Active Probe Research Articles

A new fluorescent probe for sensing Al3+ ions in the solution phase and CH3COO- in the solid state with aggregation induced emission (AIE) activity.

An AIE (aggregation induced emission) active probe DFP-AMQ was designed and synthesized as a hexa-coordinated N2O donor chelator for the selective sensing of Al3+ colorimetrically as well as fluorimetrically with a 27-fold fluorescence enhancement for CH3CN-H2O (9 : 1, v/v, pH 7.2, HEPES buffer). The fluorescence enhancement occurred through the blocking of ESIPT, chelation enhanced fluorescence effect (CHEF) arose, and as a result fluorescence enhancement was observed through 1 : 1 complexation with Al3+ ions. Detailed spectroscopic studies including UV-Vis, FTIR, 1H NMR, and HRMS studies were carried out to characterize the probable structure of DFP-AMQ including the complexation of DFP-AMQ with Al3+ ions. The spectrophotometric and spectrofluorimetric titrations revealed strong binding towards Al3+ and the K d values were obtained from UV-Vis (3.26 × 10-5 M-1) and fluorescence titration (2.02 × 10-5 M-1). The limit of detection of Al3+ by DFP-AMQ was 1.11 μM. The quantum yields of DFP-AMQ and [DFP-AMQ-Al]+ were calculated to be 0.008 and 0.211, respectively. Dynamic light scattering (DLS) studies showed that the sizes of the particles increased with increasing water percentage due to aggregation. SEM (scanning electron microscopy) studies revealed interesting morphological changes in microstructures in which DFP-AMQ demonstrated a rod-like shape, which was converted to a spherical-like shape in the presence of Al3+ and when DFP-AMQ aggregated in H2O it showed aggregated block-like shape. In the solid phase, DFP-AMQ with nitrate has no particular shape, but in the presence of acetate, it converts to stone-like shape. This probe (DFP-AMQ) could be employed for on-site Al3+ ion detection in the solid state.

Interrogating the nature of aggregates formed in a model azine based ESIPT coupled AIE active probe: stark differences in photodynamics in the solid state and aggregates in water.

A novel Schiff base 4-bromo-2-((E)-((E)-(1-(naphthalen-2-yl)ethylidene)hydrazono)methyl)phenol (BNHMP) was synthesized and characterized by NMR, ESI-MS, FTIR and single crystal X-ray diffraction studies. In the solution phase, BNHMP shows prominent emission from the keto-form, a consequence of excited state intramolecular proton transfer (ESIPT). The quantum yield and excited state lifetime decrease in polar solvent THF compared to relatively non-polar solvent DCM. Interestingly, in aqueous solution (pH 7.0), the quantum yield along with the excited state lifetime undergoes tremendous increment. Dynamic light scattering experiments and FESEM reveal the formation of aggregates in water as reflected by the increased hydrodynamic radius of BNHMP in water. Hence, aqueous phase studies revealed BNHMP to be an AIE active probe. On the other hand, BNHMP shows huge emission intensity in the solid state. Interestingly, the emission decay behavior of BNHMP changes upon excitation, as BNHMP shows very broad absorption in the solid state. Upon excitation at 360 nm, a triexponential decay pattern is found, which changes to a biexponential one upon excitation at 450 nm. Meticulous analysis of the fluorescence lifetimes led to the assignment of J and H aggregates coexisting in the solid state with the former dominating the photodynamics. A judicious comparison of the lifetime behavior in the solid state to that in water leads to the conclusion that BNHMP undergoes AIE by the formation of J and H aggregates to an equal extent, a phenomenon starkly different from the solid-state scenario. The current results hold significance as this is among a few reports where such comprehensive spectrodynamic dissection has been performed for an ESIPT-AIE active Schiff base in solution as well as in the solid phase, thereby giving a holistic vision of the nature and fate of aggregation occurring in such azine based systems and subsequently advancing the understanding of such systems in terms of their photo behavior.

Optogenetic stimulation reveals a latent tipping point in cortical networks during ictogenesis.

