Molecular Interpretation of the Compaction Performance and Mechanical Properties of Caffeine Cocrystals: A Polymorphic Study.

The 1:1 caffeine (CAF) and 3-nitrobenzoic acid (NBA) cocrystal (CAF:NBA) displays polymorphism. Each polymorph shares the same docking synthon that connects individual CAF and NBA molecules within the asymmetric unit; however, the extended intermolecular interactions are significantly different between the two polymorphic modifications. These alternative interaction topologies translate to distinct structural motifs, mechanical properties, and compaction performance. To assist our molecular interpretation of the structure-mechanics-performance relationships for these cocrystal polymorphs, we combine powder Brillouin light scattering (p-BLS) to determine the mechanical properties with energy frameworks calculations to identify potentially available slip systems that may facilitate plastic deformation. The previously reported Form 1 for CAF:NBA adopts a 2D-layered crystal structure with a conventional 3.4 Å layer-to-layer separation distance. For Form 2, a columnar structure of 1D-tapes is displayed with CAF:NBA dimers running parallel to the (110) crystallographic direction. Consistent with the layered crystal structure, the shear modulus for Form 1 is significantly reduced relative to Form 2, and moreover, our p-BLS spectra for Form 1 clearly display the presence of low-velocity shear modes, which support the expectation of a low-energy slip system available for facile plastic deformation. Our energy frameworks calculations confirm that Form 1 displays a favorable slip system for plastic deformation. Combining our experimental and computational data indicates that the structural organization in Form 1 of CAF:NBA improves the compressibility and plasticity of the material, and from our tabletability studies, each of these contributions confers superior tableting performance to that of Form 1. Overall, mechanical and energy framework data permit a clear interpretation of the functional performance of polymorphic solids. This could serve as a robust screening approach for early pharmaceutical solid form selection and development.

Imaging the dynamics of individual electropores.

Electroporation is a widely used technique to permeabilize cell membranes. Despite its prevalence, our understanding of the mechanism of voltage-mediated pore formation is incomplete; methods capable of visualizing the time-dependent behavior of individual electropores would help improve our understanding of this process. Here, using optical single-channel recording, we track multiple isolated electropores in real time in planar droplet interface bilayers. We observe individual, mobile defects that fluctuate in size, exhibiting a range of dynamic behaviors. We observe fast (25 s(-1)) and slow (2 s(-1)) components in the gating of small electropores, with no apparent dependence on the applied potential. Furthermore, we find that electropores form preferentially in the liquid disordered phase. Our observations are in general supportive of the hydrophilic toroidal pore model of electroporation, but also reveal additional complexity in the interactions, dynamics, and energetics of electropores.

Velocity dispersion and backscatter in marrow-filled and water-filled trabecular bone samples in vitro.

The phase velocity and the backscatter coefficient were measured in 28 bovine femoral trabecular bone samples filled with marrow and water in vitro from 0.2 to 0.6 MHz. The phase velocities decreased approximately linearly with increasing frequency and the average dispersion rate of -34 ms-1 MHz-1 in the marrow-filled samples was higher than that of -42 ms-1 MHz-1 in the water-filled samples. The backscatter coefficients exhibited nonlinear, monotonically increasing dependences on the frequency and the average value of the exponent n = 2.92 (frequency dependence) in the marrow-filled samples was higher than the value of n = 2.79 in the water-filled samples.

Characterisation of potato crisp effective porosity using micro-CT.

BACKGROUND: The effective porosity is an important quantitative parameter for food products that has a significant effect on taste and quality. It is challenging to quantify the apparent porosity of fried potato crisps as they have a thin irregularly shaped cross section containing oil and water. This study uses a novel micro-CT technique to determine the solid volume fraction and hence the effective porosity of three types of potato crisps: standard continuously fried crisps, microwaved crisps, and continuously fried 'kettle' crisps. RESULTS: It was found that continuously fried kettle crisps had the lowest effective porosity at 0.54, providing the desired crunchy taste and lower oil contents. Crisps produced using a microwave process designed to mimic the dehydration process of standard continuous fried crisps had an effective porosity of 0.65, which was very similar to the effective porosity of 0.63 for standard continuously fried crisps. The results were supported by the findings of a forced preference consumer test. CONCLUSION: The effective porosity affects the product taste and is therefore a critical parameter. This study shows that micro-CT analysis can be used to characterise the change in effective porosity of a thin irregularly shaped food product, caused by a change of cooking procedure. © 2016 Society of Chemical Industry.

