O2CMe)4]2[Ni(CN)4] with the targeted layered structure possessing Ru–Nh name="sbnd" />Ni linkages, albeit strained, with Ru–N#x2013;Cin the range of 147–167°. The magnetic properties of [Ru2(O2CMe)4]2[Ni(CN)4] can be fit to a zero-field splitting model with D/k B =95K (66cm−1). [ABSTRACT FROM AUTHOR]

The reaction of MnII and KCN in aqueous and non-aqueous media leads to the isolation of three-dimensional (3-D) Prussian blue analogues, K2Mn[Mn(CN)6] (1a-d, 1e, respectively). Use of RbCN forms Rb2Mn[Mn(CN)6] (2). 1 and 2 are isomorphic (monoclinic, P21/n: 1 [a = 10.1786(1) Å, b = 7.4124(1) Å, Ca 6.9758(1) Å, β = 90.206(1)°]; 2 [a= 10.4101(1)Å, b = 7.4492(1) Å, c = 7.2132(1) Å, β=90.072(1)°]),with a small monoclinic distortion from the face centered cubic (fcc) structure that is typical of Prussian blue structured materials that was previously reported for K2Mn[Mn(CN)6]. Most notably the average Mn-N-C angles are 148.8° and 1 53,3° for 1 and 2, respectively, which are significantly reduced from linearity. This is attributed to the ionic nature of high spin MnII accommodating a reduced M -CN-M' angle and minimizing void space. Compounds 1a,b have a sharp, strong vOH band at 3628 cm-1,while 1e lacks a vOH absorption. The vOH absorption in 1a,b is attributed to surface water, as use of D2O shifts the absorption to 2677 cm-1, and that 1a-e are isostructural. Also, fcc Prussian blue-structured Cs2Mn[Mn(CN)6] (3) has been structurally [Fm3m: a = 10.6061(1) Å] and magnetically characterized. The magnetic ordering temperature, T, increases as K+ (41 K)> Rb+ (34.6 K) > Cs+ (21 K) for A2Mn[Mn(CN)6] in accord with the increasing deviation for linearity of the Mn-N-C linkages [148.8 (K+) > 153.3 (Rb+) > 180 (Cs+], decreasing Mn(ll)…Mn(ll) separations [5.09 (K+) <5.19 (Rb+) < 5.30 A (Cs+), and decreasing size of the cation (increasing electrostatic interactions). Hence, the bent cyanide bridges play a crucial role in the superexchange mechanism by increasing the coupling via shorter Mn(ll)…Mn(ll) separations, and perhaps enhanced overlap. In addition, the temperature dependent magnetic behavior of K4[MnII(CN)6]·3H2O is reported. [ABSTRACT FROM AUTHOR]

The article discusses a study on the crystal and molecular structures of the organic compound 2-ethoxybenzamide or C9H11NO2. The ribbon-like packing motifs were instigated by additional hydrogen bonds between adjacent dimers. A T-shaped herringbone pattern characterized the ribbons. The simulated annealing global optimization algorithm was used to solve the crystal structure.

The reaction of Cr(C6H6)2 and 1,2,4,5-tetracyanopyrazine (TCNP) forms [Cr(C6H6)2][TCNP], and TCNP is reduced and forms the eclipsed π[TCNP]22- dimer. Diamagnetic [TCNP]22- has an intradimer separation of 3.14(2) Å. The intradimer C⋯C and N⋯N separations are 3.29(2) and 3.42(2) Å, respectively, and increase with the distance from the center Of the molecule, due to nitriles bending away from the plane of themolecule by 5 ± 1°. [TCNP]22- is best described by an atoms-in-molecules analysis as having a 2e-/8c C-C bond involving the four C atoms from each six-member ring. The results of B3LYP/6-31 +G(d)- computed interactions indicate that the [TCNP]-⋯[TCNP]- interactions in an isolated [TCNP]22- are repulsive by 58.9 kcal/rnol, and that the stability of [TCNP]22- primarily originates from [TCNP]-⋯cation+ electrostatic interactions, whose sum (-209.8 kcal/mol) exceeds the sum of the repulsive [TCNP]-⋯[TCNP]- and cation+⋯cation+ interactions (140.3 kcal/mol). [ABSTRACT FROM AUTHOR]

