Pot-in-pot reactions: a simple and green approach to efficient organic synthesis

Incompatible organic reactions impede efficient green synthesis by making multi-component or cascade reactions a big challenge. This review highlights pot-in-pot reactions (multiple reactions carried out in one pot by separating key reactions with a thin polymeric membrane) as an efficient, green synthetic alternative to conventional synthesis. We discuss the advantages of homogeneous processes to develop new cascade reaction sequences by reviewing the use of polymeric thimbles as selective semi-permeable walls. These thimbles allow small organic molecules to diffuse through while retaining polar reagents, polar solvents, and/or organometallic catalysts. The dynamic and versatile nature of this technique is demonstrated by performing 2- and 3-step cascade reactions in one glass pot. A pot-in-pot reaction approach to synthesis circumvents the need to isolate intermediates, or handling of toxic/unpleasant by-products, therefore enabling synthesis of otherwise challenging molecules, improving the efficiency, or enabling greener approaches to modular synthesis

Synthesis of Liquid Core−Shell Particles and Solid Patchy Multicomponent Particles by Shearing Liquids Into Complex Particles (SLICE)

We report a simple method that uses (i) emulsion shearing with oxidation to make core–shell particles, and (ii) emulsion shearing with surface-tension driven phase segregation to synthesize particles with complex surface compositions and morphologies. Subjecting eutectic gallium–indium, a liquid metal, to shear in an acidic carrier fluid we synthesized smooth liquid core–shell particles 6.4 nm to over 10 μm in diameter. Aggregates of these liquid particles can be reconfigured into larger structures using a focused ion beam. Using Field’s metal melts we synthesized homogeneous nanoparticles and solid microparticles with different surface roughness and/or composition through shearing and phase separation. This extension of droplet emulsion technique, SLICE, applies fluidic shear to create micro- and nanoparticles in a tunable, green, and low-cost approach

Rapid acquisition of wideline MAS solid-state NMR spectra with fast MAS, proton detection, and dipolar HMQC pulse sequences

The solid-state NMR spectra of many NMR active elements are often extremely broad due to the presence of chemical shift anisotropy (CSA) and/or the quadrupolar interaction (for nuclei with spin I \u3e 1/2). These NMR interactions often give rise to wideline solid-state NMR spectra which can span hundreds of kHz or several MHz. Here we demonstrate that by using fast MAS, proton detection and dipolar hetero-nuclear multiple-quantum (D-HMQC) pulse sequences, it is possible to rapidly acquire 2D spectra which correlate 1H chemical shifts to the indirectly detected wideline MAS powder patterns of dipolar coupled hetero-nuclei. The D-HMQC pulse sequence enables broadband excitation of the wideline hetero-nuclear NMR spectrum and provides higher sensitivity by detecting the narrower and more sensitive 1H NMR signal. This approach is demonstrated for the rapid acquisition of 2D 1H detected 195Pt solid-state NMR spectra of cisplatin and transplatin and the 71Ga solid-state NMR spectrum of a self-assembled Ga coordination polymer of unconfirmed structure. This approach should be broadly applicable for the rapid acquisition of wideline MAS solid-state NMR spectra of moderately abundant NMR nuclei

Statistical Tools for Analyzing Measurements of Charge Transport

This paper applies statistical methods to analyze the large, noisy data sets produced in measurements of tunneling current density (J) through self-assembled monolayers (SAMs) in large-area junctions. It describes and compares the accuracy and precision of procedures for summarizing data for individual SAMs, for comparing two or more SAMs, and for determining the parameters of the Simmons model (β and J0). For data that contain significant numbers of outliers (i.e., most measurements of charge transport), commonly used statistical techniques—e.g., summarizing data with arithmetic mean and standard deviation and fitting data using a linear, least-squares algorithm—are prone to large errors. The paper recommends statistical methods that distinguish between real data and artifacts, subject to the assumption that real data (J) are independent and log-normally distributed. Selecting a precise and accurate (conditional on these assumptions) method yields updated values of β and J0 for charge transport across both odd and even n-alkanethiols (with 99% confidence intervals) and explains that the so-called odd–even effect (for n-alkanethiols on Ag) is largely due to a difference in J0 between odd and even n-alkanethiols. This conclusion is provisional, in that it depends to some extent on the statistical model assumed, and these assumptions must be tested by future experiments.Chemistry and Chemical BiologyEngineering and Applied Science

The Rate of Charge Tunneling through Self-Assembled Monolayers Is Insensitive to Many Functional Group Substitutions

