Association between serum 25-hydroxyvitamin D concentrations and hypertension among adults in North Sudan: a community-based cross-sectional study.

BACKGROUND: Globally, hypertension represents a major public health problem. The association between 25-hydroxyvitamin D (25[OH]D) levels and hypertension remains unclear. The current study aimed to investigate the association between serum 25(OH)D levels and hypertension among adults in Sudan. METHODS: A community-based cross-sectional study was conducted among adults in North Sudan. Sociodemographic and clinical data were collected using a questionnaire and face-to-face interviews. Serum 25(OH)D was measured using an enzyme-linked immunosorbent assay. Multivariate logistic regression and multiple linear regression analyses were performed. RESULTS: Of the total of 391 participants, 202 (51.7%) were females. The median (interquartile range [IQR]) of participants' ages was 45(32-55) years. Of the total, 219(56.0%) had hypertension. The median (IQR) of serum25(OH)D was 13.3(9.9-19.7) ng/mL, and 295 (75.4%) participants had vitamin D deficiency (< 20 ng/mL). In multivariable logistic regression, the adjusted odds ratio (AOR) for age = 1.05, 95% confidence interval (CI)1.03‒1.061, the AOR for being female = 2.02, 95% CI, 1.12‒3.66, and body mass index was AOR = 1.09, 95% CI, 1.05‒1.14, all of which were significantly associated with hypertension. However, serum 25(OH)D levels were not associated with hypertension (AOR = 1.01, 95% CI 0.99‒1.05, P = 0.317). In multiple linear regression, while systolic blood pressure was negatively associated with 25(OH)D (coefficient = - 0.28, P = 0.017), there was no significant association between serum 25(OH)D level and diastolic blood pressure (coefficient = - 0.10, P = 0.272) or mean blood pressure (coefficient =-0.03, P = 0.686). CONCLUSION: The current study revealed a negative association between vitamin D and systolic blood pressure. The mechanism of such an association needs further study.

Organoboron Complexes as Thermally Activated Delayed Fluorescence (TADF) Materials for Organic Light-Emitting Diodes (OLEDs): A Computational Study.

We report on organoboron complexes characterized by very small energy gaps (ΔEST) between their singlet and triplet states, which allow for highly efficient harvesting of triplet excitons into singlet states for working as thermally activated delayed fluorescence (TADF) devices. Energy gaps ranging between 0.01 and 0.06 eV with dihedral angles of ca. 90° were registered. The spin-orbit couplings between the lowest excited S1 and T1 states yielded reversed intersystem crossing rate constants (KRISC) of an average of 105 s-1. This setup accomplished radiative decay rates of ca. 106 s-1, indicating highly potent electroluminescent devices, and hence, being suitable for application as organic light-emitting diodes.

Zn2+-Schiff's Base Complex as an "On-Off-On" Molecular Switch and a Fluorescence Probe for Cu2+ and Ag+ Ions.

The present study presents a thorough theoretical analysis of the electronic structure and conformational preference of Schiff's base ligand N,N-bis(2-hydroxybenzilidene)-2,4,6-trimethyl benzene-1,3-diamine (H2L) and its metal complexes with Zn2+, Cu2+ and Ag+ ions. This study aims to investigate the behavior of H2L and the binuclear Zn2+ complex (1) as fluorescent probes for the detection of metal ions (Zn2+, Cu2+ and Ag+) using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The six conformers of the H2L ligand were optimized using the B3LYP/6-311 + + G** level of theory, while the L-2-metal complexes were optimized by applying the B3LYP functional with the LANL2DZ/6-311 + + G** mixed basis set. The gas-phase and solvated Enol-cis isomer (E-cis) was found to be the most stable species. The absorption spectra of the E-cis isomer and its metal complexes were simulated using B3LYP, CAM-B3LYP, M06-2X and ωB97X functionals with a 6-311 + + G** basis set for C, O, N and H atoms and a LANL2DZ basis set for the metal ions (Zn2+, Cu2+ and Ag+). The computational results of the B3LYP functional were in excellent agreement with the experimental results. Hence, it was adopted for performing the emission calculations. The results indicated that metal complex (1) can act as a fluorescent chemosensor for the detection of Ag+ and Cu2+ ions through the mechanism of intermolecular charge transfer (ICT) and as a molecular switch "On-Off-On" via the replacement of Cu2+ by Ag+ ions, as proved experimentally.

