Inkjet-Printed Paper-Based Colorimetric Polyion Sensor Using a Smartphone as a Detector

The first paper-based polyion-sensitive optodes are reported. Dinonylnaphthalene sulfonic acid (a cation exchanger) and chromoionophore I (a lipophilic optical pH indicator) are printed on filter paper in the absence of any plasticizer and/or additional hydrophobic polymeric phase. The resulting optodes exhibit sensitive colorimetric response to polycations such as protamine but not to small inorganic cations because only polycations are able to form cooperative ion pairs with dinonylnaphthalenesulfonate adsorbed to the cellulose paper. The color change of the optode is recorded via an iPhone camera and analyzed by an iPhone App. The protamine-sensing optode platform is used to indirectly detect protease activity (trypsin) based on proteolytic digestion of protamine, and polyanions (pentosan polysulfate and heparin) based on the strong binding reaction of polyanions with protamine. The indirect sensing system is further simplified on a multilayer membrane device that consists of an optode paper site modified with buffer to prevent optode dependence on sample pH, and an underlying cellulose acetate filter membrane coated with protamine to eliminate addition of the indicator polycation into the sample. The detection of pentosan polysulfate concentrations in an undiluted urine sample is successfully demonstrated via this approach. Lastly, it is shown that plasticizer-free polyanion-sensitive optodes based on an adsorbed layer of quaternary ammonium type anion exchanger and a phenolic azo type proton chromoionophore can also be fabricated directly on cellulose paper strips

Label-Free and Substrate-Free Potentiometric Aptasensing Using Polycation-Sensitive Membrane Electrodes

A potentiometric label-free and substrate-free (LFSF) aptasensing strategy which eliminates the labeling, separation, and immobilization steps is described in this paper. An aptamer binds specifically to a target molecule via reaction incubation, which could induce a change in the aptamer conformation from a random coil-like configuration to a rigid folded structure. Such a target binding-induced aptamer conformational change effectively prevents the aptamer from electrostatically interacting with the protamine binding domain. This could either shift the response curve for the potentiometric titration of the aptamer with protamine as monitored by a conventional polycation-sensitive membrane electrode or change the current-dependent potential detected by a protamine-conditioned polycation-sensitive electrode with the pulsed current-driven ion fluxes of protamine across the polymeric membrane. Using adenosine triphosphate (ATP) as a model analyte, the proposed concept offers potentiometric detection of ATP down to the submicromolar concentration range and has been applied to the determination of ATP in HeLa cells. In contrast to the current LFSF aptasensors based on optical detection, the proposed strategy allows the LFSF biosensing of aptamer/target binding events in a homogeneous solution via electrochemical transduction. It is anticipated that the proposed strategy will lay a foundation for development of potentiometric sensors for LFSF aptasensing of a variety of analytes where target binding-induced conformational changes such as the formation of folded structures and the opening of DNA hairpin loops are involved

Polymeric Membrane Neutral Phenol-Sensitive Electrodes for Potentiometric G‑Quadruplex/Hemin DNAzyme-Based Biosensing

The first potentiometric transducer for G-quadruplex/hemin DNAzyme-based biosensing has been developed by using potential responses of electrically neutral oligomeric phenols on polymeric membrane electrodes. In the presence of G-quadruplex/hemin DNAzyme and H₂O₂, monomeric phenols (e.g., phenol, methylphenols, and methoxyphenols) can be condensed into oligomeric phenols. Because both substrates and products are nonionic under optimal pH conditions, these reactions are traditionally not considered in designing potentiometric biosensing schemes. However, in this paper, the electrically neutral oligomeric phenols have been found to induce highly sensitive potential responses on quaternary ammonium salt-doped polymeric membrane electrodes owing to their high lipophilicities. In contrast, the potential responses to monomeric phenolic substrates are rather low. Thus, the G-quadruplex/hemin DNAzyme-catalyzed oxidative coupling of monomeric phenols can induce large potential signals, and the catalytic activities of DNAzymes can be probed. A comparison of potential responses induced by peroxidations of 13 monomeric phenols indicates that <i>p</i>-methoxyphenol is the most efficient substrate for potentiometric detection of G-quadruplex/hemin DNAzymes. Finally, two label-free and separation-free potentiometric DNA assay protocols based on the G-quadruplex/hemin DNAzyme have been developed with sensitivities higher than those of colorimetric and fluorometric methods. Coupled with other features such as reliable instrumentation, low cost, ease of miniaturization, and resistance to color and turbid interferences, the proposed polymeric membrane-based potentiometric sensor promises to be a competitive transducer for peroxidase-mimicking DNAzyme-involved biosensing

