Calumet College of Saint Joseph

The goal is to share policy implications of sensitive, specific internet-based tests in place of current approaches to lowering violence, namely fewer mass murders, suicides, homicides. When used, internet-based tests save lives and money. From 2009-2015, a Chicago field test had 324 fewer homicides (saving $2,089,848,548, ROI=6.42). In 60 yrs., conventional approaches for high risk persons (e.g.,. inappropriately releasing poor, severely mentally ill) led to unnecessary expense including yearly: (a) 300 mass murders (59$100/test, require 2-4 hrs.

In the current study, CO2 capturing ability of encapsulated ionic liquids (ENILs) i.e., tetramethylammonium chloride (TMACl), 1,3-dimethylimidazolium chloride (MIMCl), and methylpyridinium hexafluorophosphate (MPHP) encapsulated in self assembled belt[14]pyridine (BP) has been studied. The results show that strong van der Waals forces are involved in capturing of CO2 by these encapsulated ionic liquids. Strong attractive forces arise from synergistic effect of ionic liquid (encapsulated) and atoms of belt. The interaction energies (Eint) ranging from −12.54 to −18.64 kcal mol⁻¹ reveal the capturing of CO2 by these systems as thermodynamically feasible process. The type and strength of interactions between CO2 and encapsulated ionic liquids is studied through QTAIM and NCI analyses. NCI analysis clearly shows that capturing of CO2 is assisted by van der Waals forces between CO2 and encapsulated ionic liquid complexes. The same feature is confirmed through QTAIM analysis as well. Natural bond orbital (NBO) analysis' results show the charge transfer between the fragments (encapsulated ionic liquids and CO2) which is validated further through electron density differences (EDD) analysis. Overall, transfer of charge towards CO2 from encapsulated ionic liquids is proved through the charge accumulation over CO2 (i.e., blue isosurfaces on CO2 molecules) through EDD analysis. The FMO analyses show the decrease in H–L gaps of encapsulated ionic liquids after CO2 capturing. The successful charge transfer and reduction in H–L gap indicate better interaction in the designed systems thus revealing these systems as a potential candidates for CO2 capturing. Overall, the best results for CO2 capture i.e., the highest interaction energy, the lowest H–L gap, and the strongest forces of interactions are shown by methylpyridinium hexafluorophosphate (MPHP) encapsulated belt[14]pyridine (BP–MPHP) system. This is due to the larger anion of methylpyridinium hexafluorophosphate as compared to the other two encapsulated ionic liquids with Cl⁻ as anion which enables it to develop strong interactions with CO2. The designed belt[14]pyridine based encapsulated ionic liquid systems are promising prospects with better CO2 capture performance and represent a new entrant in the CO2 capturing systems.

Nitroaromatics impose severe health problems and threats to the environment. Therefore, the detection of such hazardous substances is essential to save the whole ecosystem. Herein, the C5N2 sheet is used as an electrochemical sensor for the detection of 1,3-dinitrobenzene (1,3-DNB), trinitrotoluene (TNT), and picric acid (PA) using the PBE0/def2SVP level of theory as implemented in Gaussian 16. The highest interaction energy was observed for the picric acid@C5N2 complex. The trend in interaction energies for the studied system is PA@C5N2 >TNT@C5N2 >1,3-DNB@C5N2. The studied systems were further analysed by qualitative and quantitative analyses to determine the interactions between the nitroaromatic analytes and the C5N2 sheet. Electronic properties of all analytes@C5N2 complexes have been examined by NBO, EDD, FMO and DOS analysis. QTAIM analysis depicts the stronger non-covalent interactions for the PA@C5N2, which shows consistency with interaction energy and NCI analysis. Furthermore, NBO and FMO analyses show that the C5N2 substrate exhibits high sensitivity and selectivity towards the picric acid compared to TNT and 1,3-DNB nitroaromatics. EDD and DOS analyses are in agreement with NBO and FMO analyses. Furthermore, the recovery time of the studied system has been computed to determine the efficiency of C5N2 material as an electrochemical sensor. Overall, the results show that carbon nitride can be a good sensor for the detection of nitroaromatics.