Brain-state transitions are readily apparent from changes in brain rhythms,1 but are difficult to predict, suggestive that the underlying cause is latent to passive recording methods. Among the most important transitions, clinically, are the starts of seizures. We here show that an 'active probing' approach may have several important benefits for epileptic management, including by helping predict these transitions. We used mice expressing the optogenetic actuator, channelrhodopsin, in pyramidal cells, allowing this population to be stimulated in isolation. Intermittent stimulation at frequencies as low as 0.033 Hz (period = 30 s) delayed the onset of seizure-like events in an acute brain slice model of ictogenesis, but the effect was lost if stimulation was delivered at even lower frequencies (1/min). Notably, active probing additionally provides advance indication of when seizure-like activity is imminent, revealed by monitoring the postsynaptic response to stimulation. The postsynaptic response, recorded extracellularly, showed an all-or-nothing change in both amplitude and duration, a few hundred seconds before seizure-like activity began-a sufficient length of time to provide a helpful warning of an impending seizure. The change in the postsynaptic response then persisted for the remainder of the recording, indicative of a state change from a pre-epileptic to a pro-epileptic network. This occurred in parallel with a large increase in the stimulation-triggered Ca2+ entry into pyramidal dendrites, and a step increase in the number of evoked postsynaptic action potentials, both consistent with a reduction in the threshold for dendritic action potentials. In 0 Mg2+ bathing media, the reduced threshold was not associated with changes in glutamatergic synaptic function, nor of GABAergic release from either parvalbumin or somatostatin interneurons, but simulations indicate that the step change in the optogenetic response can instead arise from incremental increases in intracellular [Cl-]. The change in the response to stimulation was replicated by artificially raising intracellular [Cl-], using the optogenetic chloride pump, halorhodopsin. By contrast, increases in extracellular [K+] cannot account for the firing patterns in the response to stimulation, although this, and other cellular changes, may contribute to ictal initiation in other circumstances. We describe how these various cellular changes form a synergistic network of positive feedback mechanisms, which may explain the precipitous nature of seizure onset. This model of seizure initiation draws together several major lines of epilepsy research as well as providing an important proof-of-principle regarding the utility of open-loop brain stimulation for clinical management of the condition.

AIEE active J-aggregates of naphthalimide based fluorescent probe for detection of Nitrobenzene: Combined experimental and theoretical approaches for Non-covalent interaction analysis

A new naphthalimide-based fluorescent probe NS with exceptional J-aggregates based aggregation-induced emission enhancement (AIEE) properties was rationally synthesized through a single-step imidation reaction. Probe NS exhibited excellent AIEE properties in aqueous media through the formation of J-aggregates with remarkable red-shift. The AIEE active probe NS was used for selective and sensitive detection of nitrobenzene (NB) based on fluorescence quenching response. Formation of J-aggregates was assessed through fluorescence titration. These J-aggregates contributed significantly to produce favorable interaction between probe NS and NB. The highly selective fluorescence detection of NB was accredited to the adjustable smaller size of NB that can easily penetrate into interstitial spaces of probe molecules. Ability of sensor to detect NB in solid state was also accomplished through solid state fluorescence spectroscopy. Nature of interaction and sensitivity of probe NS for NB has also been investigated through 1H NMR titration and density functional theory (DFT) including non-covalent interaction (NCI), quantum theory of atom in molecule (QTAIM), electron density differences (EDD), frontier molecular orbitals (FMO) and density of states (DOS) analysis. Advantageously, probe exhibited colorimetric and vapor phase detection of NB. Moreover, probe was quite sensitive for the trace detection of NB in real samples.

De Novo Design of a Highly Selective Nonpeptide Fluorogenic Probe for Chymotrypsin Activity Sensing in a Living System.