Computational Identification of Druggable Bioactive Compounds from Catharanthus roseus and Avicennia marina against Colorectal Cancer by Targeting Thymidylate Synthase.

Colorectal cancer (CRC) is the second most common cause of death worldwide, affecting approximately 1.9 million individuals in 2020. Therapeutics of the disease are not yet available and discovering a novel anticancer drug candidate against the disease is an urgent need. Thymidylate synthase (TS) is an important enzyme and prime precursor for DNA biosynthesis that catalyzes the methylation of deoxyuridine monophosphate (dUMP) to deoxythymidine monophosphate (dTMP) that has emerged as a novel drug target against the disease. Elevated expression of TS in proliferating cells promotes oncogenesis as well as CRC. Therefore, this study aimed to identify potential natural anticancer agents that can inhibit the activity of the TS protein, subsequently blocking the progression of colorectal cancer. Initially, molecular docking was implied on 63 natural compounds identified from Catharanthus roseus and Avicennia marina to evaluate their binding affinity to the desired protein. Subsequently, molecular dynamics (MD) simulation, ADME (Absorption, Distribution, Metabolism, and Excretion), toxicity, and quantum chemical-based DFT (density-functional theory) approaches were applied to evaluate the efficacy of the selected compounds. Molecular docking analysis initially identified four compounds (PubChem CID: 5281349, CID: 102004710, CID: 11969465, CID: 198912) that have better binding affinity to the target protein. The ADME and toxicity properties indicated good pharmacokinetics (PK) and toxicity ability of the selected compounds. Additionally, the quantum chemical calculation of the selected molecules found low chemical reactivity indicating the bioactivity of the drug candidate. The global descriptor and HOMO-LUMO energy gap values indicated a satisfactory and remarkable profile of the selected molecules. Furthermore, MD simulations of the compounds identified better binding stability of the compounds to the desired protein. To sum up, the phytoconstituents from two plants showed better anticancer activity against TS protein that can be further developed as an anti-CRC drug.

Effects of dietary supplementation with different concentration of molasses on growth performance, blood metabolites and rumen fermentation indices of Nubian goats.

BACKGROUND: Molasses is a potential energy supplement; extensively used to improve growth performance, milk and meat characteristics in goats at relatively low concentrations of 5-40% of the diet. Few data are available concerning feeding molasses to goat kids; therefore, the current study aimed to investigate the effects of dietary supplementation with higher concentrations of molasses on growth performance, blood metabolites and rumen fermentation indices. Twenty male Nubian goat kids (4-6 months old; 9-10 kg BW) were randomly assigned to 4 groups receiving different concentration of molasses: 0% (M-0), 30% (M-30), 40% (M-40) and 45% (M-45) for 5 weeks. Feed (DFI) and water intake (DWI) were measured daily, while the blood and rumen liquor samples were collected weekly. RESULTS: The DFI increased and feed conversion ratio (FCR) decreased in all molasses-supplemented groups (P ≤ 0.05), whereas DWI increased in M-30 and decreased in M-45 (P ≤ 0.05). The final BW and average daily gain (ADG) increased (P < 0.0001) in groups M-30 and M-40 compared to the control and M-45. Blood pH was significantly influenced by dietary molasses concentration (MC) and the duration of molasses supplementation (MD), where it decreased in groups M-30 and M-45 compared to the control and M-40 (P < 0.05). The MC had no significant effect on blood Hb, HCT, TLC, albumin, [K+], AST, ALT and total protozoa count (TPC), as well as ruminal-[Na+], [K+], strong ion difference concentration ([SID3]) and [NH3]; however, only [NH3] was significantly affected by MD and the interaction between MC and MD (MC × MD). Serum TP, globulins, [Na+] and [Cl-] increased (P ≤ 0.05) in all supplemented groups, while A/G ratio and [SID3] decreased (P ≤ 0.05). Ruminal pH decreased (P < 0.0001) in M-40 and M-45 compared to the control and M-30. However, [VFAs] increased (P < 0.04) in M-30 and M-40 compared to the control and M-45, while osmolality increased (P ≤ 0.05) in M-30 compared to the other groups. CONCLUSIONS: Dietary supplementation with molasses at a concentration of 30% for 3 weeks improved growth performance, protein metabolism and rumen fermentation without compromising animal health, immunity, and electrolytes and acid-base homeostasis.

Prevalence and associated factors of hypertension among adults in Gadarif in eastern Sudan: a community-based study.

