Can a shock-induced phonon up-pumping model relate to impact sensitivity of molecular crystals, polymorphs and cocrystals?

Impact sensitivity engineering of high-energy molecular crystals requires accurate predictive models. For this purpose, the promising multi-phonon based approach is selected, assessing a bit more its strengths and weaknesses. Presently used with high-quality phonon calculations of 22 molecular crystals, using a physics-based criterion to determine the phonon bath extent, the resulting intrinsic shock sensitivity index (SSI) is compared to the most common marker of impact sensitivity, h 50, as determined from drop-weight impact tests. Selecting a data subset from experiments performed under very similar conditions (2.5 kg hammer with grit and 30-40 mg samples), the model can predict h 50 values for mono-molecular crystals with very good accuracy, including the ability to discriminate the polymorphs of HMX and CL20. This very good agreement validates an initial indirect up-pumping mechanism occurring under these conditions, where the doorway modes also interact with the phonon bath. However, the phonon bath criterion for mono-molecular crystals does not transfer well to cocrystals. Owing to the vibrational coupling of the co-molecules, it seems a broader phonon bath should be considered. Additionally recalling experimental uncertainty and various experimental factors affecting h 50 values for a given compounds, we recommend that the density of the sample, granularity and morphology be systematically considered and reported along with measurements, which will in turn allow for more systematic data and predictive capabilities for sensitivity models.

Improved predictions of thermomechanical properties of molecular crystals from energy and dispersion corrected DFT.

Thermal stability and pressure-dependent changes are key to molecular crystals and their properties. The determination of their thermal properties from ab initio methods is, however, a challenging task. While the low-frequency phonon spectrum related to intermolecular vibrations remains difficult to describe, the Quasi-Harmonic Approximation (QHA) also induces for molecular crystals a significant volume deviation, which makes their thermal behavior ill-determined. To overcome these difficulties, we consider a pragmatic energy correction (EC) that has long been used for atomic crystals, and we presently report the first ever use for molecular crystals. Applying the QHA in dispersion-corrected density functional theory (DFT-D) calculations with an ab initio parameterized EC, the resulting model can simultaneously and accurately derive thermal and mechanical properties of high-explosive molecular crystals. When compared to experiments, the mean absolute percent error of previous DFT-based thermomechanical models is 12% for mechanical and 31% for thermal properties. Our model performs significantly better and reduces these uncertainties to 4.1% and 9.8%, respectively. In particular, the agreement between our model and experiments for the thermal properties is three times better. This significant improvement greatly benefits the determination of thermomechanical properties such as the Grüneisen parameter and the shock properties. The method has been successfully applied to molecular crystals showing a large diversity of weak intermolecular interactions (ß-1,3,5,7-tetranitro-1,3,5,7-tetrazoctane (HMX), α-1,1-diamino-2,2-dinitroethylene (FOX-7), Triaminotrinitrobenzene (TATB), ε-Hexanitrohexaazaisowurtzitane (CL20), and Pentaerythritol tetranitrate (PETN)-I). Due to its accuracy and transferability, our model is expected to work for a large class of computationally designed molecular crystals and co-crystals, providing a basis for a predictive framework.

Half metallicity in Cr substituted Fe2TiSn.

Band structure tailoring has been a great avenue to achieve the half-metallic electronic ground state in materials. Applying this approach to the full Heusler alloy Fe2TiSn, Cr is introduced systematically at Ti site that conforms to the chemical formula [Formula: see text]Sn. Compositions so obtained have been investigated for its electronic, magnetic, and electrical transport properties with an aim to observe the half-metallic ferromagnetic ground state, anticipated theoretically for Fe2CrSn. Our experimental study using synchrotron X-ray diffraction reveals that only compositions with [Formula: see text] 0.25 yield phase pure L2[Formula: see text] cubic structures. The non-magnetic ground state of Fe2TiSn gets dramatically affected upon inclusion of Cr giving rise to a localized magnetic moment in the background of Ruderman-Kittel-Kasuya-Yosida (RKKY) correlations. The ferromagnetic interactions begin to dominate for x = 0.25 composition. Results of its resistivity and magnetoresistance (MR) measurement point towards a half-metallic ground state. The calculation of exchange coupling parameter, [Formula: see text], and orbital projected density of states that indicate a change in hybridization between 3d and 5p orbital, support the observations made from the study of local crystal structure made using the extended X-ray absorption fine structure spectroscopy. Our findings here highlight an interesting prospect of finding half-metallicity via band structure tailoring for wide application in spintronics devices.