Chymotrypsin, an extensively known proteolytic enzyme, plays a substantial role in maintaining physiological functions, including protein digestion, immune response, and tissue repair. To date, intense attention has been focused on the invention of efficient and sensitive chemical tools for chymotrypsin activity measurement. Among them, the "nonpeptide"-based chymotrypsin probe design strategy utilizing the esterase activity of chymotrypsin has been well-developed due to its low cost and high atom-economy feature. However, the ester-bond-based nature of these probes make them possibly vulnerable to esterases and active chemicals. These defects strictly restricted the application of the previously reported probes, especially for imaging in living systems. Therefore, to acquire fluorogenic probes with sufficient stability and specificity for chymotrypsin sensing in a complicated biological environment, a more stable skeleton for nonpeptide-based chymotrypsin probe construction is urgently needed. Herein, a novel nonpeptide-based fluorogenic probe for specific chymotrypsin activity sensing was designed and synthesized by the substitution of an ester-based linker with a heptafluorobutylamide moiety. The acquired probe, named TMBIHF, showed high selectivity toward various enzymes and reactive chemicals, while it retained high sensitivity and catalytic efficiency toward chymotrypsin. Moreover, TMBIHF was successfully applied for monitoring chymotrypsin activity and pancreas development in live zebrafish, specific sensing of exogenous and endogenous chymotrypsin in nude mice, and visualizing chymotrypsin-like activity-dependent cellular apoptosis, thus providing an alternative and reliable way for chymotrypsin-targeted biosensor or prodrug construction.

Dualistic Fluorescence as Well as Portable Smartphone-Assisted RGB-Relied Sensing Assay for the Ultra-Sensitive Determination of Pendimethalin in Food and Water Samples by AIEE Active Organic Probes.

Herein, a peculiar fluorometric as well as smartphone-assisted RGB-relied sensing assay is introduced for determining pendimethalin (PDM) herbicide contents (in parts per trillion level) based on the anthracene-incorporated pyrimidinone/thione probes (S1 to S4). These compounds offered a unique and impressive aggregation-induced emission enhancement (AIEE) behavior by aggregation in H2O-dimethylformamide medium. Furthermore, these AIEE active compounds were found to display superior selectivity and extraordinary sensitivity for PDM detection via fluorescence quenching response. The extent of quenching degree was found to be linearly varied with the PDM concentration ranging from 0 to 20 nM, with a lower limit of detection of 367.8 pM (103.4 ppt) by S3 nanoaggregates. The detailed investigation revealed that such a high sensitivity of the designed sensor toward PDM is attributable to the existence of dual "photoinduced charge transfer and Förster resonance energy transfer process mechanisms". The Stern-Volmer plots, Job's plot, Benesi-Hildebrand plot, and 1H NMR titrations as well indicated the existence of substantial interactions between the sensor and PDM. The conducted selectivity tests provided distinguishable selectivity for PDM detection over various other insecticides/pesticides as well as other structural nitro analogues. Additionally, the presented sensing assay was also applied to quantify the PDM residues in spiked food (vegetables, fruits, and grains) and water samples. In addition, the sensor-coated fluorescent paper test strips were also fabricated for on-site detection of PDM. The applicability of smartphone-relied RGB analysis significantly streamlined the operation process, speeds up the detection procedure, and also offered a novel methodology for real-time analysis of PDM in real samples.

Length-Controllable Gold-Coated Silver Nanowire Probes for High AFM-TERS Scattering Activity.

Tip-enhanced Raman scattering (TERS) microscopy is an advanced technique for investigation at the nanoscale that provides topographic and chemical information simultaneously. The TERS probe plays a crucial role in the microscopic performance. In the recent past, the development of silver nanowire (AgNW) based TERS probes solved the main tip fabrication issues, such as low mechanical strength and reproducibility. However, this fabrication method still suffers from low control of the protruded length of the AgNW. In this work, a simple water-air interface electrocutting method is proposed to achieve wide controllability of the length. This water cutting method was combined with a succedent Au coating on the AgNW surface, and the probe achieved an up to 100× higher enhancement factor (EF) and a 2× smaller spatial resolution compared to pristine AgNW. Thanks to this excellent EF, the water-cut Au-coated AgNW probes were found to possess high TERS activity even in the nongap mode, enabling broad applications.