Mobilization of Cadmium and Arsenic During Anoxic-Oxic Alteration in Paddy Soils: A Vital Role of Manganese

Flooding and drainage of paddy fields can induce the activation of soil cadmium (Cd)/arsenic (As), which will accumulate in rice grains and threaten human health. Mn oxides influence soil Cd and As availability, but few detailed studies have been reported on how Mn redox simultaneously affects Cd and As mobility during flooding and drainage. Two paddy soils with various Mn contents were incubated under three redox conditions, namely 30-d reduction, 30-d oxidation and 20-d reduction subsequent with 10-d oxidation, to investigate Cd and As migration. During reduction, the soil abundant in native Mn oxides possessed more high-valence Mn oxides, which promoted As oxidation and retarded the reductive dissolution of Fe (oxyhydro)oxides, thereby decreasing As mobility. Cd mobility mainly depended on the conversion between Fe-Mn oxides-bound Cd and exchangeable Cd. The high Mn content was conducive to decreasing Cd mobilization. Furthermore, the oxidation of As in soils was linked with a Fenton-like effect. The generated hydroxyl radicals (•OH) decreased with oxidation and the oxidation of Mn(II) by •OH inhibited As migration but promoted Cd activation. In summary, the mobility of Cd and As was lower in Mn rich soils, which may involve the immobilization, oxidation and catalytic effects of Mn oxides. Cd mobility mainly relied on the conversion between Fe-Mn oxides-bound Cd and exchangeable Cd.The redox dependence of Mn played a key role in controlling Cd and As migration in paddy soils.Soils containing higher content of Mn oxides possessed lower mobility of Cd and As.The oxidative effect of •OH on Mn(II) inhibited As mobility but promoted Cd activation. Cd mobility mainly relied on the conversion between Fe-Mn oxides-bound Cd and exchangeable Cd. The redox dependence of Mn played a key role in controlling Cd and As migration in paddy soils. Soils containing higher content of Mn oxides possessed lower mobility of Cd and As. The oxidative effect of •OH on Mn(II) inhibited As mobility but promoted Cd activation.</p

A Smart, Photocontrollable Drug Release Nanosystem for Multifunctional Synergistic Cancer Therapy

Multifunctional synergistic therapy holds promise in biomedical studies and clinical practice. However, strategies aimed at easily integrating the components of such multimodal therapies are needed. Therefore, we herein report a smart drug release nanosystem able to perform photodynamic therapy, photothermal therapy and chemotherapy in a photocontrollable manner. Doxorubicin (DOX), a chemotherapy drug, and 5, 10, 15, 20-tetrakis (1-methylpyridinium-4-yl) porphyrin (TMPyP4), a photosensitizer, were physically intercalated into a DNA assembly immobilized on gold nanorods. The drugs were efficiently delivered to target cells and released under light irradiation, resulting in a synergism that combined phototherapy and chemotherapy for cancer treatment. This smart, photocontrollable drug release nanosystem promises precisely controlled drug release for multifunctional synergistic cancer therapy

Data_Sheet_1_Mapping cover crop species in southeastern Michigan using Sentinel-2 satellite data and Google Earth Engine.docx

Cover crops are a critical agricultural practice that can improve soil quality, enhance crop yields, and reduce nitrogen and phosphorus losses from farms. Yet there is limited understanding of the extent to which cover crops have been adopted across large spatial and temporal scales. Remote sensing offers a low-cost way to monitor cover crop adoption at the field scale and at large spatio-temporal scales. To date, most studies using satellite data have mapped the presence of cover crops, but have not identified specific cover crop species, which is important because cover crops of different plant functional types (e.g., legumes, grasses) perform different ecosystem functions. Here we use Sentinel-2 satellite data and a random forest classifier to map the cover crop species cereal rye and red clover, which represent grass and legume functional types, in the River Raisin watershed in southeastern Michigan. Our maps of agricultural landcover across this region, including the two cover crop species, had moderate to high accuracies, with an overall accuracy of 83%. Red clover and cereal rye achieved F1 scores that ranged from 0.7 to 0.77, and user's and producer's accuracies that ranged from 63.3% to 86.2%. The most common misclassification of cover crops was fallow fields with remaining crop stubble, which often looked similar because these cover crop species are typically planted within existing crop stubble, or interseeded into a grain crop. We found that red-edge bands and images from the end of April and early July were the most important for classification accuracy. Our results demonstrate the potential to map individual cover crop species using Sentinel-2 imagery, which is critical for understanding the environmental outcomes of increasing crop diversity on farms.</p

