Automated, cryogen-free headspace-trap with gas chromatography-mass spectrometry analysis of ethylene oxide and 2-chloroethanol as residual fumigants in foods.

Ethylene oxide (EtO), although banned for use, is still being detected in foodstuffs that have been fumigated to eradicate pests during storage and transport. Residual levels over the European Union's (EU) maximum residue limit (MRL) pose severe health concerns. Recent detection of EtO and its by-product 2-chloroethanol (2-CE) at alarming levels have led to product recalls throughout the EU. Here, a simple, automated headspace (HS)-trap method for the simultaneous determination of EtO and its derivative 2-CE by gas chromatography-mass spectrometry (GC-MS) at the required MRL of ≤ 0.05 mg/kg has been implemented. Syringe-based HS combined with backflushed trapping technology provided enrichment of multiple extractions from the same sample vial (known as multi-step enrichment or MSE®) to increase sensitivity for EtO and 2-CE analysis by GC-MS using single-ion-monitoring (SIM) mode. Method detection limits (MDLs) of 0.00059 mg/kg and 0.00219 mg/kg for EtO and 2-CE, respectively, were obtained without the need for manual handling, solvent extraction or derivatization methods. Recoveries were shown to average (n = 5) at 98% and 107% for EtO and 2-CE, respectively, and the reproducibility was <10% for both compounds.

Understanding Dynamics of Polymorphic Conversion during the Tableting Process Using In Situ Mechanical Raman Spectroscopy.

The objective of this study is to achieve a fundamental understanding of polymorphic interconversion during the tableting process, including during compaction, dwell, decompression/unloading, and ejection using an in situ mechanical Raman spectroscopy. The fit-for-purpose in situ mechanical Raman spectroscopy developed herein can provide simultaneous measurement of Raman spectra and densification for the powder compacts. Chlorpropamide (CPA), an antidiabetic drug, was selected as a model pharmaceutical compound because of its mechanical shear-induced polymorphic conversions. The results confirm that CPA polymorph A (CPA-A) was transformed to CPA polymorph C (CPA-C) under different compaction stresses. We also observed that the converted polymorph CPA-C could be reverted to the CPA-A due to the elastic recovery of powder compacts as detected during dwelling and unloading. This study is the first depiction of the dynamics of CPA polymorphic interconversion during compression, dwell, unloading, and ejection. Mechanistically, this study illustrates a correlation between the change in the powder compact's relative density and polymorphic interconversion of the drug substance in different solid-state forms. The present research suggests that the process-induced polymorph conversion is a complicated dynamic process, which could be affected by the compaction pressure, the elasticity/plasticity of the material, the level of elastic recovery, and the dissipation of residual stress. In summary, this study demonstrates that the in situ mechanical Raman spectroscopy approach enables the simultaneous detection of mechanical and chemical information of the powder compact throughout the tableting process.

Direct measurement of internal temperatures of commercially-available 18650 lithium-ion batteries.

Direct access to internal temperature readings in lithium-ion batteries provides the opportunity to infer physical information to study the effects of increased heating, degradation, and thermal runaway. In this context, a method to insert temperature sensors into commercial 18650 cells to determine the short- and long-term effects through characterization testing is developed. Results show that sensor insertion only causes a decrease in capacity of 0.5-2.3%, and an increase in DC resistance of approximately 15 mΩ. The temperatures of the modified cells are approximately 0.5 °C higher than the control cells, the difference between the internal and external temperature readings of the modified cells is approximately 0.4 °C, and the modified cells exhibit the same temperature behavior and trend during cycling as the control cells. The cells are able to operate and collect data for 100-150 cycles before their capacities fade and resistances increase beyond what is observed in the control cells. The results of the testing show that cells modified with internal temperature sensors provide useful internal temperature data for cells that have experienced little or no cyclic aging.

Thermo-mechanical behavior measurement of polymer-bonded sugar under shock compression using in-situ time-resolved Raman spectroscopy.

Quantitative information regarding the local behavior of interfaces in an inhomogeneous material during shock loading is limited due to challenges associated with time and spatial resolution. This paper reports the development of a novel method for in-situ measurement of the thermo-mechanical response of polymer bonded sugar composite where measurements are performed during propagagtion of shock wave in sucrose crystal through polydimethylsiloxane binder. The time-resolved measurements were performed with 5 ns resolution providing an estimation on local pressure, temperature, strain rate, and local shock viscosity. The experiments were performed at two different impact velocities to induce shock pressure of 4.26 GPa and 2.22 GPa and strain rate greater than 106/s. The results show the solid to the liquid phase transition of sucrose under shock compression. The results are discussed with the help of fractography analyses of sucrose crystal in order to obtain insights into the underlying heat generation mechanism.

