Medication-related problems can cause serious adverse drug events (ADEs) that may lead to hospitalization of the patient. There are multiple screening methods to detect and reduce potentially ...inappropriate medications (PIMs) and potential prescribing omissions (PPOs). Whether this will result in less medication-related hospitalizations is unknown. The study objective was to assess the risk of preventable medication-related hospital admissions associated with potentially inappropriate prescribing, using the Beers 2012 and the Screening Tool of Older Person's Prescriptions and the Screening Tool to Alert doctors to Right Treatment (STOPP & START) 2008 criteria.
A nested case-control study was conducted with a subset of Dutch participants from the Hospital Admissions Related to Medication (HARM) study. Cases were defined as patients aged ≥65 years with a potentially preventable medication-related hospital admission. For each case, one control was selected, matched for age and sex. The primary determinant was the presence of one or more PIMs according to the Beers 2012 and STOPP 2008 criteria. The secondary determinant was the presence of one or more PIMs and PPOs according to the STOPP & START 2008 criteria. The strength of the association between inappropriate prescribing and medication-related hospital admission was evaluated with multivariate logistic regression and expressed as odds ratios (ORs) with 95 % confidence intervals (CIs).
The prevalence of Beers 2012 criteria PIMs in the total cohort was 44.4 %. The prevalence of STOPP & START 2008 criteria PIMs and PPOs were, respectively, 34.1 and 57.7 %. STOPP 2008 criteria PIMs were associated with preventable medication-related hospital admissions OR adjusted for number of drugs and comorbidities (ORadj) 2.30, 95 % CI 1.30-4.07, whereas there was no association with Beers 2012 criteria PIMs (ORadj 1.49, 95 % CI 0.90-2.47). STOPP PIMs and START PPOs together were also associated with preventable medication-related hospital admissions (ORadj 3.47, 95 % CI 1.70-7.09).
Our study shows that patients with potentially inappropriate prescribing detected with the STOPP & START 2008 criteria are at risk of preventable medication-related hospital admissions. The STOPP & START 2008 criteria can be used to identify older people at risk of medication-related problems.
Porous heterogeneous catalysts play a pivotal role in the chemical industry. Herein a new Hf-based metal–organic framework (Hf-NU-1000) incorporating Hf6 clusters is reported. It demonstrates high ...catalytic efficiency for the activation of epoxides, facilitating the quantitative chemical fixation of CO2 into five-membered cyclic carbonates under ambient conditions, rendering this material an excellent catalyst. As a multifunctional catalyst, Hf-NU-1000 is also efficient for other epoxide activations, leading to the regioselective and enantioretentive formation of 1,2-bifuctionalized systems via solvolytic nucleophilic ring opening.
The components of the macroscopic mechanical stress tensor of a stressed thin film, coating, multilayer or the region near the surface of a bulk material can in principle be determined by X‐ray ...diffraction. The various analysis methods and measurement strategies, in dependence on specimen and measurement conditions, are summarized and evaluated in this paper. First, different X‐ray diffraction geometries (conventional or grazing incidence) are described. Then, the case of macroscopically elastically isotropic, untextured specimens is considered: from the simplest case of a uniaxial state of stress to the most complicated case of a triaxial state of stress. The treatment is organized according to the number of unknowns to be determined (i.e. the state of stress, principal axes known or unknown), the use of one or several values of the rotation angle ϕ and the tilt angle ψ of the sample, and one or multiple hkl reflections. Next, the focus is on macroscopically elastically anisotropic (e.g. textured) specimens. In this case, the use of diffraction (X‐ray) elastic constants is not possible. Instead, diffraction (X‐ray) stress factors have to be used. On the basis of examples, it is demonstrated that successful diffraction stress analysis is only possible if an appropriate grain‐interaction model is applied.
Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based ...metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation of colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively—ultimately giving rise to the lowest-density MOF reported to date.
Molybdenum(VI) oxide was deposited on the Zr6 node of the mesoporous metal–organic framework NU-1000 via condensed-phase deposition where the MOF is simply submerged in the precursor solution, a ...process named solvothermal deposition in MOFs (SIM). Exposure to oxygen leads to a monodisperse, porous heterogeneous catalyst, named Mo-SIM, and its structure on the node was elucidated both computationally and spectroscopically. The catalytic activity of Mo-SIM was tested for the epoxidation of cyclohexene. Near-quantitative yields of cyclohexene oxide and the ring-opened 1,2-cyclohexanediol were observed, indicating activity significantly higher than that of molybdenum(VI) oxide powder and comparable to that of a zirconia-supported analogue (Mo-ZrO2) prepared in a similar fashion. Despite the well-known leaching problem of supported molybdenum catalysts (i.e., loss of Mo species thus causes deactivation), Mo-SIM demonstrated no loss in the metal loading before and after catalysis, and no molybdenum was detected in the reaction mixture. In contrast, Mo-ZrO2 led to significant leaching and close to 80 wt % loss of the active species. The stability of Mo-SIM was further confirmed computationally, with density functional theory calculations indicating that the dissociation of the molybdenum(VI) species from the node of NU-1000 is endergonic, corroborating the experimental data for the Mo-SIM material.