Hydrogen is currently considered as the best alternative for traditional fuels due to its sustainable and ecofriendly nature. Additionally, hydrogen dissociation is a critical step in almost all hydrogenation reactions, which is crucial in industrial chemical production. A cost-effective and efficient catalyst with favorable activity for this step is highly desirable. Herein, transition-metal-doped fullerene (TM@C60) complexes are designed and investigated as single-atom catalysts for the hydrogen splitting process. Interaction energy analysis (Eint) is also carried out to demonstrate the stability of designed TM@C60 metallofullerenes, which reveals that all the designed complexes have higher thermodynamic stability. Furthermore, among all the studied metallofullerenes, the best catalytic efficiency for hydrogen dissociation is seen for the Sc@C60 catalyst Ea = 0.13 eV followed by the V@C60 catalyst Ea = 0.19 eV. The hydrogen activation and dissociation processes over TM@C60 metallofullerenes is further elaborated by analyzing charge transfer via the natural bond orbital and electron density difference analyses. Additionally, quantum theory of atoms in molecule analysis is carried out to investigate the nature of interatomic interactions between hydrogen molecules and TMs@C60 metallofullerenes. Overall, results of the current study declare that the Sc@C60 catalyst can act as a low cost, highly efficient, and noble metal-free single-atom catalyst to efficiently catalyze hydrogen dissociation reaction.

Nanographene provides a wide range of possibilities in graphene engineering for future applications due to the higher degrees of configurational freedom with the electronic parameters that may also be continuous or discrete, depending on the intended application. Therefore, the optical and electronic properties of nanographene are of substantial technological interest. Moreover, doping of graphene with heteroatoms (B, P, N, and S, etc.) alters their chemical and electronic characteristics which are suitable for the economical construction of optoelectronic devices. Herein, geometric, electronic, and optical properties of nanographene are evaluated as a function of the nature and position of dopant. Three different nanographene including coronene, hexabenzocoronene (HBC), and dodecabenzocoronene (DBC) are considered for doping (N and B as dopants) in this study with the key focus on DBC-doped systems. For any dopant number, all possible dopant sites are studied except edge position in order to avoid the edge effect. Frontier molecular orbital (FMO) analysis is performed to evaluate the perturbations in electronic characteristics of doped nanographene. A decrease in energy gap is seen for all doped systems. Natural bond orbital (NBO) analysis indicates that doping of boron (B) and nitrogen (N) results in variation in distribution of charges over the nanographene surfaces. The density of states (DOS) analysis reveals that Fermi level ([Formula: see text] is shifted for all B- and N-doped systems. The UV-visible (UV-Vis) absorption spectra are computed to evaluate the changes in the intensity and maximum adsorption wavelength ([Formula: see text] in all doped DBC. Various chemical reactivity descriptors are also evaluated which reveal the degree of stability and chemical reactivity of doped systems. The results indicate that multiple B and N atoms doping offers a new possibility for fine-tuning of electronic and optical properties of nanographene at atomic level, thus providing guidance in development of future advanced optoelectronic devices.

Enantiomers have the same physical properties but different chemical properties due to the difference in the orientation of groups in space and thus Chiral discrimination is quite necessary, as an enantiomer of drug can have lethal effects. In this study, we used the CC2 cage for chiral discrimination of amino acids using density functional theory. The results indicated the physisorption of amino acids in the central cavity of the cage. Among the four selected amino acids, proline showed maximum interactions with the cage and maximum chiral discrimination energy is also observed in the case of proline that is 2.78 kcal/mol. Quantum theory of atoms in molecules and noncovalent interaction index analyses showed that the S enantiomer in each case has maximum interactions. The charge transfer between the analyte and surface is further studied through natural bond orbital analysis. It showed sensitivity of cage for both enantiomers, but a more pronounced effect is seen for S enantiomers. In frontier molecular orbital analysis, the least EH-L gap is observed in the case of R proline with a maximum charge transfer of -0.24 e-. Electron density difference analysis is carried out to analyze the pattern of the charge distribution. The partial density of state analysis is computed to understand the contribution of each enantiomer in overall density of the complexes. Our results show that S-CC2 porous organic cages have a good ability to differentiate between two enantiomers. S-CC2 porous organic cages efficiently differentiated the S enantiomer from the R enantiomers of selected amino acids.

We report the determination of the absolute configuration of a diterpenoid, namely, ballonigrin lactone A (BLA), by comparison of the computed optical rotations, [α]D, of its two diastereomers using density functional theory (DFT) calculations to the experimental [α]D value of +22.4. One of the diastereomers having configurations 4S, 5R, 6S, 10S, 15S was named "α-BLA," and the other one with configuration 4S, 5R, 6S, 10S, 15R was called "β-BLA". Six conformers for each diastereomer (α-BLA and β-BLA) of BLA were identified through their conformational analysis. [α]D values of these six conformations for each diastereomer were calculated using DFT at the mPW1PW91/6-311G(d,p)/SMDChloroform level of theory, leading to the conformationally averaged [α]D values of -96.8 for α-BLA and +65.1 for β-BLA. Thus, it was found that the experimental [α]D value of +22.4 was of 4S, 5R, 6S, 10S, 15R, i.e., β-BLA. Experimental and computed nuclear magnetic resonance (NMR) data were also compared, and this comparison was in accordance with the conclusion drawn from the comparison of [α]D values. Finally, the results were augmented with the calculation of the DP4 analysis, and the probability obtained also endorsed our earlier calculations.

