The dipyridophenazine (dppz) based ruthenium polypyridyl complexes are known as molecular ‘light-switches’ for DNA. This property is poised to serve in diagnostic and therapeutic applications, but the poor cellular uptake restricts their use in live cells. Herein, we show that the cellular uptake, and more interestingly and surprisingly, the nuclear...
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information (
and crystallographic data in CIF or
10.1039/c5sc03796d
Cite this: Chem. Sci., 2016, 7, 4016
The study of the effects of diethyldithiocarbamate (DEDTC) in some diseases is in focus for many years. However, DEDTC is a metal chelator that can present neurotoxicity as side effects. Here we investigate the effect of DEDTC on brain Zinc (Zn) content and behavior. To address this issue we used...
A series of combined measurements was made at the Naval Air Station North Island (NASNI) Installation Restoration Site 5, Unit 2 during July and August 2013. Combined measurements included CO₂ respiration rate, CO₂ radiocarbon content to estimate chlorinated hydrocarbon (CH) mineralization and a zone of influence (ZOI) model. CO₂ was...
Porous substrates transport fluid via capillary action and can be inexpensive, making them ideal for field-use sensors. Direct wax printing is one of the most commonly used fabrication methods to define fluid paths in standard substrates like cellulose and nitrocellulose. However, direct wax printing is not possible for flexible materials...
ZIF-8, a zeolitic imidazolate framework that consists of zinc ions and imidazolate linkers, is of great interest due to its simple synthesis methods, low-cost raw materials, chemical and thermal stability, as well as its stability in moist environments. Furthermore, due to its unique structure, it contains well-defined pores that have...
We demonstrate a novel synthetic route to fabricate a one-dimensional
peapod-like Sb@C structure with disperse Sb
submicron-particles encapsulated in carbon submicron-tubes.
The synthetic route may well serve as a general methodology
for fabricating carbon/metallic fine structures by thermally
reducing their carbon-coated metal oxide composites.
Acenes larger than pentacene are predicted to possess enticing electronic properties, but are insoluble and prone to rapid decomposition. Utilizing a combination of functionalization strategies, we present stable, solution processable hexacenes and an evaluation of their hole and electron transport properties.
Plastic pollution is an ever-increasing environmental threat. As large-scale plastics break down to form nanoscale plastics, it is essential to investigate their effects on freshwater ecosystems. With many plastic nanoparticle (NP) studies favoring the effects of common polystyrene (PS) plastics, a gap is formed for other common plastic types like...
NMR spectroscopy is the go-to technique for determining the solution structures of organic,
organometallic, and even macromolecular species. However, structure determination of nanoscale
aqueous inorganic clusters by NMR spectroscopy remains an unexplored territory. The few hydroxobridged
inorganic species well characterized by ¹H Nuclear Magnetic Resonance spectroscopy (¹H-NMR)
do not provide...
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≤ x ≤ 6) clusters by
¹H-NMR and QM computations. Chemical Science, 6(7), 4071-4085.
doi:10.1039
This study describes the combined experimental and computational elucidation of the mechanism and
origins of stereoselectivities in the NHC-catalyzed dynamic kinetic resolution (DKR) of α-substituted-β-ketoesters. Density functional theory computations reveal that the NHC-catalyzed DKR proceeds by two
mechanisms, depending on the stereochemistry around the forming bond: 1) a concerted, asynchronous...
A low-voltage plateau at ∼0.3 V is discovered during the deep sodiation of Na₃V₂(PO₄)₃ by combined computational and experimental studies. This new low-voltage plateau doubles the sodiation capacity of Na₃V₂(PO₄)₃, thus turning it into a promising anode for Na-ion batteries.
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-ion batteries. Chemical Communications, 51(29), 6381-6383.
doi:10.1039/c5cc00944h
10.1039/C5CC00944H
The reaction conditions for the synthesis of Cu-BTC (BTC = benzene-1,3,5-tricarboxylic acid) were elucidated using a continuous-flow microreactor-assisted solvothermal system to achieve crystal size and phase control. A high-rate synthesis of Cu-BTC metal-organic frameworks with BET surface area of more than 1600 m²/g (Langmuir surface area of more than 2000...