Effect of changes in tropocollagen residue sequence and hydroxyapatite mineral texture on the strength of ideal nanoscale tropocollagen-hydroxyapatite biomaterials.

Changes in mineral texture (e.g. hydroxyapatite (HAP) or aragonite) and polypeptide (e.g. tropocollagen (TC)) residue sequence are characteristic features of a disease known as osteogenesis imperfecta (OI). In OI, different possibilities of changes in polypeptide residue sequence as well as changes in polypeptide helix replacement (e.g. 3 alpha1 chains instead of 2 alpha1 and 1 alpha2 chain in OI murine) exist. The cross section of the HAP crystals could be needle like or plate like. Such texture and residue sequence related changes can significantly affect the material strength at the nanoscale. In this work, a mechanistic understanding of such factors in determining strength of nanoscale TC-HAP biomaterials is presented using three dimensional molecular dynamics (MD) simulations. Analyses point out that the peak interfacial strength for failure is the highest for supercells with plate shaped HAP crystals. TC molecules with higher number of side chain functional groups impart higher strength to the TC-HAP biomaterials at the nanoscale. Overall, HAP crystal shape variation, the direction of applied loading with respect to the relative TC-HAP orientation, and the number of side chain functional groups in TC molecules are the factor that affect TC-HAP biomaterial strength in a significant manner.

The role of interface thermal boundary resistance in the overall thermal conductivity of Si-Ge multilayered structures.

Nanoscale engineered materials with tailored thermal properties are desirable for applications such as highly efficient thermoelectric, microelectronic and optoelectronic devices. It has been shown earlier that by judiciously varying the interface thermal boundary resistance (TBR), thermal conductivity in nanostructures can be controlled. In the presented investigation, the role of TBR in controlling thermal conductivity at the nanoscale is analyzed by performing non-equilibrium molecular dynamics (NEMD) simulations to calculate thermal conductivity of a range of Si-Ge multilayered structures with 1-3 periods, and with four different layer thicknesses. The analyses are performed at three different temperatures (400, 600 and 800 K). As expected, the thermal conductivity of all layered structures increases with the increase in the number of periods as well as with the increase in the monolayer thickness. Invariably, we find that the TBR offered by the interface nearest to the hot reservoir is the highest. This effect is in contrast to the usual notion that each interface contributes equally to the heat transfer resistance in a layered structure. Findings also suggest that for high period structures the average TBR offered by the interfaces is not equal. Findings are used to derive an analytical expression that describes period-length-dependent thermal conductivity of multilayered structures.

The effect of tensile and compressive loading on the hierarchical strength of idealized tropocollagen-hydroxyapatite biomaterials as a function of the chemical environment.

Hard biomaterials such as bone, dentin and nacre have primarily a polypeptide phase (e.g. tropocollagen (TC)) and a mineral phase (e.g. hydroxyapatite (HAP) or aragonite) arranged in a staggered manner. It has been observed that the mechanical behaviour of such materials changes with the chemical environment and the direction of applied loading. In the presented investigation, explicit three-dimensional molecular dynamics (MD) simulations based analyses are performed on idealized TC-HAP composite biomaterial systems to understand the effects of tensile and compressive loadings in three different chemical environments: (1) unsolvated, (2) solvated with water and (3) calcinated and solvated with water. The MD analyses are performed on two interfacial supercells corresponding to the lowest structural level (level n) of TC-HAP interactions and on two other supercells with HAP supercells arranged in a staggered manner (level n+1) in a TC matrix. The supercells at level n+1 are formed by arranging level n interfacial supercells in a staggered manner. Analyses show that at level n, the presence of water molecules results in greater stability of TC molecules and TC-HAP interfaces during mechanical deformation. In addition, water also acts as a lubricant between adjacent TC molecules. Under the application of shear stress dominated loading, water molecules act to strengthen the TC-HAP interfacial strength in a manner similar to the action of glue. An overall effect of the observed mechanisms is that, in a staggered arrangement, tensile strength increases in the presence of water and calcinated water environments. On the other hand, corresponding compressive strength decreases under similar circumstances. Fundamentally, supercells with primarily normal load transfer at the TC-HAP interfaces are stronger in tensile shear loading. On the other hand, supercells with primarily tangential or shear load transfer at the TC-HAP interfaces are stronger in compressive shear loading. A combination of changes in chemical environment from vacuum to calcinated water and changes in interfacial configurations in a staggered arrangement could be chosen to make the TC-HAP material stronger under applied deformation.

