Transition metal doped ZnO nanoclusters for carbon monoxide detection: DFT studies

Metal doped ZnO nanomaterials have attracted considerable attention as a chemical sensor for toxic gases. Here, the electronic sensitivity of pristine and Sc-, Ti-, V-, Cr-, Mn-, and Fe-doped Zn₁₂O₁₂ nanoclusters toward CO gas is investigated using density functional theory calculations. It is found that replacing a Zn atom by a Sc or Ti atom does not change the sensitivity of cluster but doping V and Cr atoms significantly increase the sensitivity. Also, Mn, or Fe doping slightly improves the sensitivity. It is predicted that among all, the Cr-doped ZnO cluster may be the most favorable sensor for CO detection because its electrical conductivity considerably changes after the CO adsorption, thereby, generating an electrical signal. The calculated Gibbs free energy change for the adsorption of CO molecule on the Cr-doped cluster is about -51.2 kcal mol^-1 at 298.15 K and 1 atm, and the HOMO-LUMO gap of the adsorbent is changed by about 117.8 %.     

Theoretical study on the initial reaction mechanisms of <Emphasis Type="Italic">ansa</Emphasis>-metallocene zirconium precursor on hydroxylated Si(1 0 0) surface

The initial reaction mechanisms for depositing ZrO₂ thin films using ansa-metallocene zirconium (Cp₂CMe₂)ZrMe₂ precursor were studied by density functional theory (DFT) calculations. The (Cp₂CMe₂)ZrMe₂ precursor could be absorbed on the hydroxylated Si(1 0 0) surface via physisorption. Possible reaction pathways of (Cp₂CMe₂)ZrMe₂ were proposed. For each reaction, the activation energies and reaction energies were compared, and stationary points along the reaction pathways were shown. In addition, the influence of dispersion effects on the reactions was evaluated by non-local dispersion corrected DFT calculations.     

Theoretical insight into the sensitive mechanism of multilayer-shaped cocrystal explosives: compression and slide

Multilayer-shaped compression and slide models were employed to investigate the complex sensitive mechanisms of cocrystal explosives in response to external mechanical stimuli. Here, density functional theory (DFT) calculations implementing the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) with the Tkatchenko-Scheffler (TS) dispersion correction were applied to a series of cocrystal explosives: diacetone diperoxide (DADP)/1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB), DADP/1,3,5-tribromo-2,4,6-trinitrobenzene (TBTNB) and DADP/1,3,5-triiodo-2,4,6-trinitrobenzene (TITNB). The results show that the GGA-PBE-TS method is suitable for calculating these cocrystal systems. Compression and slide models illustrate well the sensitive mechanism of layer-shaped cocrystals of DADP/TCTNB and DADP/TITNB, in accordance with the results from electrostatic potentials and free space per molecule in cocrystal lattice analyses. DADP/TCTNB and DADP/TBTNB prefer sliding along a diagonal direction on the a?c face and generating strong intermolecular repulsions, compared to DADP/TITNB, which slides parallel to the b?c face. The impact sensitivity of DADP/TBTNB is predicted to be the same as that of DADP/TCTNB, and the impact sensitivity of DADP/TBTNB may be slightly more insensitive than that of DADP and much more sensitive than that of TBTNB.

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Graphical Abstract Theoretical insights into the sensitive mechanism of multilayer-shaped cocrystal explosives: compression and slide

     

Theoretical study of the interaction between molecular oxygen and tetraaza macrocyclic manganese complexes

Theoretical chemistry calculations using the Density Functional Theory (DFT) were carried out to understand the interaction between oxygen (O₂) and MnN₄ type manganese-based complexes during the formation of MnN₄-O₂ adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O₂ was bonded to manganese-porphyrin (MnP), manganese-octamethylporphyrin (MnOMP), manganese-tetraaza[14]annulene (MnTAA), manganese-dibenzo [b,i] [1, 4, 8, 11]-tetraaza [14] annulene (MnDBTAA), manganese-2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene ([(tim)Mn]²⁺), and manganese-2,3,9,10-tetraphenyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene ([(ph-tim)Mn]²⁺). The binding and activation of the oxygen molecule was facilitated by an increasing trend in the O-O bond lengths and a decreasing one in the O-O vibrational frequency, with preference for the O₂ side-on interaction among MnN₄ macrocycles. The catalytic activities of the MnN₄ complexes toward the O₂ binding process increased in the following order: [(ph-tim)Mn]²⁺?<?MnP?<?MnOMP?<?MnDBTAA?<?MnTAA?<?[(tim)Mn]²⁺. Therefore, it was concluded that the [(tim)Mn]²⁺complex was the most active for the binding and activation of molecular oxygen.     