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:10.1039/c3cc46049e
10.1039/c3cc46049e
Royal Society of Chemistry
Accepted Manuscript
http
A novel method of copper indium diselenide nanoparticle
(CuInSe₂ NP) synthesis using a two-step, continuous flow,
solar microreactor is reported here. This method allows for
exceedingly fast heating and short reaction times using only
radiative heat transfer from simulated, concentrated solar
radiation. Chalcopyrite and sphalerite CuInSe₂ phases have
both been...
Solvent extraction is an integral chemical and biochemical separation process that is drastically intensified in microfluidic systems. A novel high-throughput micro-separator was additively manufactured for the intensification of liquid–liquid separation. The micro-posts array within the flow plate generated a capillary pressure gradient on the non-wetting organic phase, enabling continuous, membrane-free,...
Desferrioxamine B (DFOB) was reversibly and covalently conjugated to polystyrene microspheres via N-succinimidyl 3-(2-pyridyldithio)propionate (SPDP) crosslinker. DFOB retained post-immobilization activity with at least 89% able to bind Fe(III)-citrate under pH 7.4 and a citrate:iron molar ratio = 100:1. Comparing iron capture by DFOB-activated beads and sulfhydryl (−SH) control beads demonstrated...
A simple Janus-type membrane-based wicking microfluidic device fabricated on a polycaprolactone-filled glass microfiber membrane enables separation and collection of blood plasma or serum from whole blood. This device bridges the wicking and cut-capillary-based solution transport mechanisms in a single membrane. The initial portion of the device is fabricated using selective...
Combined plasmonic nanocrystals and metal–organic framework
thin-films are fabricated for sensing gases in the near-infrared
range. This nanocomposite thin-film shows a highly sensitive response
in near-infrared absorption, which is attributed to preconcentration
of gas molecules in metal–organic framework pores causing close
proximity to the electromagnetic fields at the plasmonic nanocrystal...
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Chemistry
C, 3(12), 2763-2767. doi:10.1039/C4TC02846E
10.1039/C4TC02846E
Royal Society of Chemistry
Small-angle X-ray scattering (SAXS) studies of aqueous [Ta₆O₁₉]⁸⁻
compared to prior studies of aqueous [Nb₆O₁₉]⁸⁻ reveals key
differences in behaviour, which is likely at the root of the difficultly
in developing polyoxotantalate chemistry. Specifically, where
contact ion-pairing dominates between [Nb₆O₁₉]⁸⁻ and its
counterions, solvent-separated ion-pairing between [Ta₆O₁₉]⁸⁻
and its counterions...
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and Nb polyoxometalates. Dalton Transactions,
43(41), 15295-15299. doi:10.1039/C4DT02394C
10.1039
Despite the considerable advances of deposition technologies, it remains a significant challenge to form conformal deposition on surface of nanoporous carbons. Here, we introduce a new ambient hydrolysis deposition method that employs and controls pre-adsorbed water vapor on nanoporous carbons to define the deposition of TiO₂. We converted the deposited...
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this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039
TAML activators promise a novel water treatment approach
by efficiently catalysing peroxide-based degradation of
chemicals of high concern at environmental concentrations.
Green design ethics demands an exploration of TAML
toxicity. Exposure to high concentrations of certain activators
caused adverse effects in zebrafish. At typical TAML
operational concentrations, development was not...
We, for the first time, employ magnesiothermic reaction to convert microwave-irradiated graphite oxide to pure graphene. The magnesiothermic reaction raises the carbon to oxygen atomic ratio from 22.2 to 165.7 and maintains a high surface area. The new strategy demonstrates an efficient method for obtaining highly pure graphene materials.
Environmental archives provide records of natural and anthropogenic variation in the environment at different temporal and spatial scales. Lead (Pb) concentrations and isotopic ratios are useful tracers of anthropogenic emissions from industrial activities including mining, smelting, and leaded gasoline use, however, methods of measuring Pb are largely limited in low...