Lithium-ion Battery Thermal Safety by Early Internal Detection, Prediction and Prevention.

Temperature rise in Lithium-ion batteries (LIBs) due to solid electrolyte interfaces breakdown, uncontrollable exothermic reactions in electrodes and Joule heating can result in the catastrophic failures such as thermal runaway, which is calling for reliable real-time electrode temperature monitoring. Here, we present a customized LIB setup developed for early detection of electrode temperature rise during simulated thermal runaway tests incorporating a modern additive manufacturing-supported resistance temperature detector (RTD). An advanced RTD is embedded in a 3D printed polymeric substrate and placed behind the electrode current collector of CR2032 coin cells that can sustain harsh electrochemical operational environments (acidic electrolyte without Redox, short-circuiting, leakage etc.) without participating in electrochemical reactions. The internal RTD measured an average 5.8 °C higher temperature inside the cells than the external RTD with almost 10 times faster detection ability, prohibiting thermal runaway events without interfering in the LIBs' operation. A temperature prediction model is developed to forecast battery surface temperature rise stemming from measured internal and external RTD temperature signatures.

In situ Study Unravels Bio-Nanomechanical Behavior in a Magnetic Bacterial Nano-cellulose (MBNC) Hydrogel for Neuro-Endovascular Reconstruction.

Surgical clipping and endovascular coiling are well recognized as conventional treatments of Penetrating Brain Injury aneurysms. These clinical approaches show partial success, but often result in thrombus formation and the rupture of aneurysm near arterial walls. The authors address these challenging brain traumas with a unique combination of a highly biocompatible biopolymer hydrogel rendered magnetic in a flexible and resilient membrane coating integrated to a scaffold stent platform at the aneurysm neck orifice, which enhances the revascularization modality. This work focuses on the in situ diagnosis of nano-mechanical behavior of bacterial nanocellulose (BNC) membranes in an aqueous environment used as tissue reconstruction substrates for cerebral aneurysmal neck defects. Nano-mechanical evaluation, performed using instrumented nano-indentation, shows with very low normal loads between 0.01 to 0.5 mN, in the presence of deionized water. Mechanical testing and characterization reveals that the nano-scale response of BNC behaves similar to blood vessel walls with a very low Young´s modulus, E (0.0025 to 0.04 GPa), and an evident creep effect (26.01 ± 3.85 nm s-1 ). These results confirm a novel multi-functional membrane using BNC and rendered magnetic with local adhesion of iron-oxide magnetic nanoparticles.

An investigation into mechanical strength of exoskeleton of hydrothermal vent shrimp (Rimicaris exoculata) and shallow water shrimp (Pandalus platyceros) at elevated temperatures.

This investigation reports a comparison of the exoskeleton mechanical strength of deep sea shrimp species Rimicaris exoculata and shallow water shrimp species Pandalus platyceros at temperatures ranging from 25°C to 80°C using nanoindentation experiments. Scanning Electron Microscopy (SEM) observations suggest that both shrimp exoskeletons have the Bouligand structure. Differences in the structural arrangement and chemical composition of both shrimps are highlighted by SEM and EDX (Energy Dispersive X-ray) analyses. The variation in the elastic moduli with temperature is found to be correlated with the measured compositional differences. The reduced modulus of R. exoculata is 8.26±0.89GPa at 25°C that reduces to 7.61±0.65GPa at 80°C. The corresponding decrease in the reduced modulus of P. platyceros is from 27.38±2.3GPa at 25°C to 24.58±1.71GPa at 80°C. The decrease in reduced moduli as a function of temperature is found to be dependent on the extent of calcium based minerals in exoskeleton of both types of shrimp exoskeletons.

Influence of interfacial interactions on deformation mechanism and interface viscosity in α-chitin-calcite interfaces.

