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Visible light-mediated selective and efficient oxidation of various primary/secondary benzyl alcohols to aldehydes/ketones and oxidative dehydrogenation (ODH) of partially saturated heterocycles using a scalable and reusable heterogeneous photoredox catalyst in aqueous medium are described. A systematic study led to a selective synthesis of aldehydes under an argon atmosphere while the ODH of partially saturated heterocycles under an oxygen atmosphere resulted in very good to excellent yields. The methodology is atom economical and exhibits excellent tolerance towards various functional groups, and broad substrate scope. Furthermore, a one-pot procedure was developed for the sequential oxidation of benzyl alcohols and heteroaryl carbinols followed by the Pictet–Spengler cyclization and then aromatization to obtain the β-carbolines in high isolated yields. This methodology was found to be suitable for scale up and reusability. To the best of our knowledge, this is the first report on the oxidation of structurally diverse aryl carbinols and ODH of partially saturated N-heterocycles using a recyclable and heterogeneous photoredox catalyst under environmentally friendly conditions. [ABSTRACT FROM AUTHOR]

Herein, a simple and efficient method for the oxidative dehydrogenation (ODH) of tetrahydro-β-carbolines, indolines and tetrahydro-(iso)quinolines is described using a reusable, homogeneous cobalt-phthalocyanine photoredox catalyst in a biphasic medium. A biphasic system offers an advantage of easy separation of the product and an efficient reusability of the homogeneous photoredox catalyst. Also, the current system significantly helps to overcome the solubility issue of the substrate and catalyst at room temperature. Its potential applications to organic transformations are demonstrated by the synthesis of various biologically active N-heterocycles such as indoles, (iso)quinolines and β-carbolines and natural products such as eudistomin U, norharmane, and harmane and precursors to perlolyrine and flazin. Without isolation and purification, the catalyst solution can be reused up to 5 times with almost comparable reactivity. Furthermore, the efficiency of the reaction was demonstrated on a gram scale. To the best of our knowledge, this is the first report on ODH reactions using a non noble, reusable and homogeneous cobalt photoredox catalyst under environmentally friendly conditions. [ABSTRACT FROM AUTHOR]

Herein, a novel transition-metal-free thiol-based donor-acceptor organophotocatalyst-assisted, singlet-oxygen-mediated tandem oxidative cyclization for the synthesis of substituted oxazoles in moderate-to-good yields is described. The developed method demonstrates applicability for the synthesis of various substituted quinoxalines in good-to-excellent yields. The metal-free methodology shows a practical route for the synthesis of oxazole and quinoxaline derivatives, which are privileged moieties prevalent in various biologically active compounds and natural products. To the best of our knowledge, both the thiol photocatalyst and synthesis of oxazoles by visible-light irradiation are reported for the first time.

Accelerating the development of π-conjugated molecules for applications such as energy generation and storage, catalysis, sensing, pharmaceuticals, and (semi)conducting technologies requires rapid and accurate evaluation of the electronic, redox, or optical properties. While high-throughput computational screening has proven to be a tremendous aid in this regard, machine learning (ML) and other data-driven methods can further enable orders of magnitude reduction in time while at the same time providing dramatic increases in the chemical space that is explored. However, the lack of benchmark datasets containing the electronic, redox, and optical properties that characterize the diverse, known chemical space of organic π-conjugated molecules limits ML model development. Here, we present a curated dataset containing 25k molecules with density functional theory (DFT) and time-dependent DFT (TDDFT) evaluated properties that include frontier molecular orbitals, ionization energies, relaxation energies, and low-lying optical excitation energies. Using the dataset, we train a hierarchy of ML models, ranging from classical models such as ridge regression to sophisticated graph neural networks, with molecular SMILES representation as input. We observe that graph neural networks augmented with contextual information allow for significantly better predictions across a wide array of properties. Our best-performing models also provide an uncertainty quantification for the predictions. To democratize access to the data and trained models, an interactive web platform has been developed and deployed., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Magnetic Mn x Fe 3- x O 4 nanoparticles and polymer coated magnetic-luminescent Mn x Fe 3- x O 4 @(Y,Dy/Eu)VO 4 nanocomposites were prepared to study their comparative heat generation efficiency and biocompatibilities. Cubic crystalline phases were obtained for the nanoparticles and cubic-tetragonal biphasic phases were observed for the nanocomposites. The successful doping of Mn 2+ was also confirmed by inductively coupled plasma optical emission spectroscopy. The compositions and the surface modification chemistry were confirmed by infrared spectroscopy. The formation of near-spherical and cubic/cuboid nanoparticles was observed from electron microscopy. Comparative analysis of induction heating efficiencies and magnetization values of the synthesized materials was performed for the samples. The samples showed an efficient heating effect under the influence of alternating magnetic field strengths - 3.05 × 10 6 kA m -1 s -1 and 4.58 × 10 6 kA m -1 s -1 . A higher Mn 2+ content was found to possess higher magnetization and perform better in heat generation. The nanocomposites give brilliant color emission on excitation using ultraviolet wavelengths - 300 and 315 nm. Their hydrodynamic radii and zeta potential values indicate good stability of the dispersions. Hemocompatibility studies were carried out to ascertain the effect on red blood cells. The materials were also found to exhibit excellent biocompatibility towards HeLa cell lines. This article will provide a new insight into the use of Mn x Fe 3- x O 4 based nanocomposites for magnetic fluid hyperthermia in cancer therapy.