Femtosecond laser high-efficiency drilling of high-aspect-ratio microholes based on free-electron-density adjustments.

We studied the micromachining of high-aspect-ratio holes in poly(methylmethacrylate) using a visible double-pulse femtosecond laser based on free-electron-density adjustments. Hole depth and aspect ratio increased simultaneously upon decreasing the wavelength in the visible-light zone. When the pulse energy reached a high level, the free-electron density was adjusted by using a double-pulse laser, which induced fewer free electrons, a lower reflectivity plasma plume, and more pulse energy deposition in the solid bottom. Thus, the aspect ratio of the hole was improved considerably. At a moderate pulse energy level, a 1.3-1.4 times enhancement of both the ablation depth and the aspect ratio was observed when the double-pulse delay was set between 100 and 300 fs, probably due to an enhanced photon-electron coupling effect through adjusting the free-electron density. At a lower pulse energy level, this effect also induced the generation of a submicrometer string. In addition, the ablation rate was improved significantly by using visible double pulses.

Near-infrared femtosecond laser-triggered nanoperforation of hollow microcapsules.

Fabrication of a nanopore in a hollow microcapsule was demonstrated using near-infrared femtosecond laser irradiation. The shape of the irradiated microcapsules was kept spherical except for a pore in the shell owing to the nonthermal processing by a femtosecond laser. The simulation results for the near-field and far-field scattering around a microcapsule revealed that highly-enhanced optical intensity can be generated at a spot on the shell of a microcapsule, which would in turn contribute to localized ablation. To the best of our knowledge, this is the first demonstration of the nanoperforation of transparent hollow microcapsules by a near-infrared laser without any doping with absorbing metals or dyes that may cause cell toxicity. The presented method is a promising approach for safer drug delivery and the controlled release of therapeutic drugs.

Electrically pumped random lasing from FTO/porous insulator/n-ZnO/p(+)-Si devices.

Electrically pumped random lasing (RL) has been realized in FTO/porous insulator/n-ZnO/p(+)-Si devices. It is demonstrated that RL originates from the confining and recurrent scattering of light in the random cavities within the insulating layer, which are formed due to the glow discharge. The glow discharge also induces the observed negative differential resistance (NDR) effect following the normal I-V characteristics. The results present a new strategy to realize electrically pumped RL in ZnO-based metal-insulator-semiconductor device by simply modifying the morphology of the insulating layer.

Hierarchically porous materials from layer-by-layer photopolymerization of high internal phase emulsions.

A combination of high internal phase emulsion (HIPE) templating and additive manufacturing technology (AMT) is applied for creating hierarchical porosity within an acrylate and acrylate/thiol-based polymer network. The photopolymerizable formulation is optimized to produce emulsions with a volume fraction of droplet phase greater than 80 vol%. Kinetic stability of the emulsions is sufficient enough to withstand in-mold curing or computer-controlled layer-by-layer stereolithography without phase separation. By including macroscale cellular cavities within the build file, a level of controlled porosity is created simultaneous to the formation of the porous microstructure of the polyHIPE. The hybrid HIPE-AMT technique thus provides hierarchically porous materials with mechanical properties tailored by the addition of thiol chain transfer agent.

Bacteria-directed construction of hollow TiO2 micro/nanostructures with enhanced photocatalytic hydrogen evolution activity.