The interfaces between organic and inorganic phases in natural materials have a significant effect on their mechanical properties. This work presents a quantification of the interface stress as a function of interface chemical changes (water, organic molecules) in chitin-calcite (CHI-CAL) interfaces using classical non-equilibrium molecular dynamics (NEMD) simulations and steered molecular dynamics (SMD) simulations. NEMD is used to investigate interface stress as a function of applied strain based on the virial stress formulation. SMD is used to understand interface separation mechanism and to calculate interfacial shear stress based on a viscoplastic interfacial sliding model. Analyses indicate that interfacial shear stress combined with shear viscosity can result in variations to the mechanical properties of the examined interfacial material systems. It is further verified with Kelvin-Voigt and Maxwell viscoelastic analytical models representing viscous interfaces and outer matrix. Further analyses show that overall mechanical deformation depends on maximization of interface shear strength in such materials. This work establishes lower and upper bounds of interface strength in the interfaces examined.

Haemophilic pseudotumour: surgical management of a rare case.

Haemophilia is a common cause of genetically inherited bleeding disorders. Pseudotumours occur in 1-2 % of persons with severe forms of haemophilia. These are a result of repeated haemorrhage into soft tissues, subperiosteum or a site of bone fracture with inadequate resorption of the extravasated blood. There are a number of therapeutic alternatives for this dangerous condition: surgical removal, percutaneous management, irradiation, embolization etc. In this case report, we describe the natural history, clinical course and successful surgical management of a patient with haemophilia who presented with a massive pseudotumour. We also briefly review the relevant literature on the various therapeutic modalities that have been implemented in the management of this rare complication. Though surgeons may be averse to operate on haemophiliacs, primary surgical management as done in our case may prove to be the definitive treatment option for such patients.

An analysis of the effects of temperature and structural arrangements on the thermal conductivity and thermal diffusivity of tropocollagen-hydroxyapatite interfaces.

The ability of a biomaterial to transport energy by conduction is best characterized in the steady state by its thermal conductivity and in the non-steady state by its thermal diffusivity. The complex hierarchical structure of most biomaterials makes the direct determination of the thermal diffusivity and thermal conductivity difficult using experimental methods. This study presents a classical molecular simulation based approach for the thermal diffusivity and thermal conductivity prediction for a set of tropocollagen and hydroxyapatite based idealized biomaterial interfaces. The thermal diffusivity and thermal conductivity values are calculated using the presented approach at three different temperatures (300 K, 500 K and 700 K). The effects of temperature, structural arrangements, and size of simulated systems on the thermal properties are analyzed. Analyses point out important role played by the interface orientation, interface area, and structural hierarchy. Ensuing discussions establish that the interface structural arrangement and interface orientation combined with biomimetic structural hierarchy can lead to non-intuitive thermal property variations as a function of structural features.

An investigation into environment dependent nanomechanical properties of shallow water shrimp (Pandalus platyceros) exoskeleton.

The present investigation focuses on understanding the influence of change from wet to dry environment on nanomechanical properties of shallow water shrimp exoskeleton. Scanning Electron Microscopy (SEM) based measurements suggest that the shrimp exoskeleton has Bouligand structure, a key characteristic of the crustaceans. As expected, wet samples are found to be softer than dry samples. Reduced modulus values of dry samples are found to be 24.90 ± 1.14 GPa as compared to the corresponding values of 3.79 ± 0.69 GPa in the case of wet samples. Hardness values are found to be 0.86 ± 0.06 GPa in the case of dry samples as compared to the corresponding values of 0.17 ± 0.02 GPa in the case of wet samples. In order to simulate the influence of underwater pressure on the exoskeleton strength, constant load creep experiments as a function of wet and dry environments are performed. The switch in deformation mechanism as a function of environment is explained based on the role played by water molecules in assisting interface slip and increased ductility of matrix material in wet environment in comparison to the dry environment.

An in situ platform for the investigation of Raman shift in micro-scale silicon structures as a function of mechanical stress and temperature increase.

Raman spectroscopy provides an accurate approach to measure temperature and stress in semiconductors at micro-scale and nano-scale. In the present work an in situ experimentation-based approach to separate a measured room to high temperature Raman shift signal into mechanical and thermal components when a uniaxial compressive load is applied in situ is presented. In situ uniaxial compressive loads were applied on examined silicon cantilever specimens from room temperature to 150 °C. The Raman shift measurements were performed as a function of strain at constant temperature and as a function of temperature at constant strain levels. The results show that the Raman shift measured at a given temperature under a given level of applied stress can be expressed as a summation of stress-induced Raman shift signal and temperature-induced Raman shift signal measured separately. For silicon, the stress-induced Raman shift is caused by inelastic interaction between the incident laser and the vibration of crystal lattice, while the temperature-induced Raman shift is caused by the anharmonic terms in the vibrational potential energy. Analyses indicate that such separation of Raman shift signal can be used to measure localized change in thermal conductivity and mechanical stress of semiconductor structures under applied stress.