T11TS immunotherapy potentiates the repressed calcineurin-NFAT signalling pathway of T cells in Cryptococcus neoformans infected rats: a cue towards T-cell activation for antifungal immunity.

AIMS: To examine the modulation of the interacting partners of the calcineurin (CaN)-NFAT pathway in T cells during Cryptococcus neoformans fungal infection and post-T11TS immunotherapy. METHODS AND RESULTS: Wistar rats were infected with C. neoformans and followed by immunotherapy with immune-potentiator T11TS. T cells were analysed by flow cytometry, immunoblotting and nuclear translocation study. The signalling proteins LCK, FYN, LAT, PLCγ1 and CaN in T cells were regulated by C. neoformans infection resulting in reduced nuclear translocation of NFAT and IL-2 expression. Following T11TS immunotherapy, the expressions of the above-mentioned proteins were boosted and thus resulting in the clearance of C. neoformans from lung and spleen. CONCLUSIONS: The precise mechanism of suppression of the T-cell function by C. neoformans is still unknown. Previously, we have shown that T11TS positively regulates the function of T cells to abrogate glioma and other immunosuppressive conditions. T11TS immunotherapy increased the expression of the above signalling partners of the CaN-NFAT pathway in T cells and improved nuclear retention of NFAT. As a result, an increased IL-2 expression leads to activation and proliferation of T cells. SIGNIFICANCE AND IMPACT OF THE STUDY: Our results demonstrate the role of T11TS in restoring the CaN-NFAT signalling pathway in T cells. It identifies T11TS as an immunotherapeutic agent with potential clinical outcomes to counteract C. neoformans infection.

Optimization of Time- and Code-Division-Multiplexed Readout for Athena X-IFU.

Readout of a large, spacecraft-based array of superconducting transition-edge sensors (TESs) requires careful management of the layout area and power dissipation of the cryogenic-circuit components. We present three optimizations of our time- (TDM) and code-division-multiplexing (CDM) systems for the X-ray Integral Field Unit (X-IFU), a several-thousand-pixel-TES array for the planned Athena-satellite mission. The first optimization is a new readout scheme that is a hybrid of CDM and TDM. This C/TDM architecture balances CDM's noise advantage with TDM's layout compactness. The second is a redesign of a component: the shunt resistor that provides a dc-voltage bias to the TESs. A new layout and a thicker Pd-Au resistive layer combine to reduce this resistor's area by more than a factor of 5. Third, we have studied the power dissipated by the first-stage SQUIDs (superconducting quantum-interference devices) and the readout noise versus the critical current of the first-stage SqUIDs. As a result, the X-IFU TDM and C/TDM SQUIDs will have a specified junction critical current of 5 µA. Based on these design optimizations and TDM experiments described by Durkin, et al. (these proceedings), TDM meets all requirements to be X-IFU's backup-readout option. Hybrid C/TDM is another viable option that could save spacecraft resources.

Demonstration of Athena X-IFU Compatible 40-Row Time-Division-Multiplexed Readout.