BACKGROUND: Hypertension is becoming an increasingly common health issue worldwide, especially in countries in Sub-Saharan Africa. Hypertension is the leading risk factor for premature death and disability worldwide, and it is the leading risk factor for mortality from cardiovascular diseases worldwide. The data on hypertension in Sudan that has been published is limited. We conducted this study to assess the prevalence of hypertension and its associated risk factors. METHODS: A multistage sampling survey was conducted in Gadarif, Eastern Sudan, from January to May 2018 to investigate the prevalence of hypertension and associated factors in adults in Eastern Sudan. The World Health Organization (WHO) three-level stepwise approach questionnaire was used to gather sociodemographic characteristics (age, sex, height, weight marital status, education level, smoking habit, alcohol consumption habit, and family history of hypertension). Hypertension was defined as the presence of an average blood pressure of ≥140/90 mmHg or the reported use of anti-hypertensive medications for high blood pressure. RESULTS: A total of 600 participants (mean age: 44.9 years) were enrolled in this study. Four hundred twenty-two (70.3%) participants were women, and 196 (32.7%) participants were obese. Of the 600 enrolled participants, 245 (40.8%) individuals had hypertension, 44 (7.3%) had been previously diagnosed with hypertension, and 201 (33.5%) were newly diagnosed with hypertension. A logistic regression analysis showed no significant associations across the education level, marital status, overweight and hypertension factors. However, an older age (adjusted OR = 3.20, 95% CI = 2.28-4.51, P < 0.001) and obesity (adjusted OR = 2.41, 95% CI = 1.57-3.69, P < 0.001) were associated with the presence of hypertension. CONCLUSION: There is a high rate of hypertension in Eastern Sudan, especially among older and obese individuals. Preventive measures, such as dietary measures, should be implemented.

Assessment of blood pressure control in adult hypertensive patients in eastern Sudan.

BACKGROUND: The rate of blood pressure (BP) control in adult hypertensive patients is poor and the reasons for poor control of BP pressure are not fully understood globally. This study aimed to assess the rate and factors associated with BP control in adult hypertensive patients in Sudan. METHODS: A hospital-based cross-sectional study was conducted in adult hypertensive Sudanese patients at Gadarif Hospital in eastern Sudan from November 2016 to March 2017. Information on sociodemographic characteristics of the participants, comorbidities, antihypertensive medication, and adherence to antihypertensive medication was gathered from patients using a questionnaire. Fasting cholesterol and triglyceride levels were measured. RESULTS: A total of 380 patients were enrolled. Of them, 234 (61.6%) were women. The mean (SD) age of the participants was 57.8 (11.1) years (range: 25-93 years). Over one-third (n = 147, 38.7%) of the participants were taking more than one antihypertensive medication. Approximately one-third (29.5%) of the participants were non-adherent to medication. The rate of BP control was 45.3%. In binary logistic regression analyses, age, sex, physical inactivity, adding salt to food, drinking coffee, body mass index, and the lipid profile were not associated with uncontrolled BP. However, non-adherence to medication was the main factor associated with uncontrolled BP (odds ratio = 5.29, 95% confidence interval = 3.16-8.83, P <  0.001). CONCLUSIONS: Almost half of hypertensive patients in follow-up have uncontrolled BP, mainly due to non-adherence to medicine. We recommend further research on drug adherence to improve the rate of BP control in this setting (Gadarif) of the Sudan.

DFT Study of the Structure, Reactivity, Natural Bond Orbital and Hyperpolarizability of Thiazole Azo Dyes.

