Regioselective Tip-Enhanced Raman Spectroscopy of Lipid Membranes with Sub-Nanometer Axial Resolution.

Noninvasive and label-free analysis of cell membranes at the nanoscale is essential to comprehend vital cellular processes. However, conventional analytical tools generally fail to meet this challenge due to the lack of required sensitivity and/or spatial resolution. Herein, we demonstrate that tip-enhanced Raman spectroscopy (TERS) is a powerful nanoanalytical tool to analyze dipalmitoylphosphatidylcholine (DPPC) bilayers and human cell membranes with submolecular resolution in the vertical direction. Unlike the far-field Raman measurements, TERS spectra of the DPPC bilayers reproducibly exhibited a uniquely shaped C-H band. These unique spectral features were also reproducibly observed in the TERS spectrum of human pancreatic cancer cells. Spectral deconvolution and DFT simulations confirmed that the TERS signal primarily originated from vibrations of the CH3 groups in the choline headgroup of the lipids. The reproducible TERS results obtained in this study unequivocally demonstrate the ultrahigh sensitivity of TERS for nanoanalysis of lipid membranes under ambient conditions.

Association of per- and polyfluoroalkyl substances with hepatic steatosis and metabolic dysfunction-associated fatty liver disease among patients with acute coronary syndrome.

Etiology of hepatic steatosis and metabolic dysfunction-associated fatty liver disease (MAFLD) among acute coronary syndrome (ACS) remains unclear. Existing studies suggested the potential role of per- and polyfluoroalkyl substances (PFAS) in comorbidity of hepatic steatosis among ACS patients. Therefore, we conducted a cross-sectional study based on the ACS inpatients to assess the associations of plasma PFAS congeners and mixtures with hepatic steatosis and MAFLD. This study included 546 newly diagnosed ACS patients. Twelve PFAS were quantified using ultra-high-performance liquid chromatography-tandem mass spectrometry. Hepatic steatosis was defined by hepatic steatosis index (HSI). MAFLD was defined as the combination of hepatic steatosis based on the risk factor calculation with metabolic abnormalities. Generalized linear model was used to examine the associations of PFAS congeners with HSI and MAFLD. Adaptive elastic net (AENET) was further used for PFAS congeners selection. Mixture effects were also assessed with Bayesian kernel machine regression model (BKMR). Congeners analysis observed significant greater percent change of HSI for each doubling in PFOS (1.82%, 95% CI: 0.87%, 2.77%), PFHxS (1.17%, 95% CI: 0.46%, 1.89%) and total PFAS (1.84%, 95% CI: 0.56%, 3.14%). Moreover, each doubling in PFOS (OR=1.42, 95% CI: 1.13, 1.81), PFHxS (OR=1.31, 95% CI: 1.09, 1.59) and total PFAS (OR=1.43, 95% CI: 1.06, 1.94) was associated with increased risk of MAFLD. In AENET regression, only PFOS presented significant positive associations with HSI. Mixture analysis indicated significant positive associations between PFAS mixtures and HSI. This is the first study to demonstrate associations of PFAS congeners and mixtures with hepatic steatosis and MAFLD among ACS patients, which provides hypothesis into the mechanisms behind comorbidity of hepatic steatosis among ACS patients, as well as tertiary prevention of ACS.

Oligothiophene molecular wires at graphene-based molecular junctions.

The use of graphene as a new type of electrode at molecular junctions has led to a renewal of molecular electronics. Indeed, the symmetry breaking induced by the graphene electrode yields different electronic behaviors at the molecular junction and in particular enhanced conductance for longer molecules. In this respect, several studies involving different molecular backbones and anchoring groups have been performed. Here in the same line, we consider oligopthiophene based hybrid gold-graphene junctions and we measure their electrical properties using the STM-I(s) method in order to determine their attenuation factor and the effect of specific anchoring groups. The results are supported by density functional theory (DFT) calculations, and exhibit a similar behavior to what is observed at alkane-based junctions.

Correction to: A glassy carbon electrode modified with N-doped carbon dots for improved detection of hydrogen peroxide and paracetamol.

The authors of "A glassy carbon electrode modified with N-doped carbon dots for improved detection of hydrogen peroxide and paracetamol (Microchimica Acta 185, no. 2 (2018): 87)" wish to replace the incorrect images of Fig. 1C, 1D shown below.

Fast and straightforward analysis approach of charge transport data in single molecule junctions.

In this study, we introduce an efficient data sorting algorithm, including filters for noisy signals, conductance mapping for analyzing the most dominant conductance group and sub-population groups. The capacity of our data analysis process has also been corroborated on real experimental data sets of Au-1,6-hexanedithiol-Au and Au-1,8-octanedithiol-Au molecular junctions. The fully automated and unsupervised program requires less than one minute on a standard PC to sort the data and generate histograms. The resulting one-dimensional and two-dimensional log histograms give conductance values in good agreement with previous studies. Our algorithm is a straightforward, fast and user-friendly tool for single molecule charge transport data analysis. We also analyze the data in a form of a conductance map which can offer evidence for diversity in molecular conductance. The code for automatic data analysis is openly available, well-documented and ready to use, thereby offering a useful new tool for single molecule electronics.

