Structure of the Hexadecane Rotator Phase: Combination of X-ray Spectra and Molecular Dynamics Simulation.

Rotator phases are rotationally disordered plastic crystals, some of which can form upon freezing of alkane at alkane-water interfaces. Existing X-ray diffraction studies show only partial unit cell information for rotator phases of some alkanes. This includes the rotator phase of n-hexadecane, which is a transient metastable phase in pure alkane systems, but shows remarkable stability at interfaces when mediated by a surfactant. Here, we combine synchrotron X-ray diffraction data and molecular dynamics (MD) simulations, reporting clear evidence of the face-centered orthorhombic RI rotator phase from spectra for two hexadecane emulsions, one stabilized by Brij C10 and another by Tween 40 surfactants. MD simulations of pure hexadecane use the recently developed Williams 7B force field, which is capable of reproducing crystal-to-rotator phase transitions, and it also predicts the crystal structure of the RI phase. Full unit cell information is obtained by combining unit cell dimensions from synchrotron data and molecular orientations from MD simulations. A unit cell model of the RI phase is produced in the crystallographic information file (CIF) format, with each molecule represented by a superposition of four rotational positions, each with 25% occupancy. Powder diffraction spectra computed using this model are in good agreement with the experimental spectra.

Minimum surfactant concentration required for inducing self-shaping of oil droplets and competitive adsorption effects.

Surfactant choice is key in starting the phenomena of artificial morphogenesis, the bottom-up growth of geometric particles from cooled emulsion droplets, as well as the bottom-up self-assembly of rechargeable microswimmer robots from similar droplets. The choice of surfactant is crucial for the formation of a plastic phase at the oil-water interface, for the kinetics, and for the onset temperature of these processes. But further details are needed to control these processes for bottom-up manufacturing and understand their molecular mechanisms. Still unknown are the minimum concentration of the surfactant necessary to induce the processes, or competing effects in a mixture of surfactants when only one is capable of inducing shapes. Here we systematically study the effect of surfactant nature and concentration on the shape-inducing behaviour of hexadecane-in-water emulsions with both cationic (CTAB) and non-ionic (Tween, Brij) surfactants over up to five orders of magnitude of concentration. The minimum effective concentration is found approximately equal to the critical micelle concentration (CMC), or the solubility limit below the Krafft point of the surfactant. However, the emulsions show low stability at the vicinity of CMC. In a mixed surfactant experiment (Tween 60 and Tween 20), where only one (Tween 60) can induce shapes we elucidate the role of competition at the interface during mixed surfactant adsorption by varying the composition. We find that a lower bound of ∼75% surface coverage of the shape-inducing surfactant with C14 or longer chain length is necessary for self-shaping to occur. The resulting technique produces a clear visual readout of otherwise difficult to investigate molecular events. These basic requirements (minimum concentration and % surface coverage to induce oil self-shaping) and the related experimental techniques are expected to guide academic and industrial scientists to formulations with complex surfactant mixtures and behaviour.

End-to-end system for rapid and sensitive early-detection of SARS-CoV-2 for resource-poor and field-test environments using a $51 lab-in-a-backpack.

COVID-19 has exposed stark inequalities between resource-rich and resource-poor countries. International UN- and WHO-led efforts, such as COVAX, have provided SARS-CoV-2 vaccines but half of African countries have less than 2% vaccinated in their population, and only 15 have reached 10% by October 2021, further disadvantaging local economic recovery. Key for this implementation and preventing further mutation and spread is the frequency of voluntary [asymptomatic] testing. It is limited by expensive PCR and LAMP tests, uncomfortable probes deep in the throat or nose, and the availability of hardware to administer in remote locations. There is an urgent need for an inexpensive "end-to-end" system to deliver sensitive and reliable, non-invasive tests in resource-poor and field-test conditions. We introduce a non-invasive saliva-based LAMP colorimetric test kit and a $51 lab-in-a-backpack system that detects as few as 4 viral RNA copies per µL. It consists of eight chemicals, a thermometer, a thermos bottle, two micropipettes and a 1000-4000 rcf electronically operated centrifuge made from recycled computer hard drives (CentriDrive). The centrifuge includes a 3D-printed rotor and a 12 V rechargeable Li-ion battery, and its 12 V standard also allows wiring directly to automobile batteries, to enable field-use of this and other tests in low infrastructure settings. The test takes 90 minutes to process 6 samples and has reagent costs of $3.5 per sample. The non-invasive nature of saliva testing would allow higher penetration of testing and wider adoption of the test across cultures and settings (including refugee camps and disaster zones). The attached graphical procedure would make the test suitable for self-testing at home, performing it in the field, or in mobile testing centers by minimally trained staff.

Enhanced microwave absorption performance of light weight N-doped carbon nanoparticles.

Microwave absorbents with specific morphology and structure have fundamental significance for tuning microwave absorption (MA). Herein, N-doped carbon sphere nanoparticles and hollow capsules were successfully fabricated via oxidative polymerization of dopamine in different mixed solutions, without any template preparation or etching process. Compared to solid particles, the microwave absorbents consisting of N-doped carbon with a hollow structure showed enormously enhanced MA performance, exhibiting a broad effective absorption bandwidth (from 12.7 GHz to 17.9 GHz) and a minimum reflection loss of -27.2 dB with a sample thickness of 2.0 mm. This work paves an attractive way for simple and eco-friendly preparation of advanced light weight microwave absorbents.

A molecular dynamics study on the mechanical properties of Fe-Ni alloy nanowires and their temperature dependence.

Fe-Ni alloy nanowires are widely used in high-density magnetic memories and catalysts due to their unique magnetic and electrochemical properties. Understanding the deformation mechanism and mechanical property of Fe-Ni alloy nanowires is of great importance for the development of devices. However, the detailed deformation mechanism of the alloy nanowires at different temperatures is unclear. Herein, the deformation mechanism of Fe-Ni alloy nanowires and their mechanical properties were investigated via the molecular dynamics simulation method. It was found that the local atomic pressure fluctuation of the Fe-Ni alloy nanowire surface became more prominent with an increase in the Ni content. At low temperature conditions (<50 K), the plastic deformation mechanism of the Fe-Ni alloy nanowires switched from the twinning mechanism to the dislocation slip mechanism with the increase in the Ni content from 0.5 at% to 8.0 at%. In the temperature range of 50-800 K, the dislocation slip mechanism dominated the deformation. Simulation results indicated that there was a significant linear relationship between the Ni content, temperature, and ultimate stress in the temperature range of 50-800 K. Our research revealed the association between the deformation mechanism and temperature in Fe-Ni alloy nanowires, which may facilitate new alloy nanowire designs.

Radical Hydroboration and Hydrosilylation of gem-Difluoroalkenes: Synthesis of α-Difluorinated Alkylborons and Alkylsilanes.

A first example of radical hydroboration and hydrosilylation of gem-difluoroalkenes using ABIN as the radical initiator is described. This protocol features good functional group tolerance, operational simplicity, high atom economy, and easy scale-up, enabling efficient assembly of a wide range of α-difluorinated alkylborons and alkylsilanes in moderate to excellent yields. The synthetic utility of these products is demonstrated by further transformation of the C-B bond and C-Si bond into valuable CF2-containing molecules.