The structure, reactivity, natural bond orbital (NBO), linear and nonlinear optical (NLO) properties of three thiazole azo dyes (A, B and C) were monitored by applying B3LYP, CAM-B3LYP and ωB97XD functionals with 6-311++G** and aug-cc-pvdz basis sets. The geometrical parameters,dipolemoments,HOMO-LUMO(highest occupied molecular orbital,lowest unoccupied molecular orbital) energy gaps, absorption wavelengths and total hyperpolarizabilities were investigated in carbon tetrachloride (CCl4) chloroform (CHCl3), dichloromethane (CH2Cl2) and dimethlysulphoxide (DMSO). The donor methoxyphenyl group deviates from planarity with the thiazole azo moiety by ca. 38◦; while the acceptor dicyanovinyl, indandione and dicyanovinylindanone groups diverge by ca. 6◦. The HOMOs for the three dyes are identical. They spread over the methoxyphenyl donor moiety, the thiazole and benzene rings as π-bonding orbitals. The LUMOs are shaped up by the nature of the acceptor moieties. The LUMOs of the A, B and C dyes extend over the indandione, malononitrile and dicyanovinylindanone acceptor moieties, respectively, as π-antibonding orbitals. The HOMO-LUMO splittings showed that Dye C is much more reactive than dyes A and B. Compared to dyes A and B, Dye C yielded a longer maximum absorption wavelength because of the stabilization of its LUMOs relative to those of the other two. The three dyes show solvatochromism accompanied by significant increases in hyperpolarizability. The enhancement of the total hyperpolarizability of C compared to those of A and B is due to the cumulative action of the long π-conjugation of the indanone ring and the stronger electron-withdrawing ability of the dicyanovinyl moiety that form the dicyanovinylindanone acceptor group. These findings are facilitated by a natural bond orbital (NBO) technique. The very high total hyperpolarizabilities of the three dyes define their potent nonlinear optical (NLO) behaviour.

Fluorescence, Photophysical Behaviour and DFT Investigation of E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP).

E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP) has been prepared by aldol condensation between 2,5-dimethylpyrazine and pyridine-3-carboxaldehyde. It is characterized by IR, (1)H NMR, and (13)C NMR. The electronic absorption and emission properties of BPEP were studied in different solvents. BPEP displays a slight solvatochromic effect of the absorption and emission spectrum, indicating a small change in dipole moment of BPEP upon excitation. The dye solutions (1 × 10(-4) M) in CHCl3, EtOH and dioxane give laser emission in blue region upon excitation by a 337.1 nm nitrogen pulse (λ = 337 nm). The tuning range, gain coefficient (α) and emission cross - section (σe) have been determined. Ground and excited states electronic geometric optimizations were performed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. A DFT natural bond analysis complemented the ICT. The simulated maximum absorption and emission wavelengths are in line the observed ones in trend, and are proportionally red-shifted with the increase of the solvent polarity. The stability, hardness and electrophilicity of BPEP in different solvents were correlated with the polarity of the elected solvents. BPEP dye displays fluorescence quenching by colloidal silver nanoparticles (AgNPs). The fluorescence data reveal that radiative and non-radiative energy transfer play a major role in the fluorescence quenching mechanism.

Photophysical Behavior and Computational Investigation of Novel 1,4-Bis(2-(2-Phenylpyrimido[1,2-a]Benzimidazol-4-Yl)Phenoxy)Butan (BPPB) Macromolecule.

A new macromolecule pyrimido[l,2-a]benzimidazole derivative named 1,4-bis(2-(2-phenylpyrimido[1,2-a]benzimidazol-4-yl)phenoxy)butan (BPPB) has been synthesized in accepted yield using microwave assistance. The new compound BPPB has been formed by the interaction of 3,3'-((butane-1,4-diylbis(oxy))bis(2,1-phenylene))bis(1-phenylprop-2-en-1-one) (3) with 2- aminobenzimidazole (4) in the presence of potassium hydroxide as a basic catalyst in dimethylformamide (DMF) under microwave radiation for 20 min. The chemical structure of this novel compound was elucidated by elemental and spectral techniques including: FT-IR, (1)H-NMR, (13)C-NMR and mass spectra. The electronic absorption and emission spectra of BPPB were measured in different solvents. BPPB displayed a solvatochromic effect of the emission spectrum that is reflected by red shifts of its fluorescence emission maxima on increasing the solvent polarity, indicating a change of electronic charge distribution upon excitation. BPPB crystalline solids gave excimer-like emission at 535 nm with a bandwidth of ca. 60 nm. Ground and excited states electronic geometry optimizations using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively, complemented these spectral findings. The intramolecular charge transfer was investigated by natural bond orbital (NBO) technique.

The Thermodynamic and Kinetic Properties of 2-Hydroxypyridine/2-Pyridone Tautomerization: A Theoretical and Computational Revisit.