The structures of three temperature-dependent polymorphs of solvent-free decamethylferrocenium tetracyanoethenide, [FeCp*[sub2]][TCNE], are determined from high-resolution synchrotron powder diffraction data. [FeCp*[sub2]][TCNE] is the first organic-based ferromagnetic material to be synthesized and is known to have two structural phase transitions at 249 and 282 K. The low-temperature phase, which exhibits spontaneous ferromagnetic order below 4.8 K, was determined at 12 K. At that temperature, it has monoclinic space group P2[sub1]/c [a = 9.6637(4) Å, b = 14.1217(5) Å, c = 18.6256(7) A, β = 113.231 (2)°, Z = 4] and consists of parallel chains of alternating [Fe(C[sub5]Me[sub5])[sub2]][sup∙+] and [TCNE][sup∙-] ions, with an intrachain Fe⋯Fe distance of 10.45 Å. Structures of the intermediate and ambient temperature phases, also studied here, are characterized by increasing disorder. At 250 K, the unit cell space group is F2[sub1]/m [a = 9.7100(3) Å, b = 14.4926(4) Å, c = 9.4997(3) Å, β = 113.153(1)°, Z= 2]. At ambient temperature, the lattice, albeit quite disordered, belongs to the orthorhombic space group Cmcm [a = 10.629(1) Å, b = 16.128(1) Å, c 14.593(1) Å, Z = 4]. Nearest-neighbor magnetic interactions were evaluated for the 12 K structure by CASSCF and CASSCF/MCQDPT calculations (a methodology similar to the CASPT2 method). Similar trends are observed in computations with and without inclusion of spin-orbit coupling. The strongest are two intrachain [FeCp*[sub2]][sup&3x2219;-]⋯[TCNEI interactions (ferromagnetic with values of ∼45 and ∼29 cm[sup1]), although weaker, nonnegligible, ferro- or antiferromagnetic interchain interactions of less than ±0.2 cm[sup1] are also present. Magnetic interactions that lead to ordering are therefore three-dimensional, despite the vastly different intra- and interchain coupling strengths. [ABSTRACT FROM AUTHOR]

We have determined the structures of two phases of unsolvated Mg(BH4)2, a material of interest for hydrogen storage. One or both phases can be obtained depending on the synthesis conditions. The first, a hexagonal phase with space group P61, is stable below 453 K. Upon heating above that temperature it transforms to an orthorhombic phase, with space group Fddd, stable to 613 K at which point it decomposes with hydrogen release. Both phases consist of complex networks of corner-sharing tetrahedra consisting of a central Mg atom and four BH4 units. The high-temperature orthorhombic phase has a strong antisite disorder in the a lattice direction, which can be understood on the basis of atomic structure. [ABSTRACT FROM AUTHOR]

Bullinger present his understanding of infant baptism not only in systematic of summary from the Decades and confessional works but also in dialogue eat discussion form in other works. From 1525, what is fundamental in expounding his view and in challenging his opponents' views is the argument from the covenant, which is one and eternal. In 1525 he begins with this and then examines Anabaptist objections. However in 1531 and 1560 he begins with his opponents' case, though with different elements in it. The substance of his defence of infant baptism is unchanged between 1525 and 1560, though some new arguments emerge over the years. There is continuity between Zwingli and Bullinger, both in the argument from the covenant and in range of biblical arguments. However, unlike Zwingli, Bullinger makes no use of election in support of his case and later expounds Acts 19 differently from Zwingli. [ABSTRACT FROM AUTHOR]

Reports on the crystal structure of beta-hematin. Use of simulated annealing techniques; Analysis of different powder diffraction data; Heme groups released from the digestion of the hemoglobin of malaria-infected red blood cells; Aggregation into an insoluble material called hemozoin; Action of antimalarial drugs.