A Polymeric Liquid Membrane Electrode Responsive to 3,3′,5,5′-Tetramethylbenzidine Oxidation for Sensitive Peroxidase/Peroxidase Mimetic-Based Potentiometric Biosensing

The oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) has great utility in bioanalysis such as peroxidase/peroxidase mimetic-based biosensing. In this paper, the behaviors of TMB oxidation intermediates/products in liquid/liquid biphasic systems have been investigated for the first time. The free radical, charge transfer complex, and diimine species generated by TMB oxidation are all positively charged under acidic and near-neutral conditions. Electron paramagnetic resonance and visible absorbance spectroscopy data demonstrate that these cationic species can be effectively transferred from an aqueous phase into a water-immiscible liquid phase functionalized by an appropriate cation exchanger. Accordingly, sensitive potential responses of TMB oxidation have been obtained on a cation exchanger-doped polymeric liquid membrane electrode under mildly acidic and near-neutral conditions. By using the membrane electrode responsive to TMB oxidations, two sensitive potentiometric biosensing schemes including the peroxidase-labeled sandwich immunoassay and G-quadruplex DNAzyme-based DNA hybridization assay have been developed. The obtained detection limits for the target antigen and DNA are 0.02 ng/mL and 0.1 nM, respectively. Coupled with other advantages such as low cost, high reliability, and ease of miniaturization and integration, the proposed polymeric liquid membrane electrode holds great promise as a facile and efficient transducer for TMB oxidation and related biosensing applications

Synthesis of Structurally Defined Cationic Polythiophenes for DNA Binding and Gene Delivery

Water-soluble conjugated polymers (<b>WCP</b>s) have prospective applications in the field of bioimaging, disease diagnosis, and therapy. However, the use of <b>WCP</b>s with controllability and regioregularity for bioapplications have scarcely been reported. In this work, we synthesized polythiophenes containing ester side chains (<b>P3ET</b>) via Kumada catalyst-transfer polycondensation (KCTP) and confirmed a quasi-“living” chain-growth mechanism. In addition, we obtained cationic regioregular polythiophenes (<b>cPT</b>s) by aminolysis of <b>P3ET</b> with varied chain lengths, and studied DNA binding capability and gene delivery performance. Benefiting from photocontrolled generation of intracellular reactive oxygen species (ROS), the cationic polythiophenes successfully delivered DNA into tumor cells without additional polymer species

Protein Nanocage-Based Photo-Controlled Nitric Oxide Releasing Platform

A photoactive NO releasing system was constructed by incorporation of NO-bound Fe–S clusters into horse spleen apoferritin cavities with high loading efficacy. The composites retained intact core–shell structure and indicated advantages such as enhanced stability, reduced cytotoxicity, efficient cellular uptake, and photocontrolled NO releasing property

Overexpression of the Global Regulator LaeA in <i>Chaetomium globosum</i> Leads to the Biosynthesis of Chaetoglobosin Z

Overexpression of laeA in <i>Chaetomium globosum</i> CBS148.51 up-regulated expression of the chaetoglobosin gene cluster and resulted in the isolation of a new cytochalasan, chaetoglobosin Z (<b>1</b>), together with six known analogues, chaetoglobosins A (<b>2</b>), B (<b>3</b>), D (<b>4</b>), E (<b>5</b>), O (<b>6</b>), and V (<b>7</b>). RT-PCR analysis confirmed that the key genes in the chaetoglobosin gene cluster were significantly up-regulated. The structure of the new compound chaetoglobosin Z (<b>1</b>) was elucidated using NMR data. The relative and absolute configurations were determined by NOESY and electronic circular dichroism combined with quantum-chemical calculations adopting time-dependent density functional theory methods, respectively. These compounds displayed strong biological effects against the HepG 2 cell line compared with the positive control. The results further supported that LaeA is a global regulator that could up-regulate and/or activate cryptic gene clusters to produce new secondary metabolites