Role of molecular level interfacial forces in hard biomaterial mechanics: a review.

Biological materials have evolved over millions of years and are often found as complex composites with superior properties compared to their relatively weak original constituents. Hard biomaterials such as nacre, bone, and dentin have intrigue researchers for decades for their high stiffness and toughness, multifunctionality, and self-healing capabilities. Challenges lie in identifying nature's mechanisms behind imparting such properties and her pathways in fabricating these composites. The route frequently acquired by nature is embedding submicron- or nano-sized mineral particles in protein matrix in a well-organized hierarchical arrangement. The key here is the formation of large amount of precisely and carefully designed organic-inorganic interfaces and synergy of mechanisms acting over multiple scales to distribute loads and damage, dissipate energy, and resist change in properties owing to events such as cracking. An important aspect to focus on is the chemo-mechanics of the organic-inorganic interfaces and its correlation with overall mechanical behavior of materials. This review focuses on presenting an overview of the past work and currently ongoing work done on this aspect. Analyses focuses on understanding role played by the interfacial mechanics on overall mechanical strength of hard biomaterials. Specific attention is given to synergy between experiments and modeling at the nanoscale to understand the hard biomaterial biomechanics.

Role of the nanoscale interfacial arrangement in mechanical strength of tropocollagen-hydroxyapatite-based hard biomaterials.

Nanoscale interfacial interactions between a polypeptide (e.g. tropocollagen (TC)) phase and a mineral (e.g. hydroxyapatite (HAP), aragonite) phase is a strong determinant of the strength of hard biological materials such as bone, dentin and nacre. This work presents a mechanistic understanding of such interfacial interactions by examining idealized TC and HAP interfacial systems. For this purpose, three-dimensional molecular dynamics analyses of tensile and compressive failure in two structurally distinct TC-HAP supercells with TC molecules arranged either along or perpendicular to a chosen HAP surface are performed. Analyses point out that the peak interfacial strength for failure results when the load is applied in the direction of TC molecules aligned along the HAP surface such that the contact area between the TC and HAP phases is at a maximum. Such an alignment also leads to the localization of peak stress over a larger length scale resulting in higher fracture strength. The addition of water is found to invariably cause an increase in the mechanical strength. Overall, analyses point out that the relative alignment of TC molecules with respect to the HAP mineral surface such that the contact area is maximal, the optimal direction of applied loading with respect to the TC-HAP orientation and the increase in strength in a hydrated environment can be important factors that contribute to making nanoscale staggered arrangement a preferred structural configuration in biomaterials.

Modeling of dynamic fracture and damage in two-dimensional trabecular bone microstructures using the cohesive finite element method.

Trabecular bone fracture is closely related to the trabecular architecture, microdamage accumulation, and bone tissue properties. Micro-finite-element models have been used to investigate the elastic and yield properties of trabecular bone but have only seen limited application in modeling the microstructure dependent fracture of trabecular bone. In this research, dynamic fracture in two-dimensional (2D) micrographs of ovine (sheep) trabecular bone is modeled using the cohesive finite element method. For this purpose, the bone tissue is modeled as an orthotropic material with the cohesive parameters calculated from the experimental fracture properties of the human cortical bone. Crack propagation analyses are carried out in two different 2D orthogonal sections cut from a three-dimensional 8 mm diameter cylindrical trabecular bone sample. The two sections differ in microstructural features such as area fraction (ratio of the 2D space occupied by bone tissue to the total 2D space), mean trabecula thickness, and connectivity. Analyses focus on understanding the effect of the rate of loading as well as on how the rate variation interacts with the microstructural features to cause anisotropy in microdamage accumulation and in the fracture resistance. Results are analyzed in terms of the dependence of fracture energy dissipation on the microstructural features as well as in terms of the changes in damage and stresses associated with the bone architecture variation. Besides the obvious dependence of the fracture behavior on the rate of loading, it is found that the microstructure strongly influences the fracture properties. The orthogonal section with lesser area fraction, low connectivity, and higher mean trabecula thickness is more resistant to fracture than the section with high area fraction, high connectivity, and lower mean trabecula thickness. In addition, it is found that the trabecular architecture leads to inhomogeneous distribution of damage, irrespective of the symmetry in the applied loading with the fracture of the entire bone section rapidly progressing to bone fragmentation once the accumulated damage in any trabeculae reaches a critical limit.