Focuses on polymeric fullerene chains in RbC60 and KC60. Single-crystal structure determinations; Three mirror plane in icosahedral C60; Pseudo-body-centered array of rotated fullerenes; Structural parameters; Formation of a partial (pi)-bond between cages; Relationship between face-centered-cubic and body-centered orthorhombic lattices; X-ray diffraction pattern of RbC60; Bonding structures.

We describe an x-ray monochromator which uses a sagittally bent crystal to focus 5.7 mrad of horizontal divergence. Complete construction details are given, enabling the reader to duplicate the device. The rocking curve width and diffraction efficiency differ insignificantly between the bent (focusing) and flat crystal geometries. The unit has been operated successfully at energies up to 18 keV, providing a seventyfold increase in x-ray flux over unfocused radiation. [ABSTRACT FROM AUTHOR]

Background: The steady supply of quality, affordable medicines is a pillar of a functioning health system. In addition to the public sector, the private, mission and not-for-profit sectors often serve a large part of the population in Africa. However, while there is generally systematic recording of public sector supply of medicines, detailed, systematic and reliable national market data including these non-public sectors are not commonly available in most countries in Africa. Understanding the total market is a missing part of the access puzzle: without this information, policy makers and health practitioners are not able to fully measure the impact of interventions, measure access to effective products, or fully evaluate the rational use of medicines. This article reports on a unique innovation which provides routine, national-level data on the total pharmaceuticals market, through a system which can be replicated elsewhere. It demonstrates how national-level market data contribute to the evidence base for policies on access to essential medicines, using the Zambian anti-malarial medicines market as a case study. Methods: A new, routine national database on pharmaceutical market size and structure was established through a multi-partner collaboration. Information was extracted from import authorizations and allows for information on local manufacture. Data included value and volume of products as well as pack details, manufacturer and importer. The system was continually updated: data for this analysis were extracted for 6 years: 2009–2014 inclusive. Data were analysed using Microsoft Excel and validated against other sources including donor procurement data. Analysis included public and private sector markets. The policy relevance was demonstrated through analysis of four aspects of national policies on access and rational use of malaria medicines: (i) volume of product relative to disease burden; (ii) distribution by sector relative to treatment-seeking; (iii) consistency of products with respect to national policy guidelines; (iv) market concentration as a proxy for security of supply. Results: The system developed provides the first accurate, systematic data on the breakdown of a national pharmaceutical market in an African context. The total value of the anti-malarials market in Zambia, including all sectors, was USD 5.5–6 million. This included 22 different molecules or combinations, produced by 56 different manufacturers, with 142 different permutations of molecule/manufacturer/strength. Such data provide a complementary mechanism to confirm key trends in malaria treatment and control in Zambia: (i) sufficient supply relative to disease burden, (ii) value and volume of the private/non-profit sector; 29%–2% of market value and 17%–2% of market volume (from 2009 to 2014), (iii) dominance of the 3 molecules recommended in the national treatment guidelines; and (iv) an evidence-base for national discussions on medicines quality, security of supply and rationale use. The system extracts information on all medicines and therefore could be used to analyse other therapeutic classes. Data have been used for several policy purposes, notably by ZAMRA to monitor the quality of products in Zambia, monitoring implementation of WHO Resolutions on artemisinin monotherapy as well as monitoring trends in product choice across sectors. Conclusion: Routine data are important for researchers and policy makers alike. This study shows how medicines data can be systematically gathered at national level—comprising range, volume and value in the public, private and not-for-profit sectors—to monitor more detailed trends in the market and allows triangulation of supply-side data against other sources. This systematic approach can contribute significantly to support access to medicines, monitor treatment and public health policies and create healthy markets. It can be used to monitor changes between therapeutic areas, for example the impact of improved malaria treatment on the use of antibiotics in the context of anti-microbial resistance monitoring. As data contain commercially confidential information, appropriate safeguards should be put in place to balance public health and commercial interests. [ABSTRACT FROM AUTHOR]