Flame detection via active plasma probing

Combustion diagnostics of highly diluted air fuel mixtures are of great importance for reducing the carbon footprint of various types of combustion systems. Flame detection techniques, such as ion sensing and optical diagnostics, have been reported for diagnosing combustion status. In this paper, a flame front detection technique based on active plasma probing is introduced and analyzed. Unlike the conventional ion sensing used in internal combustion engines, a separate electrode gap is used to detect the flame front arrival. Further, the voltage potential across the electrodes of the spark plug probe is modulated actively to be slightly below the breakdown threshold prior to flame arrival. At the arrival of the flame front, the ions in the flame tend to decrease the breakdown voltage threshold and trigger a breakdown event. An optically accessible constant volume combustion vessel is employed to investigate the efficacy of such active plasma probing for the detection of the flame front under quiescent and flow conditions. Three types of fuels are used in the tests, including methane, propane, and DME, with an air fuel ratio sweep (from stoichiometric to extremely lean) for each fuel. Efforts are made to characterize the probing criteria of minimum, yet adequate voltage to succeed in the detection of the arrival and departure of the flame front most sensitively and reliably, for all three types of fuels under various mixture strengths. For comparison, conventional ion current measurements are conducted under identical background conditions to benchmark the efficacy of flame detection. Results show that the active plasma probing can promptly detect the arrival and departure of the flame front, robustly regardless of the fuel type and excess air ratios. The precise control of the detecting voltage is key for reliable flame detection with high sensitivity.

Optical recognition of constructs using hyperspectral imaging and detection (ORCHID)

Challenges to deep sample imaging have necessitated the development of special techniques such as spatially offset optical spectroscopy to collect signals that have travelled through several layers of tissue. However, these techniques provide only spectral information in one dimension (i.e., depth). Here, we describe a general and practical method, referred to as Optical Recognition of Constructs Using Hyperspectral Imaging and Detection (ORCHID). The sensing strategy integrates (1) the spatial offset detection concept by computationally binning 2D optical data associated with digital offsets based on selected radial pixel distances from the excitation source; (2) hyperspectral imaging using tunable filter; and (3) digital image binding and collation. ORCHID is a versatile modality that is designed to collect optical signals deep inside samples across three spatial (X, Y, Z) as well as spectral dimensions. The ORCHID method is applicable to various optical techniques that exhibit narrow-band structures, from Raman scattering to quantum dot luminescence. Samples containing surface-enhanced Raman scattering (SERS)-active gold nanostar probes and quantum dots embedded in gel were used to show a proof of principle for the ORCHID concept. The resulting hyperspectral data cube is shown to spatially locate target emitting nanoparticle volumes and provide spectral information for in-depth 3D imaging.

Eye-Tracking Active Indicators of Insider Threats: Detecting Illicit Activity During Normal Workflow

Cyber challenges faced by organizations today involve malicious inside actors, often labeled insider threats (ITs). These present a difficult challenge in that the most well-designed cybersecurity apparatus is vulnerable to those inside the organization who have privileged access to information systems. Innovative methods must be developed to help security analysts narrow the large pool of potential ITs in large organizations to a more manageable number. The purpose of this article is to develop and validate eye-tracking metrics that are diagnostic of IT behavior. Key stimuli, or called active indicator probes, were embedded into a simulated workflow to elicit diagnostic eye-tracking responses. Two environments were simulated: financial and intelligence analysis. We evaluated participants performing as regular workers relative to ITs to identify metrics that distinguished between the two groups. Detection of illicit eye gaze behavior while using chat programs was possible when conversations with accomplices occurred in a separate chat window from normal permissible chat conversations. Validation of results in real work environments is necessary for practical application. However, if the approach proves to translate successfully, automated monitoring of eye-tracking responses may augment existing insider detection methods, within frameworks for best practices in organizational security and cyber defense.

