A Molecular Engineering Approach to Achieve Wavelength-Selective Photorelease Using a Dynamic Photocage.

We introduce a molecular engineering strategy for wavelength-selective photorelease of alcohols and carboxylic acids, employing a dynamic photocage featuring an (E)-3-(6-acetyl-2-hydroxynaphthalen-1-yl)acrylate moiety. Initially activated by visible light (λ ≥ 410 nm), it releases alcohol, generating a second photocage. Subsequent exposure to shorter wavelengths (λ ≤ 365 nm) selectively releases carboxylic acid, albeit at a reduced rate.

High speed impact on granular media: breakdown of conventional inertial drag models.

In this study, we extensively explore the impact process on granular media, particularly focusing on situations where the ratio of impact speed to acoustic speed is on the order of 0.01-1. This range significantly exceeds that considered in existing literature (0.0001-0.001). Our investigation involves a comprehensive comparison between our simulation data, obtained under high-speed conditions, and the established macroscopic drag models. In the high-speed regime, conventional drag force models prove inadequate, and the drag force cannot be separated into a depth-dependent static pressure and a depth-independent inertial drag, as suggested in previous literature. A detailed examination of the impact process in the high-speed limit is also presented, involving the spatio-temporal evolution of the force chain network, displacement field, and velocity field at the particle length scale. Unlike prior works demonstrating the exponential decay of pulses, we provide direct evidence of acoustic pulses propagating over long distances, reflecting from boundaries, and interfering with the original pulses. These acoustic pulses, in turn, induce large scale reorganization of the force chain network, and the granular medium continuously traverses different jammed states to support the impact load. Reorientation of the force chains leads to plastic dissipation and the eventual dissipation of the impact energy. Furthermore, we study the scaling of the early stage peak forces with the impact velocity and find that spatial dimensionality strongly influences the scaling.

Dipole screening in pure shear strain protocols of amorphous solids.

When amorphous solids are subjected to simple or pure strain, they exhibit elastic increase in stress, punctuated by plastic events that become denser (in strain) upon increasing the system size. It is customary to assume in theoretical models that the stress released in each plastic event is redistributed according to the linear Eshelby kernel, causing avalanches of additional stress release. Here we demonstrate that, contrary to the uniform affine strain resulting from simple or pure strain, each plastic event is associated with a nonuniform strain that gives rise to a displacement field that contains quadrupolar and dipolar charges that typically screen the linear elastic phenomenology and introduce anomalous length scales and influence the form of the stress redistribution. An important question that opens up is how to take this into account in elastoplastic models of shear induced phenomena like shear banding.

Micro-mechanical insights into the stress transmission in strongly aggregating colloidal gel.

Predicting the mechanical response of soft gel materials under external deformation is of paramount importance in many areas, such as foods, pharmaceuticals, solid-liquid separations, cosmetics, aerogels, and drug delivery. Most of the understanding of the elasticity of gel materials is based on the concept of fractal scaling with very few microscopic insights. Previous experimental observations strongly suggest that the gel material loses the fractal correlations upon deformation and the range of packing fraction up to which the fractal scaling can be applied is very limited. In addition, correctly implementing the fractal modeling requires identifying the elastic backbone, which is a formidable task. So far, there is no clear understanding of the gel's elasticity at high packing fractions or the correct length scale that governs its mechanical response. In this work, we undertake extensive numerical simulations to elucidate the different aspects of stress transmission in gel materials. We observe the existence of two percolating networks of compressive and tensile normal forces close to the gel point. We also find that the probability distribution for the compressive and tensile parts normalized by their respective mean shows a universal behavior irrespective of various values of interaction potential and thermal energy and different particle size distributions. Interestingly, there are also a large number of contacts with zero normal force, and, consequently, a peak in the normal force distribution is observed at fn ≈ 0 even at higher pressures. We also identify the critical internal state parameters, such as the mean normal force, force anisotropies, and the average coordination number, and propose simple constitutive relations that relate different components of stress to internal state parameters. The agreement between our model prediction and the simulation observation is excellent. It is shown that the anisotropy in the force networks gives rise to the normal stress difference in soft gel materials. Our results strongly demonstrate that the mechanical response of the gel system is governed mainly by the particle length scale phenomena, with a complex interplay between the compressive and tensile forces at the particle contact.

Performance of Density Functionals and Semiempirical 3c Methods for Small Gold-Thiolate Clusters.