Abstract There is an ongoing urgent need for new targeted antibacterial compounds with novel mechanisms of action for the treatment of infections caused by bacteria that are resistant to currently available materials. Since the expression of glycosidase enzymes within bacteria is unequally distributed, glycoside derivatives of antibacterial agents offer potential as targeted prodrugs for bacterial infections. Herein we report the synthesis and characterisation of four α-D-glycopyranosides and three β-D-glycopyranosides of the broad antibacterial agent triclosan, in generally good synthetic yields, and with excellent purities. Each glycoside was analysed to determine its ability to inhibit the growth of a wide range of Gram-negative and Gram-positive organisms, including many of clinical significance. All of the triclosan glycosides that were synthesized demonstrated antibacterial activity against many of the organisms that were examined. For example, β-galactoside (3a) and α-arabinoside (3c) had MIC values of 0.5 μg/ml for several strains of S. aureus and S. haemolyticus. The triclosan glycosides were also generally found to be more water soluble and much more selective than the underivatized triclosan, making them ideal both for the targeted inhibition of bacterial growth and as agents for the selective recovery of bacteria from mixed cultures. In the latter case, two Bacillus strains could be identified from various strains of Bacillus and Staphylococcus after inoculation onto Nutrient Agar No. 2 with 0.25 μg/ml triclosan-α-D-glucopyranoside (3e). This glucoside may, therefore, be of use for the isolation and identification of the food-poisoning organism Bacillus cereus. Graphical abstract Image 1 Highlights • Four α-D-glycopyranosides and three β-D-glycopyranosides of the broad antibacterial agent triclosan, were synthesised in generally good synthetic yields, and with excellent purities. • All of the triclosan glycosides demonstrated antibacterial activity against many of the organisms that were examined. • β-Galactoside (3a) and α-arabinoside (3c) had MIC values of 0.5 μg/ml for several strains of S. aureus and S. haemolyticus. • Two Bacillus strains were identified from strains of Bacillus and Staphylococcus after inoculation onto Nutrient Agar No. 2 with 0.25 μg/ml triclosan-α-D-glucopyranoside (3e). [ABSTRACT FROM AUTHOR]

Highlights a workshop on pharmaceutical application of synchrotron radiation, held on May 17, 2004 at Brookhaven National Laboratory in Long Island, New York. Purpose of the workshop; Keynote speakers; Topics discussed.

Highlights the 'Frontiers in Powder Diffraction' workshop at the 2003 Annual Users' Meeting of the National Synchrotron Light Source in Upton, New York. Discussion on in situ powder diffraction measurements at high temperature; Insights into the state of the activated catalyst to optimize the process in the chemical plant; Commentary on the concept of least square analysis.

The article offers information on the meeting of the West Midlands Branch of the British Institute of Non-Destructive Testing (NDT) which features Keith McLaughlin of Advanced NDT Ltd., who discusses the history of ultraviolet (UV) lights and its use in inspection purposes.

Substitution of Ni for In in InTaO4 is reinvestigated by synchrotron X-ray and neutron powder diffraction, diffuse reflectance spectroscopy, XANES, and magnetic susceptibility measurements, providing insights into its previously reported photoactivity. [ABSTRACT FROM AUTHOR]

Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2FeMoO6 at unparalleled low temperatures of 150-300 oC. The irreversible ionic motion at ambient pressure, as evidenced by real-time powder synchrotron X-ray and neutron diffraction, and second harmonic generation, leads to a transition from a Ni3TeO6-type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties. This work demonstrates a remarkable cationic rearrangement, with corresponding large changes in the physical properties in a bulk oxide at unprecedented low temperatures. [ABSTRACT FROM AUTHOR]

Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2FeMoO6 at unparalleled low temperatures of 150-300 oC. The irreversible ionic motion at ambient pressure, as evidenced by real-time powder synchrotron X-ray and neutron diffraction, and second harmonic generation, leads to a transition from a Ni3TeO6-type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties. This work demonstrates a remarkable cationic rearrangement, with corresponding large changes in the physical properties in a bulk oxide at unprecedented low temperatures. [ABSTRACT FROM AUTHOR]

A letter to the editor is presented in response to the article "Expert Witnesses Above the Parapet," by C. Dyer, published in the July 20, 2010 issue.