The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. ...Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.
Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor–acceptor interactions to form host–guest complexes with various ...guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed Ex n Box m 4+ for short, have been prepared by altering a number of variables: (i) n, the number of “horizontal” p-phenylene spacers between adjoining pyridinium units, to modulate the “length” of the cavity; (ii) m, the number of “vertical” p-phenylene spacers, to modulate the “width” of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex 1 Box 4+ (or simply ExBox 4+ ) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host–guest complexes allow the development of artificial photosystems. Ex 2 Box 4+ boasts the ability to bind both π-electron-rich and -poor aromatic guests in different binding sites located within the same cavity. ExBox 2 4+ forms complexes with C60 in which discrete arrays of aligned fullerenes result in single cocrystals, leading to improved material conductivities. When the substitution pattern of the Ex n Box 4+ series is changed to 1,3,5-trisubstituted benzenoid cores, the hexacationic cagelike compound, termed ExCage 6+ , exhibits different kinetics of complexation with guests of varying sizesa veritable playground for physical organic chemists. The organization of functionality with respect to structure becomes valuable as the number of analogues continues to grow. With each of these minor structural modifications, a wealth of properties emerge, begging the question as to what discoveries await and what properties will be realized with the continued exploration of this area of supramolecular chemistry based on a unique class of receptor molecules.
The natural antibiotic teixobactin kills pathogenic bacteria without detectable resistance. The difficult synthesis and unfavourable solubility of teixobactin require modifications, yet insufficient ...knowledge on its binding mode impedes the hunt for superior analogues. Thus far, teixobactins are assumed to kill bacteria by binding to cognate cell wall precursors (Lipid II and III). Here we present the binding mode of teixobactins in cellular membranes using solid-state NMR, microscopy, and affinity assays. We solve the structure of the complex formed by an improved teixobactin-analogue and Lipid II and reveal how teixobactins recognize a broad spectrum of targets. Unexpectedly, we find that teixobactins only weakly bind to Lipid II in cellular membranes, implying the direct interaction with cell wall precursors is not the sole killing mechanism. Our data suggest an additional mechanism affords the excellent activity of teixobactins, which can block the cell wall biosynthesis by capturing precursors in massive clusters on membranes.
Amino‐functionalized zirconium‐based metal‐organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non‐functionalized analogues for hydrolysis of organophosphonate‐based ...toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO‐66‐NH2, where the amino groups reside near the node, compared to UiO‐67‐m‐NH2, where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate‐based nerve agents. The generality of the observed amine‐proximity‐dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr6‐node active site and therefore increase the overall catalytic rates.
Proximity De‐pendant: The role of amino groups on the hydrolysis of a nerve agent simulant, DMNP, has been explored. Experiments and theoretical calculations reveal that not only the presence but also the proximity of the amino group is important for effective chemical detoxification of DMNP. NU‐1002‐o‐NH2, a Zr‐based mesoporous metal–organic framework (MOF) with pendant amines demonstratest1/2 of 1.2 min with only 3 mol % catalyst loading.
Inferential models have long been used to determine pollutant dry deposition to ecosystems from measurements of air concentrations and as part of national and regional atmospheric chemistry and ...transport models, and yet models still suffer very large uncertainties. An inferential network of 55 sites throughout Europe for atmospheric reactive nitrogen (Nr) was established in 2007, providing ambient concentrations of gaseous NH3, NO2, HNO3 and HONO and aerosol NH4+ and NO3− as part of the NitroEurope Integrated Project. Network results providing modelled inorganic Nr dry deposition to the 55 monitoring sites are presented, using four existing dry deposition routines, revealing inter-model differences and providing ensemble average deposition estimates. Dry deposition is generally largest over forests in regions with large ambient NH3 concentrations, exceeding 30–40 kg N ha−1 yr−1 over parts of the Netherlands and Belgium, while some remote forests in Scandinavia receive less than 2 kg N ha−1 yr−1. Turbulent Nr deposition to short vegetation ecosystems is generally smaller than to forests due to reduced turbulent exchange, but also because NH3 inputs to fertilised, agricultural systems are limited by the presence of a substantial NH3 source in the vegetation, leading to periods of emission as well as deposition. Differences between models reach a factor 2–3 and are often greater than differences between monitoring sites. For soluble Nr gases such as NH3 and HNO3, the non-stomatal pathways are responsible for most of the annual uptake over many surfaces, especially the non-agricultural land uses, but parameterisations of the sink strength vary considerably among models. For aerosol NH4+ and NO3− discrepancies between theoretical models and field flux measurements lead to much uncertainty in dry deposition rates for fine particles (0.1–0.5 μm). The validation of inferential models at the ecosystem scale is best achieved by comparison with direct long-term micrometeorological Nr flux measurements, but too few such datasets are available, especially for HNO3 and aerosol NH4+ and NO3−.
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