A general method has been developed for the synthesis of various hollow TiO2 micro/nanostructures with bacteria as templates to further study the structural effect on photocatalytic hydrogen evolution properties. TiO2 hollow spheres and hollow tubes, served as prototypes, are obtained via a surface sol-gel process using cocci and bacillus as biotemplates, respectively. The formation mechanisms are based on absorption of metal-alkoxide molecules from solution onto functional cell wall surfaces and subsequent hydrolysis to give nanometer-thick oxide layers. The UV-Vis absorption spectrum shows that the porous TiO2 hollow spheres have enhanced light harvesting property compared with the corresponding solid counterpart. This could be attributed to their unique hollow porous micro/nanostructures with microsized hollow cavities and nanovoids which could bring about multiple scattering and rayleigh scattering of light, respectively. The hollow TiO2 structures exhibit superior photocatalytic hydrogen evolution activities under UV and visible light irradiation in the presence of sacrificial reagents. The hydrogen evolution rate of hollow structures is about 3.6 times higher than the solid counterpart and 1.5 times higher than P25-TiO2. This work demonstrates the structural effect on enhancing the photocatalytic hydrogen evolution performance which would pave a new pathway to tailor and improve catalytic properties over a broad range.

Self-sacrificial templating synthesis of porous quaternary Cu-Fe-Sn-S semiconductor nanotubes via microwave irradiation.

Uniform quaternary Cu(2)FeSnS(4) (CITS) nanotubes of outer diameter 400-800 nm and thickness 100-200 nm have been synthesized for the first time by a simple, rapid and easily scaled-up microwave nonaqueous route using benzyl alcohol as the microwave absorbing solvent. An interesting in situ generated one-dimensional Cu(Tu)Cl nanorod acting as a self-sacrificial template was crucial for the formation of the well-defined CITS nanotubes. Based on the designed time-dependent experiments, a formation mechanism for the CITS nanotubes was also proposed. The resulting CITS nanotubes had a strong absorption in the visible region with a bandgap of 1.71 eV that was optimal for photovoltaic applications. Our study provided a microwave nonaqueous route generally applicable for the synthesis of quaternary chalcogenide semiconductor nanotubes.

Rapid microwave-assisted synthesis of hierarchical ZnO hollow spheres and their application in Cr(VI) removal.

A rapid one-pot synthesis of hierarchical ZnO hollow spheres consisting of nanoparticles was realized by a facile microwave-assisted solvothermal method using ethanol as the solvent. According to the time-dependent observation of the formation process, a tentative mechanism based on ethyl acetate bubble-templating self-assembly of ZnO nanoparticles was proposed for the formation of the ZnO hollow spheres. Compared with the conventional heating, the microwave irradiation resulted in a significantly shortened reaction time (within 30 min) and considerably improved quality of the ZnO hollow spheres, such as narrower size distribution and more regular morphology, owing to the high heating rate and thus the accelerated reaction rate. It was shown that the microwave-assisted synthesis of ZnO nanostructures with tunable morphologies can be realized by judicious selection of appropriate solvents. The obtained ZnO hollow spheres exhibited an excellent adsorption capacity towards Cr(VI) ions in water because of their high surface area for adsorption and a good ability to preserve the accessible surface.

Visible light photocatalytic H2-production activity of CuS/ZnS porous nanosheets based on photoinduced interfacial charge transfer.

Visible light photocatalytic H(2) production through water splitting is of great importance for its potential application in converting solar energy into chemical energy. In this study, a novel visible-light-driven photocatalyst was designed based on photoinduced interfacial charge transfer (IFCT) through surface modification of ZnS porous nanosheets by CuS. CuS/ZnS porous nanosheet photocatalysts were prepared by a simple hydrothermal and cation exchange reaction between preformed ZnS(en)(0.5) nanosheets and Cu(NO(3))(2). Even without a Pt cocatalyst, the as-prepared CuS/ZnS porous nanosheets reach a high H(2)-production rate of 4147 µmol h(-1) g(-1) at CuS loading content of 2 mol % and an apparent quantum efficiency of 20% at 420 nm. This high visible light photocatalytic H(2)-production activity is due to the IFCT from the valence band of ZnS to CuS, which causes the reduction of partial CuS to Cu(2)S and thus enhances H(2)-production activity. This work not only shows a possibility for substituting low-cost CuS for noble metals in the photocatalytic H(2) production but also for the first time exhibits a facile method for enhancing H(2)-production activity by photoinduced IFCT.

Photo-EMF sensitivity of porous silicon thin layer-crystalline silicon heterojunction to ammonia adsorption.