Presents a letter to the editor in response to the article "Parents wrongfully accused of child abuse cannot sue doctors," by C. Dyer, in the April 30, 2005 issue.

Pb2MReO6(M = Co, Cr) perovskites were preparedby high pressure–high temperature method. Rietveld refinementsof synchrotron powder X-ray diffraction show that the crystal structureof Pb2CoReO6is trigonal (space group R-3) with almost complete ordering of Co and Re cations,while Pb2CrReO6(space group Pm-3m) is a cubic perovskite with one single site for Cr and Re atoms.The difference between the symmetry and the degree of order was furtherclarified by X-ray absorption spectroscopy that establishes formaloxidation states in these phases as Pb2Co2+Re6+O6and Pb2Cr3+Re5+O6. Pb2CrReO6is a simple perovskitewith a high magnetic ordering temperature of 643 K. Pb2CoReO6is a double perovskite with −23% high fieldnegative magnetoresistance at 10 K and 9 T. First-principles calculationsof Pb2CoReO6indicate a half metallic electronicstructure. [ABSTRACT FROM AUTHOR]

Objectives: New antidiabetic medications such as insulin analogues and thiazolidinediones have been introduced over the last decade. This study compares the uptake of new agents in three emerging pharmaceutical markets: Brazil, China, and Thailand. Methods: Using longitudinal IMS Health sales data, we calculated the quarterly percentage market share for types of insulins and oral hypoglycemic agents from 2002 through 2012 in each country. New oral hypoglycemic agents included: alpha-glucosidase inhibitors, thiazolidinediones, dipeptidyl peptidase-4 inhibitors, and non-sulfonylurea secretagogues. Results: While China had the highest use of insulin cartridges and pens (85.6% in 2010), Brazil was the earliest adopter of insulin analogues and had the greatest use of these products overall (44.6% of the insulin market) in 2010, which then decreased by almost half by 2012. Together, sulfonylureas and metformin dominated the markets in Brazil and Thailand (~89% and ~96% respectively) over the 10-year period. Between 2002 and 2012, there was a shift in use from sulfonylureas to metformin; the market share of newer agents remained 10% or less in both countries. In China, however, market share of new oral agents grew rapidly from 13.1% to 44.4%. While metformin use was relatively stable in China (one-third of the market), sulfonylureas declined substantially over the 10-year period (41.5% to 20.8%). Conclusion: Given large cost differentials between newer and older insulins and among oral hypoglycemic agents, it is important to evaluate uptake of newer products over time. Uptake patterns differed in the study countries, likely due to different medicines policy approaches. Future research should evaluate how trends in use of antidiabetic products align with national clinical practice guidelines and pharmaceutical policies, as well as the impacts of different patterns of use on cost and clinical outcomes. [ABSTRACT FROM AUTHOR]

Structural investigations of a nonstoichiometric hydrate, AMG 222 tosylate, a DPP- IV inhibitor in clinical development for type II diabetes, were performed using a multitechnique approach. The moisture sorption isotherm is in good agreement with a simple Langmuir model, suggesting that the hydrate water is located in well-defined crystallographic sites, which become vacant during dehydration. Crystal structures of AMG 222 tosylate at ambient and dry conditions were determined from high-resolution X-ray diffraction using the direct space method. On the basis of these crystal structures, hydrated water is located in channels formed by the drug framework. Upon dehydration, an isostructural dehydrate is formed with the channels remaining void and accessible to water for rehydration. Kitaigorodskii packing coefficients of the solid between relative humidity of 0% and 90% indicate that the equilibrium form of AMG 222 tosylate is the fully hydrated monohydrate. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 103:2809-2818, 2014 [ABSTRACT FROM AUTHOR]

