Toward the Electrostatic Catalysis of Nucleophilic Substitutions: A Surface Chemistry Study of the Menshutkin Reaction.

The catalysis of nonredox reactions by external electric fields is one of the most rapidly expanding areas of chemistry. The Menshutkin reaction, a classic example of bimolecular nucleophilic substitution (S2), involves the conversion of a tertiary amine to a quaternary ammonium salt by coupling it with an alkyl halide. The reaction barrier of the Menshutkin reaction is theoretically predicted to be highly sensitive to the magnitude and direction of an external electric field experienced by the transition state.

Schottky Diode Leakage Current Fluctuations: Electrostatically Induced Flexoelectricity in Silicon.

Nearly four decades have passed since IBM scientists pioneered atomic force microscopy (AFM) by merging the principles of a scanning tunneling microscope with the features of a stylus profilometer. Today, electrical AFM modes are an indispensable asset within the semiconductor and nanotechnology industries, enabling the characterization and manipulation of electrical properties at the nanoscale. However, electrical AFM measurements suffer from reproducibility issues caused, for example, by surface contaminations, Joule heating, and hard-to-minimize tip drift and tilt.

Hydrophobic Coatings with Charge Permeability via Plasma Deposition of Long-Chain Perfluorocarbons.

Hydrophobization of nanotextured catalyst materials is a promising route to enhance the yield of N and CO conversion into green fuels. However, these applications require a hydrophobic coating to not only promote air trapping but also allow charge transfer at the electrode-electrolyte interface. In this work, nano thin films with thicknesses as low as 7 nm were deposited from the plasma phase of perfluorohexene, perfluorodecene, and perfluorooctane (PFO) precursors using a mild vacuum and gentle powers.

Galinstan Liquid Metal Electrical Contacts for Monolayer-Modified Silicon Surfaces.

Galinstan is the brand name for a low-melting gallium-based alloy, which is a promising nontoxic alternative to mercury, the only elemental metal found in the liquid state at room temperature. Liquid alloys such as Galinstan have found applications as electromechanical actuators, sensors, and soft contacts for molecular electronics. In this work, we validate the scope of Galinstan top contacts to probe the electrical characteristics of Schottky junctions made on Si(111) and Si(211) crystals modified with Si-C-bound organic monolayers.

Terminal Deuterium Atoms Protect Silicon from Oxidation.

In recent years, the hybrid silicon-molecular electronics technology has been gaining significant attention for applications in sensors, photovoltaics, power generation, and molecular electronics devices. However, Si-H surfaces, which are the platforms on which these devices are formed, are prone to oxidation, compromising the mechanical and electronic stability of the devices. Here, we show that when hydrogen is replaced by deuterium, the Si-D surface becomes significantly more resistant to oxidation when either positive or negative voltages are applied to the Si surface.

Printable Hydrogel Arrays for Portable and High-Throughput Shear-Mediated Assays.

Hydrogels have been widely used to entrap biomolecules for various biocatalytic reactions. However, solute diffusion in these matrices to initiate such reactions can be a very slow process. Conventional mixing remains a challenge as it can cause irreversible distortion or fragmentation of the hydrogel itself.

Effects of Supplemental Drugs on Hexaminolevulinate (HAL)-Induced PpIX Fluorescence in Bladder Cancer Cell Suspensions.

Seven different inhibitors of the heme metabolic pathway were applied in combination with HAL to study the formation of PpIX in bladder cancer HT1197 and normal fibroblast HFFF2 cells ex vivo, specifically with the aim to increase the fluorescence contrast between cancer and non-cancer cells. The mRNA expression of enzymes involved in the heme biosynthesis pathway were measured via PCR following incubation with the drugs in order to link the fluorescence levels and metabolic activity. The exogenous administration of HAL does lead to cancer-specific PpIX accumulation.

On-Surface Azide-Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?

Owing to its simplicity, selectivity, high yield, and the absence of byproducts, the "click" azide-alkyne reaction is widely used in many areas. The reaction is usually catalyzed by copper(I), which selectively produces the 1,4-disubstituted 1,2,3-triazole regioisomer. Ruthenium-based catalysts were later developed to selectively produce the opposite regioselectivity─the 1,5-disubstituted 1,2,3-triazole isomer.