The gas-phase thermal tautomerization reaction between 2-hydroxypyridine (2-HPY) and 2-pyridone (2-PY) was investigated by applying 6-311++G** and aug-cc-pvdz basis sets incorporated into some density functional theory (DFT) and coupled cluster with singles and doubles (CCSD) methods. The geometrical structures, dipole moments, HOMO-LUMO energy gaps, total hyperpolarizability, kinetics and thermodynamics functions were monitored against the effects of the corrections imposed on these functionals. The small experimental energy difference between the two tautomers of 3.23 kJ/mol; was a real test of the accuracy of the applied levels of theory. M062X and CCSD methods predicted the preference of 2-HPY over 2-PY by 5-9 kJ/mol; while B3LYP functional favoured 2-PY by 1-3 kJ/mol. The CAM-B3LYP and ωB97XD functionals yielded mixed results depending on the basis set used. The source of preference of 2-HPY is the minimal steric hindrance and electrostatic repulsion that subdued the huge hyperconjugation in 2-PY. A 1,3-proton shift intramolecular gas-phase tautomerization yielded a high average activation of 137.152 kJ/mol; while the intermolecular mixed dimer interconversion gave an average barrier height of 30.844 kJ/mol. These findings are boosted by a natural bond orbital (NBO) technique. The low total hyperpolarizabilities of both tautomers mark out their poor nonlinear optical (NLO) behaviour. The enhancement of the total hyperpolarizability of 2-HPY over that of 2-PY is interpreted by the bond length alternation.

Selective Solvent-Assisted Linker Exchange (SALE) in a Series of Zeolitic Imidazolate Frameworks.

Solvent-assisted linker exchange (SALE) has recently emerged as an attractive strategy for the synthesis of metal-organic frameworks (MOFs) that are unobtainable via traditional synthetic pathways. Herein we present the first example of selective SALE in which only the benzimiadazolate-containing linkers in a series of mixed-linker zeolitic imidazolate frameworks (ZIF-69, -78, and -76) are replaced. The resultant materials (SALEM-10, SALEM-10b, and SALEM-11, respectively) are isostructural to the parent framework and in each case contain trifluoromethyl moieties. We therefore evaluated each of these materials for their hydrophobicity in condensed and gas phases. We expect that selective SALE will significantly facilitate the design of improved, and potentially complex, MOF materials with new and unusual properties.

Synthesis, Spectral Characteristics and DFT Studies of the New Dye 2,7-diacetyl-9-((dimethylamino)methylene)-9H-fluorene (DMMF) in Different Solvents.

The photophysical parameters such as electronic absorption spectra, molar absorptivity(ε), fluorescence spectra and fluorescence quantum yield (φf) of a new dye namely 2,7-diacetyl-9-((dimethylamino)methylene)-9H-fluorene (DMMF) were determined in different solvents. The electronic absorption are less sensitive to medium polarity. A bathochromic shift was observed in emission spectra(ca. 50 nm) upon increase of solvent polarity, which indicates that the singlet excited state (S1) of DMMF is more polar than the singlet ground state (So). Solid crystals of DMMF exhibit intense yellow fluorescence maximum at 550 nm with bandwidth equal 64 nm upon excitation at wavelength 365 nm. The change in dipole moment value (Δµ) was calculated by using the variation of Stokes shift with solvent polarizability (Δf) (Lippert - Mataga plot) and was found to be 7.22 and 5.5 Debye for higher and lower energy of So - S1 (π-π*) H-1 → L and So - S1 (π-π*) H → L, respectively. These results show that, the excited state is more polar than the ground state. The net photochemical quantum yields of photodecomposition of DMMF (φc) were calculated as 7.2 × 10(-5), 1.14 × 10(-4), 1.44 × 10(-4) and 2.11 × 10(-4) in different solvents such as MeOH, CH2Cl2, CHCl3 and CCl4, respectively. DFT/TD-DFT methods were used to study the geometric and electronic structures of DMMF in different solvents. A good agreement was found between the experimental and theoretical results.

Gas-Phase Thermal Tautomerization of Imidazole-Acetic Acid: Theoretical and Computational Investigations.

The gas-phase thermal tautomerization reaction between imidazole-4-acetic (I) and imidazole-5-acetic (II) acids was monitored using the traditional hybrid functional (B3LYP) and the long-range corrected functionals (CAM-B3LYP and ωB97XD) with 6-311++G** and aug-cc-pvdz basis sets. The roles of the long-range and dispersion corrections on their geometrical parameters, thermodynamic functions, kinetics, dipole moments, Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO-LUMO) energy gaps and total hyperpolarizability were investigated. All tested levels of theory predicted the preference of I over II by 0.750-0.877 kcal/mol. The origin of predilection of I is assigned to the H-bonding interaction (nN8→σ*O14-H15). This interaction stabilized I by 15.07 kcal/mol. The gas-phase interconversion between the two tautomers assumed a 1,2-proton shift mechanism, with two transition states (TS), TS1 and TS2, having energy barriers of 47.67-49.92 and 49.55-52.69 kcal/mol, respectively, and an sp³-type intermediate. A water-assisted 1,3-proton shift route brought the barrier height down to less than 20 kcal/mol in gas-phase and less than 12 kcal/mol in solution. The relatively high values of total hyperpolarizability of I compared to II were interpreted and discussed.