The increase in the number of bacteria that are resistant to multiple antibiotics poses a serious clinical problem that threatens the health of humans worldwide. Nadifloxacin (1) is a highly potent antibacterial agent with broad-spectrum activity. However, its poor aqueous solubility has limited its use to topical applications. To increase its solubility, it was glycosylated herein to form a range of trans-linked (3a-e) and cis-linked (7a,b) glycosides, each of which was prepared and purified to afford single anomers. The seven glycoside derivatives (3a-e, 7a,b) were examined for potency against eight strains of S. aureus, four of which were methicillin-resistant. Although less potent than free nadifloxacin (1), the α-L-arabinofuransoside (3a) was effective against all strains that were tested (minimum inhibitory concentrations of 1–8 μg/mL compared to 0.1–0.25 μg/mL for nadifloxacin), demonstrating the potential of this glycoside as an antibacterial agent. Estimation of Log P as well as observations made during preparation of these compounds reveal that the solubilities of the glycosides were greatly improved compared with nadifloxacin (1), raising the prospect of its use in oral applications. [ABSTRACT FROM AUTHOR]

This observational study investigates the private sector, retail pharmaceutical market of 19 low and middle income countries (LMICs) in Latin America, Asia and the Middle East/South Africa analyzing the relationships between volume market share of generic and originator medicines over a time series from 2001 to 2011. Over 5000 individual pharmaceutical substances were divided into generic (unbranded generic, branded generic medicines) and originator categories for each country, including the United States as a comparator. In 9 selected LMICs, the market share of those originator substances with the largest decrease over time was compared to the market share of their counterpart generic versions. Generic medicines (branded generic plus unbranded generic) represent between 70 and 80% of market share in the private sector of these LMICs which exceeds that of most European countries. Branded generic medicine market share is higher than that of unbranded generics in all three regions and this is in contrast to the U.S. Although switching from an originator to its generic counterpart can save money, this narrative in reality is complex at the level of individual medicines. In some countries, the market behavior of some originator medicines that showed the most temporal decrease, showed switching to their generic counterpart. In other countries such as in the Middle East/South Africa and Asia, the loss of these originators was not accompanied by any change at all in market share of the equivalent generic version. For those countries with a significant increase in generic medicines market share and/or with evidence of comprehensive “switching” to generic versions, notably in Latin America, it would be worthwhile to establish cause-effect relationships between pharmaceutical policies and uptake of generic medicines. The absence of change in the generic medicines market share in other countries suggests that, at a minimum, generic medicines have not been strongly promoted. [ABSTRACT FROM AUTHOR]

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy‐intensive, cryogenic distillation in industry. Sustainable, non‐distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In‐situ PXRD provides a "live" picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene‐free sorbent in the solid‐state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also presented. [ABSTRACT FROM AUTHOR]

Purification of C2H4 from an C2H4 /C2H6 mixture is one of the most challenging separation processes, which is achieved mainly through energy‐intensive, cryogenic distillation in industry. Sustainable, non‐distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C2H4 /C2H6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In‐situ PXRD provides a "live" picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene‐free sorbent in the solid‐state, driven by the presence or removal of C2H4. Molecular structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also presented. [ABSTRACT FROM AUTHOR]

Background and Objectives Pharmaceutical expenditures are a major burden in China, partly because of pharmaceutical sales covering hospital operating costs, so a series of reductions in maximum retail prices of specific products, including antidiabetic medications, have been implemented. This is the first large-scale, longitudinal study evaluating effects of two rounds of price regulations on use of antidiabetic medications. Methods We used quarterly purchasing data collected by IMS Health from more than 1000 hospitals in China (1999-2009). We used interrupted time-series analysis to assess changes in the population-adjusted market volume of insulin and oral hypoglycaemic products and in the percentage market share of price-regulated products following price regulations implemented in December 2001 and December 2006. Results After the 2001 price regulation, there was a significant increase in market volume trend of insulin products (0.06 standard units/1000 population/quarter; 95% confidence interval: 0.04-0.08); utilisation of oral hypoglycaemic products remained stable. After the 2006 price regulation, there were significant increases in the market volume trend of both insulin products (0.18 standard units/1000 population/quarter; 0.12-0.23) and oral hypoglycaemic products (10.31 standard units/1000 population/quarter; 5.65-14.98). Market share of price-regulated insulin and oral hypoglycaemic products did not change significantly after either price regulation. Conclusion Our results indicate that lowering the retail prices of specific products was associated with increases in total per capita utilisation of antidiabetic medications without shifts in use between non- and price-regulated products. Broad volume increases suggest access to antidiabetic medications by additional people, increased use by those with prior access, or both. [ABSTRACT FROM AUTHOR]