In light of the recent surge in computational studies of gold thiolate clusters, we present a comparison of popular density functionals (DFAs) and three-part corrected methods (3c-methods) on their performance by taking a data set named as AuSR18 consisting of 18 isomers of Aun(SCH3)m (m ≤ n = 1-3). We have compared the efficiency and accuracy of the DFAs and 3c-methods in geometry optimization with RI-SCS-MP2 as the reference method. Similarly, the performance for accurate and efficient energy evaluation was compared with DLPNO-CCSD(T) as the reference method. The lowest energy structure among the isomers of the largest stoichiometry from our data set, AuSR18, i.e., Au3(SCH3)3, is considered to evaluate the computational time for SCF and gradient evaluations. Alongside this, the numbers of optimization steps to locate the most stable minima of Au3(SCH3)3 are compared to assess the efficiency of the methods. A comparison of relevant bond lengths with the reference geometries was made to estimate the accuracy in geometry optimization. Some methods, such as LC-BLYP, ωB97M-D3BJ, M06-2X, and PBEh-3c, could not locate many of the minima found by most of the other methods; thus, the versatility in locating various minima is also an important criterion in choosing a method for the given project. To determine the accuracy of the methods, we compared the relative energies of the isomers in each stoichiometry and the interaction energy of the gold core with the ligands. The dependence of basis set size and relativistic effects on energies are also compared. The following are some of the highlights. TPSS has shown accuracy, while mPWPW shows comparable speed and accuracy. For the relative energies of the clusters, the hybrid range-separated DFAs are the best option. CAM-B3LYP excels, whereas B3LYP performs poorly. Overall, LC-BLYP is a balanced performer considering both the geometry and relative stability of the structures, but it lacks diversity. The 3c-methods, although fast, are less impressive in relative stability.

Insights into the Active Catalyst Formation from Dinuclear Palladium Acetate in Pd-Catalyzed Coupling Reactions: A DFT Study.

We studied the steps in the formation of active palladium catalyst species from palladium acetate dimer employing density functional theory calculations. We explored the possible pathways with an automated reaction search and studied the kinetics with stochastic simulation analysis. The dimeric form of palladium acetate is considered a resting state of the catalyst. Our reaction search starting from the dimeric form by sequential ligand addition resulted in experimentally observed monomeric species. We analyzed the bonding in the palladium acetate dimer and the role of Pd in the stability of the dimeric species. We implemented the Gillespie stochastic simulation algorithm to gain more insights into multichannel reaction paths and applied it to the degradation pathways. The analysis of the thermodynamic and kinetic data for these degradation pathways suggests that the dimeric form of the catalyst can be a potential catalytic precursor in the palladium acetate-catalyzed coupling reactions under the experimental reaction conditions.

Global-scale modeling of early factors and country-specific trajectories of COVID-19 incidence: a cross-sectional study of the first 6 months of the pandemic.

BACKGROUND: Studies examining factors responsible for COVID-19 incidence have been mostly focused at the national or sub-national level. A global-level characterization of contributing factors and temporal trajectories of disease incidence is currently lacking. Here we conducted a global-scale analysis of COVID-19 infections to identify key factors associated with early disease incidence. Additionally, we compared longitudinal trends of COVID-19 incidence at a per-country level, and classified countries based on COVID-19 incidence trajectories and effects of lockdown responses. METHODS: This is an observational cross-sectional study covering COVID-19 incidence over the first 6 months of the pandemic (Jan 1, 2020 to June 30, 2020). A retrospective analysis was performed using publicly available data for total confirmed COVID-19 cases by country, and using recent data on demographic, meteorological, economic and health-related indicators per country. Data was analyzed in a regression modeling framework. Longitudinal trends were assessed via linear and non-linear model fitting. Competing models of disease trajectories were ranked by the Akaike's Information Criterion (AIC). A novel approach involving hierarchical clustering was developed to classify countries based on the effects of lockdown measures on new COVID-19 caseloads surrounding the lockdown period. RESULTS: Univariate analysis identified 11 variables (employments in the agriculture, service and industrial sectors, percent population residing in urban areas, population age, number of visitors, and temperatures in the months of Jan-Apr) as independently associated with COVID-19 infections at a global level (variable p < 1E-05). Multivariable analysis identified a 5-variable model (percent urban population, percent employed in agriculture, population density, percent population aged 15-64 years, and temperature in March) as optimal for explaining global variations in COVID-19 (model adjusted R-squared = 0.68, model p < 2.20E-16). COVID-19 case trajectories for most countries were best captured by a log-logistic model, as determined by AIC estimates. Six predominant country clusters were identified when characterizing the effects of lockdown intervals on variations in COVID-19 new cases per country. CONCLUSIONS: Globally, economic and meteorological factors are important determinants of early COVID-19 incidence. Analysis of longitudinal trends and lockdown effects on COVID-19 highlights important nuances in country-specific responses to infections. These results provide valuable insights into disease incidence at a per-country level, possibly allowing for more informed decision making by individual governments in future disease outbreaks.