Carbon-contacted single molecule electrical junctions.

A fully metal-free molecular junction (MJ) has been built by using an electrochemically etched carbon fibre STM tip as the top electrode and graphene as the bottom electrode. The corresponding conductance values for 1,n-alkanediamine and 1,n-alkanedithiol (n = 2, 4, 6, 8 and 10) have been measured using the STM-I(s) technique. The tunnelling decay constant of the alkanediamine and alkanedithiol junctions with these carbon contacts is much lower than the corresponding metal contacted junctions of 0.24 and 0.38 per -CH2 unit, but the junction conductance with these carbon contacts is also lower. The carbon fibre tip can be considered a good candidate as an electrode. Compared with a gold tip, the carbon fibre tip leads to correspondingly lower molecular junction conductance.

A glassy carbon electrode modified with N-doped carbon dots for improved detection of hydrogen peroxide and paracetamol.

Nitrogen doped carbon dots (NCDs) were synthesized using a low temperature approach and used to modify a glassy carbon electrode (GCE) via dipping. The oxygen groups on the surface of the NCDs, and the charge delocalization of the NCDs warrant an excellent electrocatalytic activity of the GCE toward oxidation of paracetamol (PA) and reduction of H2O2. PA and H2O2 were detected at 0.34 V and -0.4 V (both vs. Ag/AgCl) using differential pulse voltammetry and amperometric I-T measurement, respectively. The modified GCE has a linear response to PA in the 0.5 to 600 µM concentration range, and to H2O2 in the 0.05 µM to 2.25 mM concentration range. The detection limits are 157 nM and 41 nM, respectively. In our perception, the modified GCE holds promise for stable, selective and sensitive determination of PA and H2O2 in pharmaceutical analysis. Graphic abstract Nitrogen doped carbon dots (NCDs) were synthesized and used to modify a glassy carbon electrode. Surface functional groups on NCDs can trigger electrocatalytic reactions toward paracetamol oxidation and H2O2 reduction with high sensitivities.

Defect passivation induced strong photoluminescence enhancement of rhombic monolayer MoS2.

Growing high quality monolayer MoS2 with strong photoluminescence (PL) is essential to produce light-emitting devices on the atomic scale. In this study we show that rhombic monolayer MoS2 with PL intensity 8 times stronger than those of chemical vapour deposition (CVD)-grown triangular and mechanically exfoliated (ME) monolayer MoS2 can be prepared by using CVD. Both Raman and PL measurements indicate low density of defects in rhombic monolayer MoS2 with enhanced PL intensity. Density functional theory (DFT) calculations show that passivation of defects in MoS2 removes trapping gap states, which may finally result in PL enhancement.

Observation of Strong Anisotropic Interlayer Excitons.

Anisotropic interlayer excitons had been theoretically predicted to exist in two-dimensional (2D) anisotropy/isotropy van der Waals heterojunctions. However, experimental results consolidating the theoretical prediction and exploring the related anisotropic optoelectronic response have not been reported so far. Herein, strong photoluminescence (PL) of anisotropic interlayer excitons is observed in a symmetric anisotropy/isotropy/anisotropy heterojunction exemplified by 3L-ReS2/1L-MoS2/3L-ReS2 using monolayer (1L) MoS2 and trilayer (3L) ReS2 as components. Sharp interlayer exciton PL peaks centered at ∼1.64, ∼1.61, and ∼1.57 eV are only observed at low temperatures of ≤120 K and become more pronounced as the temperature decreases. These interlayer excitons exhibit strong anisotropic PL intensity variations with periodicities of 180° as functions of the incident laser polarization angles. The polarization ratios of these interlayer excitons are calculated to be 1.33-1.45. Our study gives new insight into the manipulation of excitons in 2D materials and paves a new way for a rational design of novel anisotropic optoelectronic devices.

Tip-enhanced nanoscopy of two-dimensional transition metal dichalcogenides: progress and perspectives.

The optoelectronic properties of two-dimensional (2D) transition metal dichalcogenide (TMD) thin layers prepared by exfoliation or chemical vapour deposition are strongly modulated by defects at the nanoscale. The mediated electronic and optical properties are expected to be spatially localised in a nanoscale width neighbouring the defects. Characterising such localised properties requires an analytical tool with nanoscale spatial resolution and high optical sensitivity. In recent years, tip-enhanced nanoscopy, represented by tip-enhanced Raman spectroscopy (TERS) and tip-enhanced photoluminescence (TEPL), has emerged as a powerful tool to characterise the localised phonon and exciton behaviours of 2D TMDs and heterojunctions (HJs) at the nanoscale. Herein, we first summarise the recent progress of TERS and TEPL in the characterisation of several typical defects in TMDs, such as edges, wrinkles, grain boundaries and other defects generated in transfer and growth processes. Then the local strain and its dynamic control of phonon and exciton behaviours characterised by TERS and TEPL will be reviewed. The recent progress in characterising TMD HJs using TERS and TEPL will be subsequently summarised. Finally, the progress of TERS and TEPL combined with optoelectronic sensitive electronic scanning probe microscopy (SPM) in the applications of TMDs will be reviewed.