Effect of Electric Fields on Silicon-Based Monolayers.

Electric fields can induce bond breaking and bond forming, catalyze chemical reactions on surfaces, and change the structure of self-assembled monolayers on electrode surfaces. Here, we study the effect of electric fields supplied either by an electrochemical potential or by conducting atomic force microscopy (C-AFM) on Si-based monolayers. We report that typical monolayers on silicon undergo partial desorption followed by the oxidation of the underneath silicon at +1.

Nanoparticles Surface Chemistry Influence on Protein Corona Composition and Inflammatory Responses.

Nanoparticles are widely used for biomedical applications such as vaccine, drug delivery, diagnostics, and therapeutics. This study aims to reveal the influence of nanoparticle surface functionalization on protein corona formation from blood serum and plasma and the subsequent effects on the innate immune cellular responses. To achieve this goal, the surface chemistry of silica nanoparticles of 20 nm diameter was tailored via plasma polymerization with amine, carboxylic acid, oxazolines, and alkane functionalities.

Prostate cancer detection: a systematic review of urinary biosensors.

Background: Current diagnostic methods for prostate cancer are invasive and lack specificity towards aggressive forms of the disease, which can lead to overtreatment. A new class of non-invasive alternatives is under development, in which urinary biomarkers are detected using biosensing devices to offer rapid and accurate prostate cancer diagnosis. These different approaches are systematically reviewed and their potential for translation to clinical practice is evaluated.

Selective Microfluidic Capture and Detection of Prostate Cancer Cells from Urine without Digital Rectal Examination.

Urine-based biomarkers have shown suitable diagnostic potential for prostate cancer (PCa) detection. Yet, until now, prostatic massage remains required prior to urine sampling. Here, we test a potential diagnostic approach using voided urine collected without prior digital rectal examination (DRE).

Fluid Flow Dependency in Immunoselective Cell Capture via Liquid Biopsy.

Liquid biopsy targets rare cells that overexpress disease-specific membrane markers and capture these cells via immunoaffinity. The diagnosis efficiency of liquid biopsy can be impaired by the presence of healthy adherent cells also expressing the same biomarkers. Here, we investigated the effect of settling times and rinsing flow rates on the efficiency of EpCAM-based immunocapture using both simulation and experiments with three different cell types.

Plasma Deposited Polyoxazoline Films Integration Into Spiral Microfluidics for the Targeted Capture of Size Selected Cells.

Biomolecules readily and irreversibly bind to plasma deposited Polyoxazoline thin films in physiological conditions. The unique reactivity of these thin films toward antibodies is driving the development of immunosensing platforms for applications in cancer diagnostics. However, in order for these coatings to be used as advanced immunosensors, they need to be incorporated into microfluidic devices that are sealed via plasma bonding.

Improving hexaminolevulinate enabled cancer cell detection in liquid biopsy immunosensors.

Hexaminolevulinate (HAL) induced Protoporphyrin IX (PpIX) fluorescence is commonly used to differentiate cancer cells from normal cells in vivo, as for instance in blue light cystoscopy for bladder cancer diagnosis. A detailed approach is here provided to use this diagnostic principle ex vivo in an immunosensor device, towards enabling non-invasive cancer diagnostic from body fluids, such as urine. Several factors susceptible to affect the applicability of HAL-assisted diagnosis in body fluids were tested.

Cancer cell detection device for the diagnosis of bladder cancer from urine.

Bladder cancer is common and has one of the highest recurrence rates. Cystoscopy, the current gold standard diagnosis approach, has recently benefited from the introduction of blue light assisted photodynamic diagnostic (PDD). While blue light cystoscopy improves diagnostic sensitivity, it remains a costly and invasive approach.

Functional nanothin films plasma-deposited from 2-isopropenyl-2-oxazoline for biosensor applications.