Why an integrated approach between search algorithms and chemical intuition is necessary?

Though search algorithms are appropriate tools for identifying low-energy isomers, fixing several constraints seems to be a fundamental prerequisite to successfully running any structural search program. This causes some potential setbacks as far as identifying all possible isomers, close to the lowest-energy isomer, for any elemental composition. The number of explored candidates, the choice of method, basis set, and availability of CPU time needed to analyze the various initial test structures become necessary restrictions in resolving the issues of structural isomerism reasonably. While one could arrive at new structures through chemical intuition, reproducing or achieving those exact same structures requires increasing the number of variables in any given program, which causes further constraints in exploring the potential energy surface in a reasonable amount of time. Thus, it is emphasized here that an integrated approach between search algorithms and chemical intuition is necessary by taking the C12O2Mg2 system as an example. Our initial search through the AUTOMATON program yielded 1450 different geometries. However, through chemical intuition, we found eighteen new geometries within 40.0 kcal mol-1 at the PBE0-D3/def2-TZVP level. These results indirectly emphasize that an integrated approach between search algorithms and chemical intuition is necessary to further our knowledge in chemical space for any given elemental composition.

Acute Toxicity Bioassay and Determination of LC50 of Cadmium Chloride in Trichogaster (Colisa) fasciata.

Cadmium chloride is a metal salt used in industries in a large scale. Trichogaster (Colisa) fasciata (common name banded gourami) is an air-breathing fresh water fish with both nutritional and ornamental values. In this present study, as per EPA guidelines, acute toxicity bioassay was performed in a 96-h static test method in four replicates, each replicate having one control and five concentrations (25, 50, 75, 100 and 125 mg/L, respectively) of the metal salt. A total of 192 fish was used in the study in four series with each replicate containing 8 fish per concentration. The water temperature was maintained at 20-22℃ during the study. The data observed were analysed statistically on the basis of Finney's Probit Analysis method using SPSS software. The estimated 96-h LC50 value of cadmium chloride for the fish was 49.5 mg/L.

Stereochemistry of the Benzylidene γ-Butyrolactone Dictates the Reductive Heck Cyclization Mode in the Asymmetric Synthesis of Aryltetralin Lignans: A Detailed Experimental and Theoretical Study.

The reductive Heck cyclization of nonracemic benzylidene γ-butyrolactone is studied toward the asymmetric synthesis of aryltetralin lignans, where the stereochemistry of the benzylidene lactone is found to control the mode of cyclization. The Z-isomer undergoes mostly 6-endo-cyclization and provides the desired (-)-isopodophyllotoxin along with a minor amount of 5-exo-cyclized product, but the E-isomer goes through exclusively 5-exo-cyclization, leading to the undesired dihydroindenolactone compound instead of (-)-podophyllotoxin. The experimental results are well-supported by the DFT studies.

Effect of ancillary ligand on DNA and protein interaction of the two Zn (II) and Co (III) complexes: experimental and theoretical study.

In the present work we have developed one mononuclear Zn(II) complex [Zn(L)(H2O)] (Complex 1) by utilizing a tetracoordinated ligand H2L, formed by simple condensation of 2, 2 dimethyl 1,3 diamino propane and 3- ethoxy salicylaldehyde and one newly designed mononuclear Co (III) complex [Co(L)(L1)] (complex 2) by utilizing (H2L) and 3- ethoxy salicylaldehyde(HL1) as an ancillary ligand. The newly developed complex 2 have been spectroscopically characterized. An interesting phenomenon has been noticed that in presence of ancillary ligand, the solubility in buffer solution and the thermal stability of complex 2 comparatively increases than 1. To check the effect of ancillary ligand, present in complex 2 towards the DNA and HSA binding efficacy, both the complexes have been taken into consideration to inspect their binding potentiality with the macromolecules. The 'on', 'off' fluorescence changes in presence of DNA and HSA, the binding constant values, obtained from electronic spectral titration, iodide induced quenching, competitive binding assay, circular dichroism (CD) spectral titration, time resolved fluorescence experiment unambiguously assure the better binding efficacy of complex 2 with the signal of minor groove binding mode with DNA along with no significant conformational changes of the macromolecules. The strong and spontaneous binding of complex 2 with CT-DNA is further supported by the Isothermal Titration Calorimetry (ITC) study. Furthermore TDDFT calculation of DNA with and without complex 2 significantly authorize the formation of complex 2-DNA adduct during the association. Finally Molecular Docking study properly verifies the experimental findings and provides justified explanation behinds experimental findings.