Investigating the effects of point mutations on the affinity between the cyanobacterial lectin microvirin and high mannose-type glycans present on the HIV envelope glycoprotein

Human immunodeficiency virus (HIV) infections continue to exert an enormous impact on global human health. This led experts to emphasize the importance of new measures for preventing HIV infections, including the development of vaccines and novel drugs. In this context, a promising approach involves the use of lectins that can bind the surface envelope glycoprotein gp120 of HIV with high affinity, preventing viral entry. The cyanobacterial lectin microvirin (MVN) has been proposed as a candidate for development as a topical microbicide because of its ability to bind to high mannose-type glycans, potently inhibiting HIV-1 entry. Thus, the aim of this computational study was to investigate the effects of four point mutations (D53Q, D53E, D53K, and D53W) on the structure and affinity of MVN with di-mannose (MAN). Molecular dynamics simulations followed by binding free energy calculations using MM-GBSA were employed. The calculated binding free energy of ligand-receptor complexation of MVN with MAN was ?26.02 kcal mol^-1. We identified in the wild-type protein that residues I45, T59, and Q81 have a major contribution to the binding free energy of di-mannose. Among the investigated mutants, the most promising one was the D53W mutation, with a theoretical binding free energy value of ?29.16 kcal mol^-1. We suggest that this increased stability is due to the introduction of extra rigidity on the hinge region connecting two key structural elements of the MVN binding site.     

Theoretical insights into the stabilities,detonation performance,and electrostatic potentials of cocrystals containing α- or β-HMX and TATB,FOX-7, NTO,or DMF in various molar ratios

A molecular dynamics method was employed to study the binding energies associated with the cocrystallization (at selected crystal planes) of either 1,3,5-triamino-2,4,6-trinitro-benzene (TATB), 1,1-diamino-2,2-dinitroethylene, 3-nitro-1,2,4-triazol-5-one (TATB, FOX-7, and NTO, respectively, all of which are explosives), or N,N-dimethylformamide (DMF, a nonenergetic solvent) in various molar ratios with 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane in its α and β conformations (α-HMX and β-HMX, respectively). The results showed that the cocrystals with low molar ratios (2:1, 1:1, 1:2, and 1:3) were the most stable. The binding energies of HMX/NTO and HMX/DMF were larger than those of HMX/TATB and HMX/FOX-7. According to the calculated stabilities, HMX prefers to adopt its α form in HMX/TATB and its β form in HMX/NTO, whereas the two forms coexist in HMX/FOX-7. For HMX/TATB, HMX/NTO, and α-HMX/FOX-7, increasing the proportion of the cocrystal component with the highest detonation heat (HMX in the first two cases, FOX-7 in the latter) increases the detonation heat, velocity, and pressure of the cocrystal. However, increasing the proportion of the component with the highest detonation heat in β-HMX/FOX-7 and γ-CL-20/FOX-7 increases the detonation heat of the cocrystal but decreases its detonation velocity. An investigation of the surface electrostatic potential revealed how the sensitivity changes upon cocrystal formation.

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Graphical Abstract Surface electrostatic potential of HMX/TATB

     

Density functional study of H<Subscript>2</Subscript>O molecule adsorption on α-U(001) surface

Periodic density functional theory (DFT) calculations were performed to investigate the adsorption of H₂O on U(001) surface. The metallic nature of uranium atom and different adsorption sites of U(001) surface play key roles in the H₂O molecular dissociate reaction. The long-bridge site is the most favorable site of H₂O-U(001) adsorption configuration. The triangle-center site of the H atom is the most favorable site of HOH-U(001) adsorption configuration. The interaction between H₂O and U surface is more evident on the first layer than that on any other two sub-layers. The dissociation energy of one hydrogen atom from H₂O is ?1.994 to ?2.215 eV on U(001) surface, while the dissociating energy decreases to ?3.351 to ?3.394 eV with two hydrogen atoms dissociating from H₂O. These phenomena also indicate that the O_ads can promote the dehydrogenation of H₂O. A significant charge transfer from the first layer of the uranium surface to the H and O atoms is also found to occur, making the bonding partly ionic.     

Auditing sex- and gender-based medicine (SGBM) content in medical school curriculum: a student scholar model

Background

Sex- and gender-based medicine (SGBM) aims to (1) delineate and investigate sex- and gender-based differences in health, disease, and response to treatment and (2) apply that knowledge to clinical care to improve the health of both women and men. However, the integration of SGBM into medical school curricula is often haphazard and poorly defined; schools often do not know the current status of SGBM content in their curricula, even if they are committed to addressing gaps and improving SGBM delivery. Therefore, complete auditing and accounting of SGBM content in the existing medical school curriculum is necessary to determine the baseline status and prepare for successful integration of SGBM content into that curriculum.

Methods

A review of course syllabi and lecture objectives as well as a targeted data analysis of the Curriculum Management and Information Tool (CurrMIT) were completed prior to a real-time curriculum audit. Subsequently, six “student scholars,” three first-year and three second-year medical students, were recruited and trained to audit the first 2 years of the medical school curriculum for SGBM content, thus completing an audit for both of the pre-clinical years simultaneously. A qualitative analysis and a post-audit comparative analysis were completed to assess the level of SGBM instruction at our institution.

Results

The review of syllabi and the CurrMIT data analysis did not generate a meaningful catalogue of SGBM content in the curriculum; most of the content identified specifically targeted women’s or men’s health topics and not sex- or gender-based differences. The real-time student audit of the existing curriculum at Texas Tech revealed that most of the SGBM material was focused on the physiological/anatomical sex differences or gender differences in disease prevalence, with minimal coverage of sex- or gender-based differences in diagnosis, prognosis, treatment, and outcomes.

Conclusions

The real-time student scholar audit was effective in identifying SGBM content in the existing medical school curriculum that was not possible with a retrospective review of course syllabi and lecture objectives or curriculum databases such as the CurrMIT. The audit results revealed the need for improved efforts to teach SGBM topics in our school’s pre-clinical curriculum.