Time-division multiplexing (TDM) is the backup readout technology for the X-ray Integral Field Unit (X-IFU), a 3,168-pixel X-ray transition-edge sensor (TES) array that will provide imaging spectroscopy for ESA's Athena satellite mission. X-0IFU design studies are considering readout with a multiplexing factor of up to 40. We present data showing 40-row TDM readout (32 TES rows + 8 repeats of the last row) of TESs that are of the same type as those being planned for X-IFU, using measurement and analysis parameters within the ranges specified for X-IFU. Singlecolumn TDM measurements have best-fit energy resolution of (1.91 ± 0.01) eV for the Al Kα complex (1.5 keV), (2.10 ± 0.02) eV for Ti Kα (4.5 keV), (2.23 ± 0.02) eV for Mn Kα (5.9 keV), (2.40 ± 0.02) eV for Co Kα (6.9 keV), and (3.44 ± 0.04) eV for Br Kα (11.9 keV). Three-column measurements have best-fit resolution of (2.03 ± 0.01) eV for Ti Kα and (2.40 ± 0.01) eV for Co Kα. The degradation due to the multiplexed readout ranges from 0.1 eV at the lower end of the energy range to 0.5 eV at the higher end. The demonstrated performance meets X-IFU's energy-resolution and energy-range requirements. True 40-row TDM readout, without repeated rows, of kilopixel scale arrays of X-IFU-like TESs is now under development.

A flexible-molecule force field to model and study hexanitrohexaazaisowurtzitane (CL-20) - polymorphism under extreme conditions.

The quantum-chemistry based force field (FF) developed for HMX by Smith and Bharadwaj (SB) [G. D. Smith and R. K. Bharadwaj, J. Phys. Chem. B, 1999, 103(18), 3570-3575] is transferred to another nitramine of different stoichiometry: hexanitrohexaazaisowurtzitane (CL-20 or HNIW). The modification of a single parameter alongside a very small number of add-ons related to carbon-carbon bonds, angles and dihedrals lead to two SB FF variants denoted SB-CL20 and SB-CL20 + CCNN. These flexible-molecule FFs should inherit the predictive capabilities of SB FF. For this purpose, we perform Molecular Dynamics simulations at ambient temperature and selected pressures. The modeled structures of the various CL-20 polymorphs are consistent with experimental data. Focusing on the ε-polymorph, we determine an equation of state which consolidates the general trend underpinned by most published results, and we confirm the increasing stiffness of the crystal under pressures up to 90 GPa. Moreover, we link some subtle pressure-induced changes of the elastic and structural properties to the flexibility and mobility of well-identified nitro groups. Finally, the simulations of the γ ↔ ζ phase transition suggest different multiple-step direct and reverse thermodynamic paths.

Unraveling the physical properties and superparamagnetism in anti-site disorder controlled Fe2TiSn.

With an aim to control the anti-site disorder between Fe and Ti atoms in the full Heusler alloy, Fe[Formula: see text]TiSn, we substitute a small percentage of Ti at Fe site to form the Fe[Formula: see text]Ti[Formula: see text]Sn ([Formula: see text]) series. Using the incident x-rays tuned to the Fe K-edge absorption energy, we record the high resolution synchrotron x-ray diffraction profiles and unambiguously show the reduction in anti-site disorder. In particular, the Fe-Ti anti-site disorder decreases up to an excess Ti content of 0.07; further increase of Ti content leads to disorder between Ti-Sn sites. Detailed characterization vis-á-vis the excess Ti content has been carried out in terms of its thermal and electrical transport, and magnetic properties. Signatures of strong spin fluctuation are seen in all the physical properties reported here. The much disputed high value of the Sommerfeld constant has been shown to be a resultant of such strong spin fluctuations, thus ruling out the long standing controversy of heavy fermionic nature of Fe[Formula: see text]TiSn. Magnetization and the Seebeck coefficient show clear dependence on the disorder. Both dc and ac magnetic measurements reveal the low temperature superparamagnetic nature of this system, comprising of large magnetic clusters [Formula: see text]3 nm in size.

Possible half-metallicity and variable range hopping transport in Sb-substituted Fe2TiSn Heusler alloys.