Anomalous elasticity and plastic screening in amorphous solids.

Amorphous solids appear to react elastically to small external strains, but in contrast to ideal elastic media, plastic responses abound immediately at any value of the strain. Such plastic responses are quasilocalized in nature, with the "cheapest" one being a quadrupolar source. The existence of such plastic responses results in screened elasticity in which strains and stresses can either quantitatively or qualitatively differ from the unscreened theory, depending on the specific screening mechanism. Here we offer a theory of such screening effects by plastic quadrupoles, dipoles, and monopoles, explain their natural appearance, and point out the analogy to electrostatic screening by electric charges and dipoles. For low density of quadrupoles the effect is to normalize the elastic moduli without a qualitative change compared to pure elasticity theory; for higher density of quadrupoles the screening effects result in qualitative changes. Predictions for the spatial dependence of displacement fields caused by local sources of strains are provided and compared to numerical simulations. We find that anomalous elasticity is richer than electrostatics in having a screening mode that does not appear in the electrostatic analog.

Frictional Granular Matter: Protocol Dependence of Mechanical Properties.

Theoretical treatments of frictional granular matter often assume that it is legitimate to invoke classical elastic theory to describe its coarse-grained mechanical properties. Here, we show, based on experiments and numerical simulations, that this is generically not the case since stress autocorrelation functions decay more slowly than what is expected from elasticity theory. It was theoretically shown that standard elastic decay demands pressure and torque density fluctuations to be normal, with possibly one of them being hyperuniform. However, generic compressed frictional assemblies exhibit abnormal pressure fluctuations, failing to conform with the central limit theorem. The physics of this failure is linked to correlations built in the material during compression from a dilute configuration prior to jamming. By changing the protocol of compression, one can observe different pressure fluctuations, and stress autocorrelations decay at large scales.

Micro-mechanical theory of shear yield stress for strongly flocculated colloidal gel.

Shear yield stress is an important parameter in the processing of colloidal suspensions as it characterizes the solid-to-fluid transition. Although shear rheology of colloidal gel is of widespread academic and industrial interest, first principles theory that connects the microscopic properties to the macroscopic mechanical response in a self-consistent manner is lacking. In this work, we derive a constitutive relation to predict the yield stress for a strongly attractive gel undergoing quasi-static shear deformation as a function of volume fraction, inter-particle potential, contact scale properties and the micro-structure of a strongly-aggregated colloidal gel. The model also predicts the strain at which the colloidal gel network will yield under shear load. To test the model, discrete element simulation is performed using a non-central potential with friction while accounting for the rolling resistance, which is important in real colloidal gel systems. The theoretical predictions are not only in good agreement with the simulation results, but also with previous experiments.

Diffusion in agitated frictional granular matter near the jamming transition.

We study agitated frictional disks in two dimensions with the aim of developing a scaling theory for their diffusion over time. As a function of the area fraction ϕ and mean-square velocity fluctuations 〈v^{2}〉 the mean-square displacement of the disks 〈d^{2}〉 spans four to five orders of magnitude. The motion evolves from a subdiffusive form to a complex diffusive behavior at long times. The statistics of 〈d^{n}〉 at all times are multiscaling, since the probability distribution function (PDF) of displacements has very broad wings. Even where a diffusion constant can be identified it is a complex function of ϕ and 〈v^{2}〉. By identifying the relevant length and time scales and their interdependence one can rescale the data for the mean-square displacement and the PDF of displacements into collapsed scaling functions for all ϕ and 〈v^{2}〉. These scaling functions provide a predictive tool, allowing one to infer from one set of measurements (at a given ϕ and 〈v^{2}〉) what are the expected results at any value of ϕ and 〈v^{2}〉 within the scaling range.

Force distributions in frictional granular media.