Naturally occurring assemblies, such as DNA and proteins, utilize intermolecular forces (i.e H-bonding and van der Waals) to assemble. Utilizing these electrostatic interactions has only just started in the past five decades to be a tool used in synthetic chemistry in what is known as supramolecular chemistry. Supramolecular chemistry has...
The development of simple, rapid, and sensitive methods for thiophenol detection is of great importance in various fields, including environmental monitoring and food quality. Here, we present a novel approach for the colorimetric detection of thiophenols using gold nanoparticles (AuNPs) as the sensing platform. AuNPs aggregate in the presence of...
Restricted rotations of chemical bonds can lead to the presence of persistent conformational chirality in molecules 10 lacking stereocenters. We report the development of first-ofa- kind predictive rules that enable identification of conformational chirality and prediction of racemization barriers in the diarylether heptanoid (DAEH) natural products that do not possess...
We report the use of MIL-120 as a water-stable and cost-effective metal-organic framework (MOF) for selectively capturing CO₂ from wet flue gas. Synthesized using inexpensive and environmentally benign reagents in water, MIL-120 possesses one-dimensional pores decorated with hydroxyl-bridged Al(III) ions and benzene rings with an interstitial spacing of 4.78 Å....
Personal health monitoring tools, a subset of point-of care-diagnostics, enable more frequent testing of chronic health conditions outside of a clinic setting and can inform personalized therapy or support telehealth diagnostic capabilities. While there is evidence that regular monitoring of chronic conditions can lead to better health outcomes and lower...
Air-cathode fabrication is currently a key factor that hinders the scaling up of microbial fuel cell (MFC) technology. A new type of cathode material that contains porous polyethylene (PE) sheet and a blended activated carbon (AC) and highly conductive carbon back (CB) layer was developed for the first time. The...
Polyoxometalates (POMs) are anions consisting of three or more early transition metals ™ (Gr V and VI) oxoanions (in their highest oxidation state) linked together by a shared oxygen bond to form a 3D framework. Polyoxometalates (POMs) are a rapidly growing class of metal oxo clusters with a wide range...
In Intense Pulsed Light (IPL) sintering, pulsed large-area visible light from a xenon lamp is absorbed by nanoparticle films or patterns and converted to heat, resulting in rapid sintering of the nanoparticles. This work experimentally characterizes IPL sintering of silver nanoparticle films. A newly observed turning point in the evolution...
Previous studies have reported that the metastable vaterite phase of calcium carbonate can be stabilized in solution by acidic additives. Here we demonstrate that vaterite can also be stabilized directly at surfaces by engineered peptides. Our data show that the mineralisation occurs in a 'self-templating' process where calcium ions restructure...
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mineralisation. See DOI: 10.1039/c5cc05830a
‡ Current address: Max Planck Institute of Colloids and Interfaces
The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (similar to pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a...
The aggregation of 12 nm citrate-stabilized gold nanoparticles (cit-AuNPs) in the presence of four
different natural organic matter (NOM) isolates and a monovalent electrolyte (KCl) was evaluated using
time-resolved dynamic light scattering. All four NOM isolates stabilized the cit-AuNPs with respect to
aggregation. However, specific effects varied among the different...
A unique microreactor-assisted nanomaterial synthesis and printing process was studied for the fabrication of patterned metal oxide nanostructured thin films. The process uses a continuous flow microreactor to control and generate a reactive chemical flux that was transported to a patterned microfluidic channel. The microreactor-assisted nanomaterial synthesis process can generate...
Additive manufacturing has become a promising method for the fabrication of inexpensive, green, flexible sensors and electronics. Printed electronics on low- temperature substrates are very appealing for the flexible hybrid electronics market for their use in disposable and biocompatible electronic applications and in areas like packaging, wearables, and consumer electronics....
The metal organic framework, MOF-74(Ni), was synthesized in a continuous flow microwave-assisted reactor obtaining a high space-time yield (~90 g h⁻¹ L⁻¹) and 96.5% conversion of reagents. Separation of the nucleation and growth steps was performed by using uniform and rapid microwave heating to induce nucleation, which allowed a substantial...