The investigation of the magnetotransport properties on [Formula: see text] [Formula: see text]Sb x with 0 [Formula: see text] 0.6 are presented in this paper. The substitution of Sb in place of Sn decreases the anti-site disorder as evident from x-ray diffraction patterns as well as from transport properties measurement. The much-disputed upturn in low temperature electrical resistivity of [Formula: see text]TiSn has been demonstrated to be a result of weak localization induced by anti-site disorder. With increased Sb substitution (⩾25%) the metallic transport behavior of [Formula: see text]TiSn changes to semiconductor-like. At low temperature, carrier transport in such compositions occurs via the variable range hopping mechanism. Moreover, a systematic increase in the anomalous Hall voltage is observed with increasing Sb-content, attributable to a side jump or Berry phase curvature effect. Electrical resistivity in the entire temperature regime hints towards half metallicity of the system. Our ab initio electronic structure calculations using generalised gradient approximation formalism further supports the results of our magnetotransport study.

A tunable coupler for superconducting microwave resonators using a nonlinear kinetic inductance transmission line.

We present a tunable coupler scheme that allows us to tune the coupling strength between a feedline and a superconducting resonator in situ over a wide range. In this scheme, we shunt the feedline with a 50-Ω lumped-element nonlinear transmission line made from a 20 nm NbTiN film. By injecting a DC current, the nonlinear kinetic inductance changes and the effective impedance shunting the resonator periodically varies from a short to an open, which tunes the coupling strength and coupling quality factor Qc . We have demonstrated Qc tuning over a factor of 40, between Qc ~ 5.5 × 104 and Qc ~ 2.3 × 106, for a 4.5 GHz resonator by applying a DC current less than 3.3 mA. Our tunable coupler scheme is easy to implement and may find broad applications in superconducting detector and quantum computing/information experiments.

Impact of silver nanoparticles on benthic prokaryotes in heavy metal-contaminated estuarine sediments in a tropical environment.

Little knowledge is available about the potential impact of commercial silver nanoparticles (Ag-NPs) on estuarine microbial communities. The Hugli river estuary, India, is susceptible to heavy metals pollution through boat traffic, and there is the potential for Ag-NP exposure via effluent discharged from ongoing municipal and industrial activities located in close proximity. This study investigated the effects of commercial Ag-NPs on native microbial communities in estuarine sediments collected from five stations, using terminal restriction fragment length polymorphism (T-RFLP) technique. An increase in the number of bacteria in consortium in sediments was observed following exposure to Ag-NPs. In general microbial communities may be resistant in estuarine systems to the antimicrobial effects of commercial Ag-NPs, but key microorganisms, such as Pelobacter propionicus, disappeared following exposure to Ag-NPs. In conclusion, the T-RFLP analysis indicated that Ag-NPs have the potential to shape estuarine sediment bacterial community structure.

Ecoepidemics overcoming the species barrier and being subject to harvesting.

An ecoepidemiological model in which the disease can be transmitted from one population to another one is considered. Linear harvesting on all the populations is considered. By means of numerical simulations, the role of the epidemiological parameters as well as that of harvesting are investigated. Some relevant consequences of harvesting on the system dynamics are discovered.

Operative interventions in the management of major postpartum haemorrhage.

In many recent studies in the developed world, the incidence of postpartum haemorrhage (PPH) has been rising, though the mortality has come down, suggesting improvement in the management of this condition. Since the publication of the RCOG guidelines in 2009 for management of PPH and the Sheffield guidelines for the use of Rusch balloon along with the initial small case series (Keriakos and Mukhopadhyay 2006), many units have introduced the guidelines into clinical practice. This has led to the reduction of surgical intervention in our unit. Major PPH accounted for 1.6% of the total deliveries in our hospital. Surgical interventions accounted for 7.8% of these cases and only 0.1% of the total deliveries. Risk factors for PPH were identified in 83%. In this paper, we reviewed the management of all patients who had major PPH and failed medical management over a period of about 4 years. All surgical interventions including Rusch balloon, B-Lynch suture, radiological interventions and hysterectomy were described. An update to Rusch balloon guidelines and Sheffield guidelines for management of major PPH are appended.