We report a joint experimental and theoretical investigation of the probability distribution functions (PDFs) of the normal and tangential (frictional) forces in amorphous frictional media. We consider both the joint PDF of normal and tangential forces together, and the marginal PDFs of normal forces separately and tangential forces separately. A maximum entropy formalism is utilized for all these cases after identifying the appropriate constraints. Excellent agreements with both experimental and simulation data are reported. The proposed joint PDF predicts giant slip events at low pressures, again in agreement with observations.

Universality in consolidation of colloidal gels.

Consolidation of colloidal dispersions under external load is a complex process involving inter-particle interactions, thermal forces and hydrodynamics. Despite its importance in diverse industrial applications, past studies involving experiments, scaling approaches and simulations are yet to provide a comprehensive understanding of how the microstructure determines the mechanical response in three dimensional colloidal gels. Here, we develop a model that accounts for the microstructural details and predicts the mechanical response under slow, uniaxial compression of a strongly aggregated three dimensional colloidal gel. The particle network assumes a fractal structure that is independent of the strength of inter-particle interactions. While the yield strain changes negligibly during the entire process, the yield stress increases by several orders of magnitude. The predicted yield stress and strain are in close agreement with those observed in simulations and experiments with diverse colloidal systems, suggesting a universality in the consolidation process.

Polymorphism in phenobarbital: discovery of a new polymorph and crystal structure of elusive form V.

This report highlights the discovery of a new polymorph of the anticonvulsant drug phenobarbital (PB) using polymer-induced heteronucleation (PIHn) and unravelling the crystal structure of the elusive form V. Both forms are characterized by structural, thermal and VT-Raman spectroscopy methods to elucidate phase transformation behavior and shed light on stability relationships.

Electronic structure and biologically relevant reactivity of low-spin {FeNO}8 porphyrin model complexes: new insight from a bis-picket fence porphyrin.

Because of HNO's emerging role as an important effector molecule in biology, there is great current interest in the coordination chemistry of HNO and its deprotonated form, the nitroxyl anion (NO(-)), with hemes. Here we report the preparation of four new ferrous heme-nitroxyl model complexes, {FeNO}(8) in the Enemark-Feltham notation, using three electron-poor porphyrin ligands and the bis-picket fence porphyrin H2[3,5-Me-BAFP] (3,5-Me-BAFP(2-) = 3,5-methyl-bis(aryloxy)-fence porphyrin dianion). Electrochemical reduction of [Fe(3,5-Me-BAFP)(NO)] (1-NO) induces a shift of ν(N-O) from 1684 to 1466 cm(-1), indicative of formation of [Fe(3,5-Me-BAFP)(NO)](-) (1-NO(-)), and similar results are obtained with the electron-poor hemes. These results provide the basis to analyze general trends in the properties of ferrous heme-nitroxyl complexes for the first time. In particular, we found a strong correlation between the electronic structures of analogous {FeNO}(7) and {FeNO}(8) complexes, which we analyzed using density functional theory (DFT) calculations. To further study their reactivity, we have developed a new method for the preparation of bulk material of pure heme {FeNO}(8) complexes via corresponding [Fe(porphyrin)](-) species. Reaction of [Fe(To-F2PP)(NO)](-) (To-F2PP(2-) = tetra(ortho-difluorophenyl)porphyrin dianion) prepared this way with acetic acid generates the corresponding {FeNO}(7) complex along with the release of H2. Importantly, this disproportionation can be suppressed when the bis-picket fence porphyrin complex [Fe(3,5-Me-BAFP)(NO)](-) is used, and excitingly, with this system we were able to generate the first ferrous heme-NHO model complex reported to date. The picket fence of the porphyrin renders this HNO complex very stable, with a half-life of ~5 h at room temperature in solution. Finally, with analogous {FeNO}(8) and {FeNHO}(8) complexes in hand, their biologically relevant reactivity toward NO was then explored.

Polymorph Discrimination using Low Wavenumber Raman Spectroscopy.

Characterization of crystalline polymorphs and their quantitation has become an integral part of the pre-clinical drug development process. Raman spectroscopy is a powerful technique for the rapid identification of phases of pharmaceuticals. In the present work we demonstrate the use of low wavenumber Raman vibrational spectroscopy (including phonon measurement) for discrimination among polymorphs. A total of 10 polymorphic pharmaceuticals were employed to conduct a critical assessment. Raman scattering in the low frequency region (10-400 cm-1), which includes crystal lattice vibrations, has been analyzed and the results indicate lattice phonon Raman scattering can be used for rapid discrimination of polymorphic phases with additional discriminating power compared to conventional collection strategies. Moreover structural insight and conformational changes can be detected with this approach.