The regiodivergent O- to C- or N-carboxyl transfer of pyrazolyl carbonates is described, with DMAP giving preferential N-carboxylation and triazolinylidenes promoting selective C-carboxylation (both with up to >99 : 1 regioselectivity). An enantioselective O- to C-carboxyl variant using NHC catalysis is demonstrated (up to 92% ee), while mechanistic and DFT studies outline...
The performance of an over 10 times larger microbial fuel cell (MFC) with double cloth electrode assembly (CEA) during 63 days of continuous operation demonstrates that the excellent performance of CEA-MFC can be further improved during scale-up. With a new separator material and U-shaped current collectors, the larger MFC produced...
Despite near unanimous opinion on the consequences of climate change by scientific community, the rate at which carbon is emitted into the atmosphere continues to increase. The need for a clean and sustainable source of energy is therefore one of humankind's most urgent challenges. Solar energy is the most abundant...
Aqueous, two-phase systems (ATPSs) may form upon mixing two solutions of independently water-soluble compounds. Many separation, purification, and extraction processes rely on ATPSs. Predicting the miscibility of solutions can accelerate and reduce the cost of the discovery of new ATPSs for these applications. Whereas previous machine learning approaches to ATPS...
In this work, metal-organic frameworks (MOFs) are computationally represented, generated, and evaluated. The organic linker molecules are represented as graphs and use graph grammars where the atoms are represented by nodes and the bonds are represented by arcs. The grammar rules that dictate the graph generation process work on the...
Magnetic materials can be used in modern soft robotics as a method for external stimulus actuation and motion control. By combining aspects of biology and mechanics, devices are fabricated to create a structure capable of complex movement. Applications that these devices are subject to can be broken down into four...
The ability of nanoparticles (NPs) to induce oxidative stress on organisms has been linked to NP cytotoxicity and genotoxicity for a variety of organisms. One proposed mechanism of this increased oxidative stress is the ability of NPs to generate reactive oxygen species (ROS). Due to the dynamic nature and small...
Nanoparticles (NPs) are generally defined as particles <100 nanometers (nm) in size in one dimension. Despite increasing industrial usage of TiO2 NPs in sunscreens, cosmetics, and water remediation little is known of their environmental behavior. The primary goal of this research was to develop a rapid method for determining the...
Polyoxometalates are a rapidly growing class of discrete metal oxide clusters with a wide range of applications including functional materials. These anionic clusters of the group V and VI transition metals are inexpensive and non-toxic. Within group V polyoxometalates, niobium and tantalum chemistry has been underdeveloped owing to their unique...
The rapid accumulation of plastic waste in landfill, waterways and oceans is becoming a critical problem, one that current recycling technologies are not capable of solving. Recent proposed approaches in the depolymerization of waste plastics employ an Olefin-Intermediate Process (OIP), where feedstocks like polyolefin plastics are ‘activated,’ producing an olefin...
Despite climate change requiring the cutback of fossil fuel consumption, the world continues to increase its energy demands each year. To meet the ambitious goals outlined during the Paris Agreement in 2015, which set a goal to limit global warming to 1.5°C [1], changes in energy production methods are necessary....
Metal-organic frameworks (MOFs) have emerged as promising candidates in novel cancer therapies due to their unique properties, including high surface area, tunable crystal size, and exposed metal ion active sites for catalysis. The MOF NH2-MIL-88B has shown potential use in cancer theranostics. Its open metal active sites catalyze the reduction...
Biohydrogen production via dark fermentation (DF) and microbial electrolysis cells (MEC) demonstrate great potential for sustainable hydrogen generation. In this study, DF and MEC were coupled as a hybrid reactor and evaluated using brewery wastewater. The effect of hydraulic retention time (HRT) and buffer concentration on reactor performance were assessed...
Microfluidics is an evolving field that focuses on the manipulation of small fluid volumes. Because of its micron-sized features, it is the basis for many lab-on-chip and point-of-care diagnostic devices. The devices are predominantly molded from polydimethylsiloxane (PDMS); however, production is a multi-hour or multi-day process that typically requires clean...