Insensitivity: A series of molecules containing a common head group and body as well as structurally varied tail groups (-R) has been used in junctions with the structure Ag/S(CH2)4CONH(CH2)2R//Ga2O3/EGaIn to study the rates of charge transport by tunneling. Changing the structure of R over a range of common aliphatic, aromatic, and heteroaromatic organic groups was found to not significantly influence the rate of tunneling (see plots; the dashed lines represent calibration standards).Chemistry and Chemical Biolog

Defining the Value of Injection Current and Effective Electrical Contact Area for EGaIn-Based Molecular Tunneling Junctions

Analysis of rates of tunneling across self-assembled monolayers (SAMs) of n-alkanethiolates SCn (with n = number of carbon atoms) incorporated in junctions having structure AgTS-SAM//Ga2O3/EGaIn leads to a value for the injection tunnel current density J0 (i.e., the current flowing through an ideal junction with n = 0) of 103.6±0.3 A·cm–2 (V = +0.5 V). This estimation of J0 does not involve an extrapolation in length, because it was possible to measure current densities across SAMs over the range of lengths n = 1–18. This value of J0 is estimated under the assumption that values of the geometrical contact area equal the values of the effective electrical contact area. Detailed experimental analysis, however, indicates that the roughness of the Ga2O3 layer, and that of the AgTS-SAM, determine values of the effective electrical contact area that are 10–4 the corresponding values of the geometrical contact area. Conversion of the values of geometrical contact area into the corresponding values of effective electrical contact area results in J0(+0.5 V) = 107.6±0.8 A·cm–2, which is compatible with values reported for junctions using top-electrodes of evaporated Au, and graphene, and also comparable with values of J0 estimated from tunneling through single molecules. For these EGaIn-based junctions, the value of the tunneling decay factor β (β = 0.75 ± 0.02 Å–1; β = 0.92 ± 0.02 nC–1) falls within the consensus range across different types of junctions (β = 0.73–0.89 Å–1; β = 0.9–1.1 nC–1). A comparison of the characteristics of conical Ga2O3/EGaIn tips with the characteristics of other top-electrodes suggests that the EGaIn-based electrodes provide a particularly attractive technology for physical-organic studies of charge transport across SAMs.Chemistry and Chemical Biolog

Paramagnetic Ionic Liquids for Measurements of Density Using Magnetic Levitation

Paramagnetic ionic liquids (PILs) provide new capabilities to measurements of density using magnetic levitation (MagLev). In a typical measurement, a diamagnetic object of unknown density is placed in a container containing a PIL. The container is placed between two magnets (typically NdFeB, oriented with like poles facing). The density of the diamagnetic object can be determined by measuring its position in the magnetic field along the vertical axis (levitation height, h), either as an absolute value, or relative to internal standards of known density. For density measurements by MagLev, PILs have three advantages over solutions of paramagnetic salts in aqueous or organic solutions: (i) negligible vapor pressures; (ii) low melting points; (iii) high thermal stabilities. In addition, the densities, magnetic susceptibilities, glass transition temperatures, thermal decomposition temperatures, viscosities, and hydrophobicities of PILs can be tuned over broad ranges by choosing the cation–anion pair. The low melting points and high thermal stabilities of PILs provide large liquidus windows for density measurements. This paper demonstrates applications and advantages of PILs in density-based analyses using MagLev.Chemistry and Chemical Biolog

Rethinking the Design of Low-Cost Point-of-Care Diagnostic Devices

Reducing the global diseases burden requires effective diagnosis and treatment. In the developing world, accurate diagnosis can be the most expensive and time-consuming aspect of health care. Healthcare cost can, however, be reduced by use of affordable rapid diagnostic tests (RDTs). In the developed world, low-cost RDTs are being developed in many research laboratories; however, they are not being equally adopted in the developing countries. This disconnect points to a gap in the design philosophy, where parameterization of design variables ignores the most critical component of the system, the point-of-use stakeholders (e.g., doctors, nurses and patients). Herein, we demonstrated that a general focus on reducing cost (i.e., “low-cost”), rather than efficiency and reliability is misguided by the assumption that poverty reduces the value individuals place on their well-being. A case study of clinicians in Kenya showed that “zero-cost” is a low-weight parameter for point-of-use stakeholders, while reliability and standardization are crucial. We therefore argue that a user-driven, value-addition systems-engineering approach is needed for the design of RDTs to enhance adoption and translation into the field