Linear chain thiocyanate complexes of M(NCS)2(OCMe2)2 (M = Fe, Mn, Cr) composition have been prepared and structurally, chemically, and magnetically characterized. Fe(NCS)2(OCMe2)2 exhibits metamagnetic-like behavior, and orders as an antifenomagnet at 6 K, The Mn and Cr compounds are antiferromagnets with Tc of 30 and 50 K, respectively, with J/kB -3.5 (-2.4 cm-1) and -9.9 K (-6.9 cm-1), respectively, when fit to one-dimensional (l-D) Fisher chain model (H = -2JSi-Sj:). Co(NCS)2 was prepared by a new synthetic route, and powder difcction was used to determine its structure to be a two-dimensional (2-D) layer with &mgr;NSS-NCS motif, and it is an antiferromagnet (Tc = 22 K; &thgr; = -33 K for T > 25 K). M(NCS)2(OCMe2)2 (M = Fe, Mn) and Co(NCS)2 react with (NBu4)(TCNE) in dichloromethane to form M(TCNE)[C4(CN)8]1/2, and in acetone to form M[C4(CN)fi](OCMe2)2 (M = Fe, Mn, Co). These materials possess &mgr;4-[C4(CN)nY∼ tliat form 2-D layered structural motifs, which exhibit weak antiferromagnetic coupling. Co(TCNE)[C4(CN)8]1/2 behaves as a paramagnet with strong antiferromagnetic coupling {0 = -50 K). [ABSTRACT FROM AUTHOR]

The reaction of MnII and [NEt4]CN leads to the isolation of solvated [NEt4]Mn3(CN)7 ( 1) and [NEt4]2Mn3(CN)8 ( 2), which have hexagonal unit cells [ 1: R $\bar 3$ m, a=8.0738(1), c=29.086(1) Å; 2: P $\bar 3$ m1, a=7.9992(3), c=14.014(1) Å] rather than the face centered cubic lattice that is typical of Prussian blue structured materials. The formula units of both 1 and 2 are composed of one low- and two high-spin MnII ions. Each low-spin, octahedral [MnII(CN)6]4− bonds to six high-spin tetrahedral MnII ions through the N atoms, and each of the tetrahedral MnII ions are bound to three low-spin octahedral [MnII(CN)6]4− moieties. For 2, the fourth cyanide on the tetrahedral MnII site is C bound and is terminal. In contrast, it is orientationally disordered and bridges two tetrahedral MnII centers for 1 forming an extended 3D network structure. The layers of octahedra are separated by 14.01 Å ( c axis) for 2, and 9.70 Å ( c/3) for 1. The [NEt4]+ cations and solvent are disordered and reside between the layers. Both 1 and 2 possess antiferromagnetic superexchange coupling between each low-spin ( S=1/2) octahedral MnII site and two high-spin ( S=5/2) tetrahedral MnII sites within a layer. Analogue 2 orders as a ferrimagnet at 27(±1) K with a coercive field and remanent magnetization of 1140 Oe and 22 800 emuOe mol−1, respectively, and the magnetization approaches saturation of 49 800 emuOe mol−1 at 90 000 Oe. In contrast, the bonding via bridging cyanides between the ferrimagnetic layers leads to antiferromagnetic coupling, and 3D structured 1 has a different magnetic behavior to 2. Thus, 1 is a Prussian blue analogue with an antiferromagnetic ground state [ Tc=27 K from d( χT)/d T]. [ABSTRACT FROM AUTHOR]