Meet: Rack-Level Pooling Based Load Balancing in Datacenter Networks

Datacenter networks enable multiple paths between hosts to provide large bisection bandwidth. It requires load balancers to cope with network uncertainties such as traffic dynamics and topology asymmetry. Existing edge-based load balancing schemes are usually faced with the problem of limited network visibility. This article proposes <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">Meet</small> , a rack-level pooling based load-balancer deployed at the edge that can handle the aformentioned uncertainties. <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">Meet</small> utilizes both passive information as well as active probing to comprehensively sense the network conditions with relatively low cost. <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">Meet</small> dynamically reroutes flows effectively based on the visibility of the network condition. <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">Meet</small> has been tested with extensive flow-level simulations against state-of-the-art load balancers. It outperforms Hermes by up to 10% in the experiments, and outperforms others solutions such as DRILL by up to 50%. <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">Meet</small> requires no modifications to the switches and is feasible to deploy at the edge.

Nucleobase-modified nucleosides and nucleotides: Applications in biochemistry, synthetic biology, and drug discovery.

. DNA is often referred to as the "molecule of life" since it contains the genetic blueprint for all forms of life on this planet. The core building blocks composing DNA are deoxynucleotides. While the deoxyribose sugar and phosphate group are ubiquitous, it is the composition and spatial arrangement of the four natural nucleobases, adenine (A), cytosine (C), guanine (G), and thymine (T), that provide diversity in the coding information present in DNA. The ability of DNA to function as the genetic blueprint has historically been attributed to the formation of proper hydrogen bonding interactions made between complementary nucleobases. However, recent chemical and biochemical studies using nucleobase-modified nucleotides that contain "non-hydrogen bonding" functional groups have challenged many of the dogmatic views for the necessity of hydrogen-bonding interactions for DNA stability and function. Based on years of exciting research, this area has expanded tremendously and is thus too expansive to provide a comprehensive review on the topic. As such, this review article provides an opinion highlighting how nucleobase-modified nucleotides are being applied in diverse biomedical fields, focusing on three exciting areas of research. The first section addresses how these analogs are used as mechanistic probes for DNA polymerase activity and fidelity during replication. This section outlines the synthetic logic and medicinal chemistry approaches used to replace hydrogen-bonding functional groups to examine the contributions of shape/size, nucleobase hydrophobicity, and pi-electron interactions. The second section extends these mechanistic studies to provide insight into how nucleobase-modified nucleosides are used in synthetic biology. One example is through expansion of the genetic code in which changing the composition of DNA makes it possible to site-specifically incorporate unnatural amino acids bearing unique functional groups into enzymes and receptors. The final section describes results of pre-clinical studies using nucleobase-modified nucleosides as potential therapeutic agents against diseases such as cancer.

Noninvasive measurement of subcutaneous temperature using active antenna and high gain low noise microwave radiometer

ABSTRACT This paper presents a radiometric thermometer for non-invasive measurement of the internal body temperature. The proposed radiometric thermometer designed in 1.575 GHz band consists of a near-field probe and a high gain Dick radiometer. A phantom based on Agar material was developed to emulate the real tissue of skin and muscle for experiments. The measured results show that the active probe antenna provides additional 12.5 dB gain with noise figure less than 1dB, and the radiometer has a system gain of 50 dB and total noise figure of 1.738 dB at 1.575 GHz. The output voltage measured by the proposed 1.575 GHz microwave radiometer is 2.994 V when the water temperature is set to 25 °C, while it is 3.129 V when the water temperature is set to 80 °C. The study demonstrates that using the active probe connected to the radiometer can identify temperature difference of the body.

Self-propelled Janus nanomotor as active probe for detection of pepsinogen by lateral flow immunoassay.