A study of coupling interactions in finite arbitrarily-shaped grooves in electromagnetic scattering problem.

A study of coupling between finite number of general-shaped grooves in electromagnetic plane-wave scattering problem is presented. The formulation for a single groove [1] is extended to two grooves. The importance of inclusion of coupling interaction between two grooves in scattering analysis is presented and its dependence on the grooves separation distance and the angle of incident of the electromagnetic field is demonstrated quantitatively. For larger angle of incident and smaller separation distance between grooves indicate larger discrepancy between between simulation results with and without inclusion of the coupling effects. Although the results presented here considers two grooves, the formulation can be extended to arbitrary number of grooves.

Dynamics of a robust photo-induced insulator-metal transition driven by coherent and broad-band light in epitaxial films of La(0.625-y)Pr(y)Ca(0.375)MnO(3).

A dramatic drop of ≈5 orders of magnitude in the resistance (R) of La(0.175)Pr(0.45)Ca(0.375)MnO(3) epitaxial films upon exposure to optical photons derived from both continuous and pulsed lasers, as well as broad-band sources at temperatures (T) < 30 K is reported. The strength of change is a sensitive function of both the incident photon flux and temperature. Under isothermal conditions the photo-generated low resistance state persists eternally after removal of light. This non-equilibrium state is metallic, as revealed by the positive dR/dT for T ≤ T(p) (≈120 K). This electrically conducting state is presumably ferromagnetic as T(p) coincides with the temperature where a weak ferromagnetism sets in on cooling the insulating film from room temperature. To rule out the possibility of photon-induced local heating of the sample as a mechanism of the observed effects, photo-illumination experiments were performed under identical conditions on thin films of two non-charge-ordered manganites deposited on substrates of similar thermal conductivity. Our model for the observed transition encompasses a global charge-ordered state in which ferromagnetic metallic clusters of fraction p much less than the critical fraction p(c) for percolation exists at low temperatures. Photo-induced melting of the charge-ordered state increases this fraction beyond p(c) in a cumulative manner as successive pulses of light fall on the sample.

Microalbuminuria: An inexpensive, non invasive bedside tool to predict outcome in critically ill patients.

This study was conducted to evaluate whether microalbuminuria on admission and after 24 hrs of admission to intensive care unit (ICU) predicts outcome as well as the Acute Physiology and Chronic Health Evaluation (APACHE) II severity illness score, the current accepted method of doing so. The study was carried out in a 20 bed mixed medical-surgical ICU of a tertiary care hospital. Of 525 consecutive adult patients with ICU stay of more than 24 hrs, 238 were included for the study. Patients with pregnancy, menstruation, anuria, macroscopic hematuria, urinary tract infection, marked proteinuria due to renal and post-renal structural diseases, were excluded. Spot urine samples were collected on admission to ICU and 24 hrs thereafter. Urine albumincreatinine ratio (ACR) was measured on ICU admission (ACR1) and after 24 hrs (ACR2) and expressed in mg/g. Patient demographics were noted on admission. For disease severity scoring, APACHE II scores were calculated. Each patient was followed up throughout their ICU stay for a maximum of 28 days and the following outcome data were obtained: ICU length of stay and ICU mortality. Of the 238 patients, 196 survived while 42 patients died in the ICU. Non-survivors had a significantly higher median ACR2 [162.7 mg/g (IQR 69.5-344.3)] in comparison to the survivors who had a median ACR2 = 54.4 mg/g (IQR 19.0-129.1) (P< 0.0001). The median ACR1 [161.0 mg/g (IQR 29.0-369.3)] of non-survivors was higher than the median ACR1 [80.4 mg/g (IQR 35.1-167.6)] of survivors but failed to reach statistical significance (P= 0.0948). In a receiver operating characteristic curve (ROC) analysis, ACR2 emerged as the best indicator of mortality [(area under curve (AUC) of ACR2 = 0.71 > AUC (ACR1) =0.58 > AUC (ΔACR) =0.55] similar to the currently used APACHE II scores (AUC = 0.78) (P=0.3). At a cutoff of 101 mg/g, ACR2 had a sensitivity of 69%, specificity of 67%, positive predictive value of 31% and a negative predictive value of 91% for predicting mortality in the critically ill patients. Absence of significant microalbuminuria at 24 hrs of ICU admission may help to predict survival in the ICU.