Towards understanding the decomposition/isomerism channels of stratospheric bromine species: ab initio and quantum topology study.

The present study aims at a fundamental understanding of bonding characteristics of the C-Br and O-Br bonds. The target molecular systems are the isomeric CH3OBr/BrCH2OH system and their decomposition products. Calculations of geometries and frequencies at different density functional theory (DFT) and Hartree-Fock/Møller-Plesset (HF/MP2) levels have been performed. Results have been assessed and evaluated against those obtained at the coupled cluster single-double (Triplet) (CCSD(T)) level of theory. The characteristics of the C-Br and O-Br bonds have been identified via analysis of the electrostatic potential, natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM). Analysis of the electrostatic potential (ESP) maps enabled the quantitative characterization of the Br σ-holes. Its magnitude seems very sensitive to the environment and the charge accumulated in the adjacent centers. Some quantum topological parameters, namely Ñ2ρ, ellipticity at bond critical points and the Laplacian bond order, were computed and discussed. The potential energy function for internal rotation has been computed and Fourier transformed to characterize the conformational preferences and origin of the barriers. NBO energetic components for rotation about the C-Br and O-Br bonds as a function of torsion angle have been computed and displayed.

Experimental and theoretical investigation of the pyrolysis products of iminodiacetonitrile, (N≡CCH2)2NH.

The gas-phase FTIR study of the pyrolysis products of iminodiacetonitrile, (N≡CCH2)2NH has revealed the existence of C-cyanomethanimine, N≡CCH═NH, and ketenimine, CH2═C═NH. The former has two isomers: Z and E; while the later readily taumerizes to acetonitrile, CH3C≡N. A trapping/revaporization system has been used to purify C-cyanomethanimine. The analysis of the rotational structures of the IR medium resolution C-type CNH bend, ν6, and C═N torsional mode, ν10, has led to a conformational characterization of these isomers. The Z-isomer was shown to be the major product. This conjecture was supported by ab initio MO calculations that confirmed the relative total energy stability of the Z-isomer over its E-counterpart by 0.173 to 2.326 kJ/mol. The K values indicated that the equilibrium concentration of Z-C-cyanomethanimine amounts to up to three times that of E-C-cyanomethanimine. A further investigation using NBO technique proved the predilection of the Z-isomer. In addition it relates its provenance of preference to the remote nN6 → σ*C4-N5 interaction that stabilized it by 1.10 kcal/mol. A thorough theoretical investigation of the tautomerization reaction between ketenimine and acetonitrile will be published in a separate contribution.

Fracture risk in long term care: a systematic review and meta-analysis of prospective observational studies.

BACKGROUND: The risk factors associated with fractures have been well-characterized in community dwelling populations, but have not been clearly defined in long-term care (LTC) settings. The objective of this review was to identify risk factors for fractures in LTC settings. METHODS: We searched MEDLINE, the Cochrane Library, EMBASE and CINAHL up to June 2014, scanned reference lists of articles and consulted with experts in the field to identify relevant prospective cohort studies that evaluated risk factors associated with fracture incidence in LTC. We included studies that assessed the association between risk factors included in the WHO-Fracture Risk Assessment Tool (FRAX®) or other predictors relevant to LTC (psychotropic medications, cognitive impairment, mobility, and falls). All articles were screened and extracted by two authors. Available data on the association between a given risk factor and fracture incidence were pooled when possible. We used the GRADE criteria to provide a summary of evidence. The GRADE approach defines the quality of a body of evidence as the extent to which one can be confident that an estimate of effect or association is close to the quantity of specific interest. RESULTS: We identified 13 prospective cohort studies which examined fracture incidence among LTC residents. Most predictors showed moderate increases in fracture risk, but the quality of the evidence was often low. Moderate quality evidence showed that prior fractures and falls may moderately increase the risk of fractures. Being a woman and cognitive impairment are probably associated with a small increase. The effect of mobility and psychotropic medication use is still uncertain primarily due to the various definitions used in the studies and difficulty summarising the results. CONCLUSIONS: In addition to criteria used in the FRAX assessment tool, such as a previous fracture and female gender, we found that falls and cognitive impairment are also associated with a small to moderate increases in the risk of fractures in LTC. Developing an assessment tool that includes risk factors that are specific to LTC may improve the identification of individuals who can benefit from fracture prevention programs in these settings.