Thefeasibility of using nanomotors as active probes for lateral flow immunoassay (LFIA)is demonstrated. We synthesized Au@mSiO2@Pt Janus nanomotor, where nanolayer of Pt was deposited on the half side surface of the Au@mSiO2 nanoparticles, which can catalyze the decomposition of H2O2 to produce driving force for the nanomotor. Subsequently, the motion characteristics of the Au@mSiO2@Pt nanomotor in static fluidic environment and dynamic flow field was studied to pave the way for its practical application in lateral flow immunoassay (LFIA). At last, the Au@mSiO2@Pt nanomotor was modified with antibody and thenused as active immunoassay probe in LFIA. We chose gastric function index, pepsinogen II (PG II) and pepsinogen II (PG II), as the target analytes. The results indicated that, compared with traditional Au nanoprobe, the nanomotor-based probe can significantly improve the sensitivity by increasing the probability and efficiency of antigen and antibody binding. Alimit of detection (LOD) of 2.2ng/mL for PGI, and 2.1ng/mL for PG II was achieved. This work provides a new solution for enhancing the capability of immune detection, and we believe the nanomotor-based LFIA will have great potential in high-sensitivity point-of-care-testing in the future.

Fluorescent Determination of Esterase in Living Cells by A Low-Dosage, Ultra-Sensitive Probe Based on Aggregation Induced Emission (AIE)

Esterase is an essential hydrolase in organisms. Many severe diseases are caused by its abnormal expression. Sensitive probes for the esterase activity need to be developed. However, the currently reported fluorescence probes for esterase have drawbacks, such as long response times, low sensitivity, and high dosages. In this work, three fluorophores with the cyano group were designed and synthesized. The optical properties of these fluorophores were measured. A turn-on fluorescence detector for the determination of esterase with a fast response speed and high sensitivity at low doses was developed that was based upon aggregation-induced emission (AIE). The mechanism was studied by high-resolution mass spectrometry (HRMS), dynamic light scattering (DLS), and high-performance liquid chromatography (HPLC). In addition, the probe had excellent stability and biocompatibility and specifically recognized esterase with a short response time (less than 5 min) and ultra-high sensitivity. The detection limit was 1.03 × 10−4 U/mL, with a linear range from 1.03 × 10−4 to 0.05 U/mL. Furthermore, the probe had low cytotoxicity, and cellular imaging of exogenous esterase was achieved. This probe is anticipated to offer many applications in biomedical science.

Comparison of Different Competitive Proteome Profiling Approaches in Target Identification of Covalent Inhibitors.

Competitive proteome profiling is a powerful approach for the identification of targets of small molecules. This approach usually employs an inhibitor-derived probe or a cysteine-reactive probe such as an IA-alkyne in a comparison between inhibitor-treated and untreated samples, thus enabling distinction between genuine targets and nonspecific labeling. We have developed an active probe derived from an EGFR inhibitor, afatinib, and a cysteine reactive probe, an alkyne-containing α,β-unsaturated amide, to compare their characterization of cellular targets. In both approaches, myosin heavy chain 9 (MYH9) was identified as an off-target. Subsequent functional validation experiments suggested that MYH9 might be involved in the function of afatinib.

A novel aggregation-induced emission fluorescent probe with large Stokes shift for sensitive detection of pH changes in live cells.

The detection of intracellular pH is crucial for elucidating the pathological process of cancers, as well as for medical diagnostic applications. Here, we developed an aggregation-induced emission active pH-responsive fluorescent probe (TPE-DCP) for sensitively detecting cell pH changes. The probe shows obvious pH-sensing properties at ~615 nm, with a pKa value of 6.82 and a good linear pH response ranging from 8.5 to 4.5. TPE-DCP holds advantages such as excellent anti-interference performance, good photostability, and low cytotoxicity, and has been successfully used to image intracellular pH changes in cells.