Plasma polymers derived from oxazoline precursors present a range of versatile properties that is fueling their use as biomaterials. However, coatings deposited from commonly used methyl and ethyl oxazoline precursors can be sensitive to the plasma deposition conditions. In this work, we used various spectroscopic methods (ellipsometry, x-ray photoelectron spectroscopy, and time of flight secondary ion mass spectrometry) and cell viability assays to evaluate the transferability of deposition conditions from the original plasma reactor developed by Griesser to a new wider, reactor designed for upscaled biosensors applications.

Shedding Light on Bladder Cancer Diagnosis in Urine.

Blue light cystoscopy (BLC) is the most recent clinical approach in the detection and diagnosis of bladder cancer, a common type of cancer with a high rate of recurrence. Representing a significant advance over previous approaches, this photodynamic diagnostic technique uses a photosensitiser prodrug as an adjunct to white light cystoscopy to enhance the in vivo detection of malignant tissues in the bladder based on their distinctive fluorescence. Whilst it does improve detection rates, BLC remains an invasive and costly procedure.

Plasma enabled devices for the selective capture and photodynamic identification of prostate cancer cells.

Prostate cancer is the second most common cancer in men and the second leading cause of male cancer deaths. The current blood test for detecting prostate cancers measures prostate-specific antigen. It has many limitations including a very high rate of false positives.

Probing Hexaminolevulinate Mediated PpIX Fluorescence in Cancer Cell Suspensions in the Presence of Chemical Adjuvants.

Exogenous administration of hexaminolevulinate (HAL) induces fluorescent protoporphyrin IX (PpIX) accumulation preferentially in cancer cells. However, the PpIX fluorescence intensities between noncancer and cancer cells are highly variable. The contrast between cancer and noncancer cells may be insufficient to reliably discriminate, especially at the single cell level in cancer diagnostics.

Bladder Cancer Cell Capture: Elucidating the Effect of Sample Storage Conditions on Capturing Bladder Cancer Cells via Surface Immobilized EpCAM Antibody.

The gold standard to detect bladder cancer, cystoscopy, is an invasive procedure requiring ambulant hospitalization, thus presenting an obstacle for routine diagnosis. We aim to develop a noninvasive detection method as an alternative that selectively captures shed cancer cells in the patient's urine via surface-immobilized anti-EpCAM antibody. However, the urine sample storage conditions prior to analysis affect the subsequent cancer cell capture rates by the device.

In order for the light to shine so brightly, the darkness must be present-why do cancers fluoresce with 5-aminolaevulinic acid?

Photodynamic diagnosis and therapy have emerged as a promising tool in oncology. Using the visible fluorescence from photosensitisers excited by light, clinicians can both identify and treat tumour cells in situ. Protoporphyrin IX, produced in the penultimate step of the haem synthesis pathway, is a naturally occurring photosensitiser that visibly fluoresces when exposed to light.

Biosensor device for the photo-specific detection of immuno-captured bladder cancer cells using hexaminolevulinate: An ex-vivo study.

Unlabelled: Exogenous administration of the photodynamic agent hexaminolevulinate induces Protoporphyrin IX (PpIX) accumulation in malignant tissue. This may enable differentiation from healthy tissues by emission of a distinctive red fluorescence. It provides the photo-specific detection when excited with blue light at 405 nm.

Biomaterial Surface Hydrophobicity-Mediated Serum Protein Adsorption and Immune Responses.

The nature of the protein corona forming on biomaterial surfaces can affect the performance of implanted devices. This study investigated the role of surface chemistry and wettability on human serum-derived protein corona formation on biomaterial surfaces and the subsequent effects on the cellular innate immune response. Plasma polymerization, a substrate-independent technique, was employed to create nanothin coatings with four specific chemical functionalities and a spectrum of surface charges and wettability.

Plasma Polymer Coatings To Direct the Differentiation of Mouse Kidney-Derived Stem Cells into Podocyte and Proximal Tubule-like Cells.

Kidney disease is now recognized as a global health problem and is associated with increased morbidity and mortality, along with high economic costs. To develop new treatments for ameliorating kidney injury and preventing disease progression, there is a need for appropriate renal culture systems for screening novel drugs and investigating the cellular mechanisms underlying renal pathogenesis. There is a need for in vitro culture systems that promote the growth and differentiation of specialized renal cell types.