A new method of using photo-electromotive force in detecting gas and controlling sensitivity is proposed. Photo-electromotive force on the heterojunction between porous silicon thin layer and crystalline silicon wafer depends on the concentration of ammonia in the measurement chamber. A porous silicon thin layer was formed by electrochemical etching on p-type silicon wafer. A gas and light transparent electrical contact was manufactured to this porous layer. Photo-EMF sensitivity corresponding to ammonia concentration in the range from 10 ppm to 1,000 ppm can be maximized by controlling the intensity of illumination light.

To Close or to Collapse: The Role of Charges on Membrane Stability upon Pore Formation.

Resealing of membrane pores is crucial for cell survival. Membrane surface charge and medium composition are studied as defining regulators of membrane stability. Pores are generated by electric field or detergents. Giant vesicles composed of zwitterionic and negatively charged lipids mixed at varying ratios are subjected to a strong electric pulse. Interestingly, charged vesicles appear prone to catastrophic collapse transforming them into tubular structures. The spectrum of destabilization responses includes the generation of long-living submicroscopic pores and partial vesicle bursting. The origin of these phenomena is related to the membrane edge tension, which governs pore closure. This edge tension significantly decreases as a function of the fraction of charged lipids. Destabilization of charged vesicles upon pore formation is universal-it is also observed with other poration stimuli. Disruption propensity is enhanced for membranes made of lipids with higher degree of unsaturation. It can be reversed by screening membrane charge in the presence of calcium ions. The observed findings in light of theories of stability and curvature generation are interpreted and mechanisms acting in cells to prevent total membrane collapse upon poration are discussed. Enhanced membrane stability is crucial for the success of electroporation-based technologies for cancer treatment and gene transfer.

Degradation and mineralization of bisphenol A by mesoporous Bi2WO6 under simulated solar light irradiation.

Bismuth tungstate (Bi2WO6) catalysts of different morphology were synthesized with a hydrothermal method by controlling the pH of the reaction solution. The properties of the synthesized catalysts were characterized and all catalysts presented high photoabsorption capacity in the range of UV light to visible light around 450 nm. The surface area of the catalysts decreased but the crystallinity increased with the pH of the hydrothermal reaction solution in the range of 4-11. It was found that the crystallinity of the catalysts played an important role on their degradation capacity to Bisphenol A (BPA). Bi2WO6 catalyst prepared at pH 11 displayed a mesoporous structure and it showed the highest photocatalytic activity to degrade BPA under simulated solar light irradiation. Nearly 100% of BPA with original concentration at 20 ppm was removed after 30 min irradiation in a solution with pH 10 and Bi2WO6 amount of 1.0 g L(-1). Furthermore, 86.6 and 99.1% of the total organic carbon was eliminated after 60 and 120 min irradiation, respectively. Only one intermediate at m/z 133 was observed by LC/MS and a simple pathway of BPA degradation by Bi2WO6 was proposed.

Photoresponsive block copolymers containing azobenzenes and other chromophores.

Photoresponsive block copolymers (PRBCs) containing azobenzenes and other chromophores can be easily prepared by controlled polymerization. Their photoresponsive behaviors are generally based on photoisomerization, photocrosslinking, photoalignment and photoinduced cooperative motions. When the photoactive block forms mesogenic phases upon microphase separation of PRBCs, supramolecular cooperative motion in liquid-crystalline PRBCs enables them to self-organize into hierarchical structures with photoresponsive features. This offers novel opportunities to photocontrol microphase-separated nanostructures of well-defined PRBCs and extends their diverse applications in holograms, nanotemplates, photodeformed devices and microporous films.

Electromagnetic field (EMF) effects on channel activity of nanopore OmpF protein.

In this study, the effects of nonionizing electromagnetic fields (EMF; 925 MHz) on the OmpF porin channel have been characterized at the single-channel level. Channel activity was recorded in real time by the voltage clamp method. Our results showed an increase in the frequency of channel gating and voltage sensitivity. The effects of EMF lasted for several milliseconds after the field source was terminated. However, the conductance levels of channels did not change significantly. Thermal effects of EMF on single-channel properties are a possible cause, based on theoretical evaluation of results that were comparable to those seen in conventional experiments at different temperatures. We conclude that EMF affects both the dynamics and conformation of the channel, either directly by affecting critical amino acid side-chain arrangement, or indirectly, via the electrolyte or the lipid membrane.