NIMG-68. IMAGING PHOSPHOLIPID BIOSYNTHESIS ENABLES NON-INVASIVE ASSESSMENT OF BRAIN TUMOR RESPONSE TO THERAPY

Abstract Elevated phospholipid biosynthesis is a metabolic hallmark of cancer. Due to the high membrane turnover associated with uncontrolled proliferation, tumor cells invariably upregulate phospholipid biosynthesis. Choline is a dietary nutrient that is phosphorylated to phosphocholine (PC) and subsequently incorporated into phosphatidylcholine, which is the primary membrane phospholipid in mammalian cells. Choline kinase α (CKα) is the key enzyme in this pathway and its expression is elevated in most cancers. Identifying non-invasive methods of imaging CKα activity, can, therefore, enable assessment of tumor burden and response to therapy. Deuterium magnetic resonance spectroscopy (DMRS) following administration of 2H-labeled substrates recently emerged as a simple, robust, clinically translatable method of assessing metabolic activity in vivo. The goals of the current study were to determine whether DMRS-based assessment of PC production from [2H9]-choline tracks CKα activity and to establish the utility of [2H9]-choline for glioma imaging in vivo. First, we show that [2H9]-choline metabolism to PC can be observed in live patient-derived glioma cells (GBM6 and BT88). Silencing CKα abrogates PC production from [2H9]-choline in both GBM6 and BT88 models, thereby confirming that [2H9]-choline provides a readout of CKα activity. Next, we examined the ability of [2H9]-choline to monitor tumor burden and response to therapy in vivo. [2H9]-choline metabolism to PC can be observed in mice bearing orthotopic patient-derived GBM6 or BT257 tumors, but not in tumor-free healthy controls. Importantly, following treatment of mice bearing orthotopic BT257 tumors with temozolomide, which is standard of care for glioma patients, PC production from [2H9]-choline is reduced at early timepoints when changes in tumor volume cannot be detected by anatomical imaging. Taken together, our studies, for the first time, identify [2H9]-choline as a probe of CKα activity and highlight its ability to assess tumor burden and early response to therapy, which is a challenge in glioma imaging.

A Comparative Study of PMETAC-Modified Mesoporous Silica and Titania Thin Films for Molecular Transport Manipulation.

The manipulation and understanding of molecular transport across functionalized nanopores will take us closer to mimicking biological membranes and thus to design high-performance permselective separation systems. In this work, Surface-initiated atom transfer radical polymerization (SI-ATRP) of (2-methacryloyloxy)-ethyltrimethylammonium chloride (METAC) was performed on both mesoporous silica and mesoporous titania thin films. Pores were proven to be filled using ellipsometry and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Furthermore, the employed method leads to a polymer overlayer, whose thickness could be discriminated using a double-layer ellipsometry model. Cyclic voltammetry experiments reveal that the transport of electrochemically active probes is affected by the PMETAC presence, both due to the polymer overlayer and the confined charge of the pore-tethered PMETAC. A more detailed study demonstrates that ion permeability depends on the combined role of the inorganic scaffolds' (titania and silica) surface chemistry and the steric and charge exclusion properties of the polyelectrolyte. Interestingly, highly charged negative walls with positively charged polymers may resemble zwitterionic polymer behavior in confined environments.

Fluorogenic detection of mercury ion in aqueous environment using hydrogel‐based AIE sensing films

AbstractA “turn‐on” fluorescent sensing strategy was developed for ultrasensitive detection of heavy metal mercury ion (Hg2+) directly in water. It utilized an aqueous soluble aggregation‐induced emission (AIE)‐active probe, named 1,1,2,2‐tetrakis(4‐(1H‐tetrazol‐5‐yl)phenyl)ethene (TPE‐4TA), composing of a luminescent tetraphenylene core and multiple anionic tetrazolate spawns. The probe retained dark when molecularly dissolved in water. However, mercury ions can ligate with multiple tetrazolate groups to form infinite coordination polymer particles spontaneously, thus inducing a fluorogenic AIE response for in situ analysis. Moreover, by embedding this AIE sensing molecules in a hydrophilic polyvinyl alcohol substrate, the resulting hydrogel film allowed in situ detection of Hg2+ on a laser‐induced fluorescence analysis setup in aqueous environment. This strategy worked effectively in common aqueous environments with pH from 4 to 7.5 and showed high sensitivity (limit of detection down to 0.38 ppb/1.9 nM), good selectivity and a wide linearity range for quantification. This work may lead to a reliable and promising platform for on‐site environmental water analysis.