Human cytomegalovirus interacts with toll-like receptor 2 and CD14 on syncytiotrophoblasts to stimulate expression of TNFalpha mRNA and apoptosis.

Placentae from newborns with congenital human cytomegalovirus (HCMV) infection often display shallow implantation, chronic villitis and disruptions of the syncytiotrophoblast. Little is known about how HCMV infection induces inflammation in the placenta and loss of the trophoblast. We propose that the inflammation is initiated with innate defense responses of mature syncytiotrophoblast (ST) to virus. Previously we have shown that ultraviolet irradiation-inactivated (UV-) HCMV interacts with toll-like receptor 2 (TLR2) on primary placental cytotrophoblasts (CT) differentiated into ST-like cells thereby stimulating the release of tumor necrosis factor alpha (TNFalpha) and inducing apoptosis of neighboring cells (Chan et al, J. Pathol. 210: 111, 2006). We now determine whether known co-factors of the interaction of HCMV and TLR2 (TLR1 and CD14) bind to UV-HCMV to stimulate expression of TNFalpha and apoptosis in ST-like cells but not CT. We show that CT both fail to express detectable TLR1 and express much less CD14 than ST and that ST express CD14 but not TLR1 both in vivo and in cultured cells. The interaction of UV-HCMV and HCMV with CD14 on the surface of ST-like cells increases TNFalpha expression and induces apoptosis in the population. Antibody to CD14 also inhibits infectious HCMV induction of HCMV immediate early (HCMV IE) expressing ST-like cells. We conclude that primary villous CT express low levels of CD14 and no TLR1 but that ST strongly expresses CD14 which acts upstream of TLR2 to collect even transcriptionally inactive virus particles to stimulate TNFalpha expression and villous trophoblast damage.

Local bonding and atomic environments in Ni-catalyzed complex hydrides.

The local bonding and atomic environments in the Ni-catalyzed destabilized system LiBH4/MgH2 and the quaternary borohydride-amide phase Li3BN2H8, were studied by x-ray absorption spectroscopy. In both cases the Ni catalyst was introduced as NiCl2 and a qualitative comparison of the Ni K-edge near-edge structure suggests the Ni2+ is reduced to primarily Ni0 after ball milling. The extended fine structure of the Ni K edge indicates that the Ni is coordinated by approximately 3 boron atoms with an interatomic distance of approximately 2.1 A and approximately 11 Ni atoms in a split shell at around 2.5 and 2.8 A. These results, and the lack of long-range order, suggest that the Ni is present as a disordered nanocluster with a local structure similar to that of Ni3B. In the fully hydrogenated phase of LiBH4/MgH2 a small amount Mg2NiHx was also present. Surface calculations performed using density functional theory suggest that the lowest kinetic barrier for H2 chemisorption occurs on the Ni3B(100) surface.

Harvesting as a disease control measure in an eco-epidemiological system - a theoretical study.

Epidemiology and ecology are traditionally treated as independent research areas, but there are many commonalities between these two fields. It is frequently observed in nature that the former has an encroachment into the later and changes the system dynamics significantly. In population ecology, in particular, the predator-prey interaction in presence of parasites can produce more complex dynamics including switching of stability, extinction and oscillations. On the other hand, harvesting practices may play a crucial role in a host-parasite system. Reasonable harvesting can remove a parasite, in principle, from their host. In this paper, we study theoretically the role of harvesting in a predator-prey-parasite system. Our study shows that, using impulsive harvesting effort as control parameter, it is not only possible to control the cyclic behavior of the system populations leading to the persistence of all species, but other desired stable equilibrium including disease-free can also be obtained.