The controlled fabrication of nanopores by focused electron-beam-induced etching.

The fabrication of nanometric holes within thin silicon-based membranes is of great importance for various nanotechnology applications. The preparation of such holes with accurate control over their size and shape is, thus, gaining a lot of interest. In this work we demonstrate the use of a focused electron-beam-induced etching (FEBIE) process as a promising tool for the fabrication of such nanopores in silicon nitride membranes and study the process parameters. The reduction of silicon nitride by the electron beam followed by chemical etching of the residual elemental silicon results in a linear dependence of pore diameter on electron beam exposure time, enabling accurate control of nanopore size in the range of 17-200 nm in diameter. An optimal pressure of 5.3 x 10(-6) Torr for the production of smaller pores with faster process rates, as a result of mass transport effects, was found. The pore formation process is also shown to be dependent on the details of the pulsed process cycle, which control the rate of the pore extension, and its minimal and maximal size. Our results suggest that the FEBIE process may play a key role in the fabrication of nanopores for future devices both in sensing and nano-electronics applications.

Phenol degradation in water through a heterogeneous photo-Fenton process catalyzed by Fe-treated laponite.

New photo-Fenton catalysts have been prepared from synthetic layered clay laponite (laponite RD). Two series of Fe-laponite catalysts were synthesised, with or without thermal treatment of the mixture Fe polycations-laponite in the intercalation procedure. In each series, the intercalated solids underwent calcination at four temperatures, 250, 350, 450, and 550 degrees C. The catalysts were used for photo-assisted Fenton conversion of phenol, analyzing the influence of five operating factors: the wavelength of the light source (254 nm UV-C and 360 UV-A radiation), the amount of the catalyst (between 0 and 2 g/L), the initial phenol concentration (between 0.5 and 1.5 mmol/L), the initial concentration of hydrogen peroxide (between 20 and 100 mmol/L), and the initial pH of the solution (between 2.5 and 3.5). In all experiments, the temperature was kept constant at 30 degrees C. The results have shown that the almost complete conversion of phenol was possible, after only 5 min, under the following operating conditions: UV-C radiation; a pH of the aqueous solution of 3; a dose of 1 g(catalyst)/L, and a hydrogen peroxide concentration of 50 mmol/L for a solution containing 1 mmol/L of phenol. The catalyst prepared under thermal treatment and calcined at 350 degrees C showed the best catalytic performance. A kinetic model was proposed for the process, testing its validity and estimating the rate constants.

Characterization and photocatalytic activity of vanadium-doped titanium dioxide nanocatalysts.

The vanadium (V)-doped mesoporous titanium dioxide (TiO(2)) nanoparticles with V/Ti ratios from 0-2 wt% were prepared using sol-gel method in the presence of triblock polymers, Pluronic F127. SEM images showed that the V-doped TiO(2) nanoparticles were porous structures. The surface areas and pore sizes were in the range 85-107 m(2)/g and 12-14 nm, respectively. From XRPD, the V-doped mesoporous TiO(2) after calcination at 500 degrees C was mainly anatase phase, and the crystallite sizes were in the range 14-16 nm. TEM images showed that vanadia was doped both on the surface and in the lattice of anatase TiO(2). A slight red-shift in wavelength absorption was observed when V/Ti ratio increased from 0 to 2 wt%. Addition of vanadium ion slightly decreased the photocatalytic activity of TiO(2) toward the decolorization of MB under the illumination of UV light at 305 nm. However, a 1.6-1.8 times increase in rate constants for MB photodegradation was observed when 0.5-1.0 wt% V-doped TiO(2) was illumined by solar simulator at AM 1.5. These results demonstrated that the doping of low concentrations of V ion into mesoporous TiO(2) enhance the photocatalytic activity of mesoporous TiO(2) towards photodecomposition of azo dye in the visible range.