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Bendamustine hydrochloride monohydrate (marketed as Treanda®) is a nitrogen mustard purine analog alkylator used in the treatment of chronic lymphocytic leukemia (CLL) and non-Hodgkin lymphomas. Commercial bendamustine hydrochloride monohydrate crystallizes in the monoclinic space group P21/c (14), with a = 4.71348(4) Å, b = 47.5325(3) Å, c = 8.97458 (5) Å, β = 96.6515(8)°, V = 1997.161(23) Å3, and Z = 4. A reduced cell search in the Cambridge Structural Database yielded a previously reported crystal structure (Allen, 2002), which did not include hydrogens (Reck, 2006). In this work, the sample was ordered from Santa Cruz Biotechnology, and analyzed as received. The room-temperature crystal structure was refined using synchrotron (λ = 0.413896 Å) powder diffraction data, density functional theory (DFT), and Rietveld refinement techniques. Hydrogen positions were included as part of the structure, and recalculated during the refinement. The diffraction data were collected on beamline BM-11 at the Advanced Photon Source, Argonne National Laboratory. Figure 1 shows the powder X-ray diffraction pattern of the compound. The pattern is included in the Powder Diffraction File as entry 00-064-1508.
The relationship between the oscillatory force and the depth-response during dynamic indentation was analyzed mathematically and investigated experimentally in ultrafine-grained Al–Zn alloys processed by high-pressure torsion. We have shown for the first time that the phase shift between the local oscillatory force and depth signal, caused by the internal friction, is correlated to the strain-rate sensitivity, which is a key parameter indicating the ductility of materials. This correlation enables a new application of dynamic nanoindentation for studying the rate-dependent deformation-mechanisms of materials from a novel aspect.
The crystal structures of (NH4)H2C6H5O7 and (NH4)3C6H5O7 have been determined using a combination of powder and single crystal techniques. The structure of (NH4)2HC6H5O7 has been determined previously by single crystal diffraction. All three structures were optimized using density functional techniques. The crystal structures are dominated by N-H⋅⋅⋅O hydrogen bonds, though O-H⋅⋅⋅O hydrogen bonds are also important. In (NH4)H2C6H5O7 very strong centrosymmetric charge-assisted O-H-O hydrogen bonds link one end of the citrate into chains along the b-axis. A more-normal O-H⋅⋅⋅O hydrogen bond links the other end of the citrate to the central ionized carboxyl group. In (NH4)2HC6H5O7, the very strong centrosymmetric O-H-O hydrogen bonds link the citrates into zig-zag chains along the b-axis. The citrates occupy layers parallel to the bc plane, and the ammonium ions link the layers through N-H⋅⋅⋅O hydrogen bonds. In (NH4)3C6H5O7, the hydroxyl group forms a hydrogen bond to a terminal carboxylate, and there is an extensive array of N-H⋅⋅⋅O hydrogen bonds. The energies of the density functional theory-optimized structures lead to a correlation between the energy of an N-H⋅⋅⋅O hydrogen bond and the Mulliken overlap population: E(N-H⋅⋅⋅O) (kcal/mole) = 23.1(overlap)½. Powder patterns of (NH4)H2C6H5O7 and (NH4)3C6H5O7 have been submitted to International Centre for Diffraction Data for inclusion in the powder diffraction file.
Li[Lix/3Mn2x/3M1−x]O2 (M = Ni, Mn, Co) (HE-NMC) materials, which can be expressed as a combination of trigonal LiTMO2 (TM = transition metal) and monoclinic Li2MnO3 phases, are of great interest as high capacity cathodes for lithium-ion batteries. However, structural stability prevents their commercial adoption. To address this, Si doping was applied, resulting in improved stability. Raman and differential capacity analyses suggest that silicon doping improves the structural stability during electrochemical cycling. Furthermore, the doped material exhibits a 10% higher capacity relative to the control. The superior capacity likely results from the increased lattice parameters as determined by X-ray diffraction (XRD) and the lower resistance during the first cycle found by impedance and direct current resistance (DCR) measurements. Density functional theory (DFT) predictions suggest that the observed lattice expansion is an indication of increased oxygen vacancy concentration and may be due to the Si doping.
Physical understanding of crack propagation is a fundamental issue in the industry. In the literature, crack velocities of polymer materials are strongly dependent on their visco-elastic properties and energy release rates. Recently, numerical and theoretical studies have proposed that structural sizes in polymers also influence on crack propagation. Here, using polymer sheets with similar visco-elastic properties but with different pore sizes, we vary explicitly the representative structural size and examine the effect of the size on crack propagation. Findings in this work help us to understand crack propagation in polymer materials and bio-inspired materials which have porous structures.
Optoelectronic nanoscale devices have wide applications in chemical, biological, and medical technologies. Improving the performance efficiency of these devices remains a challenge. Performance is mainly dictated by the structure and characteristics of the semiconductor materials. Once a nanodevice is fabricated, its efficiency is determined. The key to improving efficiency is to control the interfaces in the device. In this article, we describe how the piezo-phototronic effect can be effectively utilized to modulate the band at the interface of a metal/semiconductor contact or a p–n junction to enhance the external efficiency of many optoelectronic nanoscale devices such as photodetectors, solar cells, and light-emitting diodes (LEDs). The piezo-phototronic effect can be highly effective at enhancing the efficiency of energy conversion in today’s green and renewable energy technology without using the sophisticated nanofabrication procedures that have high cost and complexity.
Third-generation semiconductors, such as ZnO and GaN, exhibit strong piezoelectric polarization due to the lack of inversion symmetry. The piezotronic effect observed in these semiconductors was proposed for tuning carrier transport in electronic devices by utilizing the induced piezoelectric potential as a virtual gate. This novel concept allows effective interactions between micro-/nanoelectronic devices and external mechanical stimuli. Piezotronics provide a promising approach for designing future electronic devices beyond Moore’s Law with potential for developing smart sensors, environment monitoring systems, human–machine interaction elements, and other transducers. In this article, we review recent progress in piezotronics using one-dimensional materials, heterojunctions, and large-scale arrays. We provide guidance for future piezotronic devices based on these materials.
This article discusses recent studies of piezotronics and piezo-phototronics of two-dimensional (2D) materials. Two-dimensional semiconductor materials have demonstrated excellent electronic and optoelectronic properties, and these ultrathin materials are candidates for next-generation devices. Among 2D semiconductors, transition-metal dichalcogenides in particular have large in-place piezoelectricity due to the noncentrosymmetry along the armchair direction. A strong coupling of piezoelectric and semiconducting properties has been reported for Schottky contacts and p–n junctions, even in single-layer materials. Since the carrier concentration of ultrathin 2D materials can be easily modulated by external piezocharges, layered composites of ferroelectric/2D materials also show promising piezotronic and piezo-phototronic properties.
Piezotronics can not only afford control of electronic transport over potential barriers, but the attendant mechanical stress can also influence various physical properties of piezoelectric semiconductors. Stress significantly affects the optical properties of these materials as well as their response toward the chemical environment and magnetic fields. This article focuses on the utilization of piezotronics with regard to these physical parameters for sensor applications. Stress sensors, optical sensors (especially in the ultraviolet range), and sensors for chemicals in gas and liquid phases or magnetic fields via coupled magnetostrictive layers are discussed. The benefits of piezotronics for sensors are highlighted by discussing respective figures of merit.