In this research, epoxy resin–based hybrid natural fiber metal laminate (HNFML) composites were prepared and their mechanical properties, shear strength, and drilling behavior were analyzed. The surfaces of the reinforcements and particles were treated using sandblasting and an aqueous solution of amino silane. The composites were fabricated by vacuum bagging method and analyzed, in accordance with ASTM standards. From mechanical test, it is observed that the inclusion of 40 vol% of surface-treated reinforcements improved the mechanical properties than as-received reinforcements by 19%, 5% and 11% for tensile, flexural strength, and Izod impact test, respectively. Similarly, the interlaminar shear strength of composite without nanosilica increased up to 22.3 MPa and 26.7 Mpa for untreated and surface-treated reinforcements. However, the drilled fractography and scanning electron microscope images show the fiber pullout and delamination for as-received materials, whereas the surface treated materials show improved adhesion. Such composites with better mechanical as well as machining properties could be used in automobile, aerospace, and defense sector where high load sustaining structures are needed.

Porphyrin based 2D materials with single atom thickness and uniform pore size have not been explored for the separation of proton isotopes. We computationally designed the porphyrin and its derivatives with the doping of oxygen, sulphur and selenium atoms and computed the kinetic energy barrier for H⁺, D⁺, and T⁺ permeation through porphyrin and core modified porphyrins by using M05-2X along with 6-31G (d,p). Zero-point energy is calculated at transition state for protium ion and its relevant isotopes permeation through porphyrin derivatives. Tunneling ratio of proton isotopes through these 2D structures is calculated by using zero-point energy (ZPE) difference of protium ion to its isotopes. Core modification of porphyrin provides better tunneling ratio for proton isotopes. Among these, mono selenium heteroporphyrin provides the most suitable results. Our study provides the molecular level insight of permeation pathway for proton isotopes through these 2D materials.

Porphyrin with atomic-level thickness and uniform pore size hasn't yet been studied for the separation of gas molecules, especially for proton isotopes. Herein, we Computationally designed O, S, and Se doped hetero-porphyrin to evaluate its kinetic energy barrier and molecular level insight of the permeation pathway for protium ion and relevant isotopes. Zero-point energy (ZPE) for protium ion isotopes was observed at the transition state while Arrhenius equation has been used to calculate the tunneling ratio of H+/D+ and H+/T+. Among all investigated hetero-porphyrins, O–O doped derivative provided the most valuable results with tunneling ratio of 23 and 30 respectively with no energy barrier.

Vibrational circular dichroism (VCD) has become a standard method for determination of absolute stereochemistry, particularly now that reliable commercial instrumentation has become available. These instruments use a now well-documented Fourier transform infrared-based approach to measure VCD that has virtually displaced initial dispersive infrared-based designs. Nonetheless, many papers have appeared reporting dispersive VCD data, especially for biopolymers. Instrumentation designed with these original methods, particularly after more recent updates optimizing performance in selected spectral regions, has been shown still to have advantages for specific applications. This article presents a mini-review of dispersive VCD instrument designs and includes sample spectra obtained for various biopolymer (particularly peptide) samples. Complementary reviews of Fourier transform-VCD designs are broadly available.

This article investigates the possibility of communicating racialized suffering in meaningful and transformative ways among the triracial hierarchy now present in the U.S. The author argues that a theological tool, an analogia vulneris (analogy of the wound), may assist us to resist the gravity of the abyss of Whiteness into which we are drawn. The author suggests that the Catholic principle of analogical speech about God may be reoriented to enable individuals and groups to communicate and to create community through their wounds. The author engages with sociology and the history of racial formation in the U.S. to describe how Whiteness functions as an idolatrous space to be resisted. The author concludes that an analogia vulneris may enable “Whites” and “Honorary Whites”, in particular, to foster a historical-critical religious racialized consciousness and to create paschal communities of resistance to Whiteness that are glimpses of Christ’s wounded, resurrected Body.