Ion concentration polarization (ICP) accomplishes preconcentration for bioanalysis by localized depletion of electrolyte ions, thereby generating a gradient in electric field strength that facilitates electrokinetic focusing of charged analytes by their electromigration against opposing fluid flow. Such ICP focusing has been shown to accomplish up to a million-fold enrichment of nucleic acids and proteins in single-stage preconcentrators. However, the rate at which the sample volume is swept is limited, requiring several hours to achieve these high enrichment factors. This limitation is caused by two factors. First, an ion depleted zone (IDZ) formed at a planar membrane or electrode may not extend across the full channel cross section under the flow rate employed for focusing, thereby allowing the analyte to "leak" past the IDZ. Second, within the IDZ, large fluid vortices lead to mixing, which decreases the efficiency of analyte enrichment and worsens with increased channel dimensions. Here, we address these challenges with faradaic ICP (fICP) at a three-dimensional (3D) electrode comprising metallic microbeads. This 3D-electrode distributes the IDZ, and therefore, the electric field gradient utilized for counter-flow focusing across the full height of the fluidic channel, and its large area, microstructured surface supports smaller vortices. An additional bed of insulating microbeads restricts flow patterns and supplies a large area for surface conduction of ions through the IDZ. Finally, the resistance of this secondary bed enhances focusing by locally strengthening sequestering forces. This easy-to-build platform lays a foundation for the integration of enrichment with user-defined packed bed and electrode materials.

Flow sculpting is a powerful method for passive flow control that uses a sequence of bluff-body structures to engineer the structure of inertially flowing microfluidic streams. A variety of cross-sectional flow shapes can be created through this method, offering a new platform for flow manipulation or material fabrication useful in bioengineering, manufacturing, and chemistry applications. However, the inverse problem in flow sculpting - designing a device that produces a target fluid flow shape - remains challenging due to the complex, diverse, and enormous design space. Solutions to the inverse problem have been constrained to single-material fluid streams that are shaped into top-bottom symmetric shapes due to the bluff-body structures available in current libraries (pillars) that span the height of the channel. In this work, we introduce multi-material design and symmetry-breaking flow deformations enabled by half-height pillars, presented within an extremely fast simulation method for flow sculpting yielding a 34-fold reduction in runtime. The framework is deployed freely as a cross-platform application called "FlowSculpt". We detail its implementation and usage, and discuss the addition of enhanced search operations, which enable users to more easily design flow shapes that replicate their input drawings. With FlowSculpt, the microfluidics community can now quickly design flow shaping microfluidic devices on modest hardware, and easily integrate these complex physics into their research toolkit.

We describe a simple, scalable, modular, and frugal approach to create model ecosystems as millifluidic networks of interconnected habitats (hosting microbes or plants), which offers (i) quantitative and dynamic control over the exchange of chemicals between habitats, and (ii) independent control over their environment. Oscillatory laminar flows produce regions of vortex mixing around obstacles. When these overlap, rapid mass transport by dispersion occurs, which is quantitatively describable as diffusion, but is directional and tunable in rate over 3 orders of magnitude. This acceleration in the rate of diffusion is equivalent to reducing the distance between the habitats, and therefore, the organisms, down to the length scales characteristic of signaling in soil (<2 mm).

Reversible electrochemical potassium-ion intercalation in P2-type Na x CoO 2 was examined for the first time. Hexagonal Na 0.84 CoO 2 platelets prepared by a solution combustion synthesis technique were found to work as an efficient host for K + intercalation. They deliver a high reversible capacity of 82 mA h g -1 , good rate capability and excellent cycling performance up to 50 cycles.

The ability to control the shape of a flow in a passive microfluidic device enables potential applications in chemical reaction control, particle separation, and complex material fabrication. Recent work has demonstrated the concept of sculpting fluid streams in a microchannel using a set of pillars or other structures that individually deform a flow in a predictable pre-computed manner. These individual pillars are then placed in a defined sequence within the channel to yield the composition of the individual flow deformations - and ultimately complex user-defined flow shapes. In this way, an elegant mathematical operation can yield the final flow shape for a sequence without an experiment or additional numerical simulation. Although these approaches allow for programming complex flow shapes without understanding the detailed fluid mechanics, the design of an arbitrary flow shape of interest remains difficult, requiring significant design iteration. The development of intuitive basic operations (i.e. higher-level functions that consist of combinations of obstacles) that act on the flow field to create a basis for more complex transformations would be useful in systematically achieving a desired flow shape. Here, we show eight transformations that could serve as a partial basis for more complex transformations. We initially used in-house, freely available custom software (uFlow), which allowed us to arrive at these transformations that include making a fluid stream concave and convex, tilting, stretching, splitting, adding a vertex, shifting, and encapsulating another flow stream. The pillar sequences corresponding to these transformations were subsequently fabricated and optically analyzed using confocal imaging - yielding close agreement with uFlow-predicted shapes. We performed topological analysis on each transformation, characterizing potential sequences leading to these outputs and trends associated with changing diameter and placement of the pillars. We classify operations into four sets of sequence-building concatenations: stacking, recursion, mirroring, and shaping. The developed basis should help in the design of microfluidic systems that have a phenomenal variety of applications, such as optofluidic lensing, enhanced heat transfer, or new polymer fiber design.