A density functional theory investigation of the electronic structure and spin moments of magnetite.

We present the results of density functional theory (DFT) calculations on magnetite, Fe3O4, which has been recently considered as electrode in the emerging field of organic spintronics. Given the nature of the potential applications, we evaluated the magnetite room-temperature cubic [Formula: see text] phase in terms of structural, electronic, and magnetic properties. We considered GGA (PBE), GGA + U (PBE + U), and range-separated hybrid (HSE06 and HSE(15%)) functionals. Calculations using HSE06 and HSE(15%) functionals underline the impact that inclusion of exact exchange has on the electronic structure. While the modulation of the band gap with exact exchange has been seen in numerous situations, the dramatic change in the valence band nature and states near the Fermi level has major implications for even a qualitative interpretation of the DFT results. We find that HSE06 leads to highly localized states below the Fermi level while HSE(15%) and PBE + U result in delocalized states around the Fermi level. The significant differences in local magnetic moments and atomic charges indicate that describing room-temperature bulk materials, surfaces and interfaces may require different functionals than their low-temperature counterparts.

Does prop-2-ynylideneamine, HC≡CCH=NH, exist in space? A theoretical and computational investigation.

MP2, DFT and CCSD methods with 6-311++G** and aug-cc-pvdz basis sets have been used to probe the structural changes and relative energies of E-prop-2-ynylideneamine (I), Z-prop-2-ynylideneamine (II), prop-1,2-diene-1-imine (III) and vinyl cyanide (IV). The energy near-equivalence and provenance of preference of isomers and tautomers were investigated by NBO calculations using HF and B3LYP methods with 6-311++G** and aug-cc-pvdz basis sets. All substrates have Cs symmetry. The optimized geometries were found to be mainly theoretical method dependent. All elected levels of theory have computed I/II total energy of isomerization (ΔE) of 1.707 to 3.707 kJ/mol in favour of II at 298.15 K. MP2 and CCSD methods have indicated clearly the preference of II over III; while the B3LYP functional predicted nearly similar total energies. All tested levels of theory yielded a global II/IV tautomerization total energy (ΔE) of 137.3-148.4 kJ/mol in support of IV at 298.15 K. The negative values of ΔS indicated that IV is favoured at low temperature. At high temperature, a reverse tautomerization becomes spontaneous and II is preferred. The existence of II in space was debated through the interpretation and analysis of the thermodynamic and kinetic studies of this tautomerization reaction and the presence of similar compounds in the Interstellar Medium (ISM).

Second Trimester Spontaneous Fundal Rupture of Unscarred Bicornuate Uterus in Primipara: A Case Report and Literature Review; Jigjiga University Sheik Hassen Yabare Comprehensive Specialized Hospital, Jigjiga, Ethiopia.

Background: Primary rupture of an unscarred uterus is rare. Spontaneous rupture of an unscarred bicornuate uterus is a life-threatening obstetric emergency with high morbidity and mortality in the mother and fetus; however, it most commonly occurs in the first trimester of pregnancy. Case: A 20-year-old primigravid woman at 22 weeks of gestation, with no prior surgery, presented with severe abdominal pain, anemia, and hemodynamic instability. With a preoperative diagnosis of uterine rupture, she was transfused with three units of cross-matched whole blood and underwent emergency laparotomy. Intraoperative findings showed a ruptured bicornuate uterus and a dead fetus in the abdomen with huge hemoperitoneum. Postoperative recovery was smooth, and the patient was discharged after being counselled on family planning and subsequent pregnancy. Conclusion: A bicornuate uterus may be an independent risk factor for uterine rupture, which can occur in primigravid women at any stage of pregnancy. Each obstetrician should have a high index of suspicion for a rare condition like ruptured bicornuate uterus, especially for a pregnant woman presenting with acute abdominal pain and hemodynamic instability. Early ultrasonography plays a key role in the evaluation, follow-up, and management of these patients.