Visualizing Surface Phase Separation in PS-PMMA Polymer Blends at the Nanoscale.

Phase-separated polymer blend films are an important class of functional materials with numerous technological applications in solar cells, catalysis, and biotechnology. These technologies are underpinned by the precise control of phase separation at the nanometer length-scales, which is highly challenging to visualize using conventional analytical tools. Herein, we introduce tip-enhanced Raman spectroscopy (TERS), in combination with atomic force microscopy (AFM), confocal Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS), as a sensitive nanoanalytical method to determine lateral and vertical phase-separation in polystyrene (PS)-poly(methyl methacrylate) (PMMA) polymer blend films. Correlative topographical, molecular, and elemental information reveals a vertical phase separation of the polymers within the top ca. 20 nm of the blend surface in addition to the lateral phase separation in the bulk. Furthermore, complementary TERS and XPS measurements reveal the presence of PMMA within 9.2 nm of the surface and PS at the subsurface of the polymer blend. This fundamental work establishes TERS as a powerful analytical tool for surface characterization of this important class of polymers at nanometer length scales.

A bibliometric analysis of graphene in acetaminophen detection: Current status, development, and future directions.

Acetaminophen is a widely used analgesic throughout the world. Detection of acetaminophen has particular value in pharmacy and clinics. Electrochemical sensors assembled with advanced materials are an effective method for the rapid detection of acetaminophen. Graphene-based carbon nanomaterials have been extensively investigated for potential analytical applications in the last decade. In this article, we selected papers containing both graphene and acetaminophen. Bibliometrics was used to analyze the relationships and trends among these papers. The results show that the topic has grown at a high rate since 2009. Among them, the detection of acetaminophen by an electrochemical sensor based on graphene is the most important direction. Graphene has moved from being a primary sensing material to a substrate for immobilization of other active ingredients. In addition, the degradation of acetaminophen using graphene-modified electrodes is also an important direction. We analyzed the research history and current status of this topic through bibliometrics. Authors, institutions, countries, and key literature were discussed. We also proposed perspectives for this topic.

Electrochemical detection of Sudan red series azo dyes: Bibliometrics based analysis.

Sudan red azo dyes are banned from food because of their carcinogenic properties. It is necessary to establish a method for the detection of Sudan azo dyes in food. Among them, electrochemical sensing technology has become a very potential analytical method for food detection because of its fast, sensitive and low price. In this paper, we analyze the electrochemical detection of Sudan red azo dyes by bibliometric method. A total of 161 articles were analyzed from 2007 to 2021. The geographical and institutional distribution of these papers is used to understand the form of collaboration on this topic. Keyword analysis in these papers is used to understand the different directions in which the topic is studied at different stages. The results show that the topic reached its peak in 2015. The development of novel materials with excellent electrochemical activity has promoted the research on this topic. As detection limits continue to be lowered and sensors continue to be optimized, this topic currently does not continue to attract much attention.

Probing Nanoscale Exciton Funneling at Wrinkles of Twisted Bilayer MoS2 Using Tip-Enhanced Photoluminescence Microscopy.

In twisted bilayer (t2L) two-dimensional (2D) transition metal dichalcogenides, local strain at wrinkles strongly modulates the local exciton density and PL energy resulting in an exciton funneling effect. Probing such exciton behaviors especially at nanometer length scales is beyond the limit of conventional analytical tools due to the limited spatial resolution and low sensitivity. To address this challenge, herein we applied high-resolution tip-enhanced photoluminescence (TEPL) microscopy to investigate exciton funneling at a wrinkle in a t2L MoS2 sample with a small twist angle of 0.5°. Owing to a spatial resolution of <10 nm, excitonic behavior at nanoscale sized wrinkles could be visualized using TEPL imaging. Detailed investigation of nanoscale exciton funneling at the wrinkles revealed a deformation potential of -54 meV/%. The obtained results provide novel insights into the inhomogeneities of excitonic behaviors at nanoscale and would be helpful in facilitating the rational design of 2D material-based twistronic devices.

Association of metabolic dysfunction-associated fatty liver disease, type 2 diabetes mellitus, and metabolic goal achievement with risk of chronic kidney disease.

Background: Although type 2 diabetes mellitus (T2DM) plays a significant role in the association between metabolic dysfunction-associated fatty liver disease (MAFLD) and chronic kidney disease (CKD), how T2DM development and glycemic deterioration affect CKD and its renal function indicators, estimated glomerular filtration rate (eGFR) and urine albumin-to-creatinine ratio (UACR), remains unknown. We aimed to assess the association between MAFLD, along with T2DM, and risk of CKD, and then evaluate the effect of metabolic goal achievement in MAFLD on the risk of CKD. Methods: In this cross-sectional study, 5,594 participants were included. Multivariate logistic regression and linear regression were used to examine the association between MAFLD with its T2DM status and metabolic goal achievement and risk of CKD, as well as eGFR and UACR. Results: The MAFLD group had a higher prevalence of CKD (16.2 vs. 7.6%, P < 0.001) than the non-MAFLD group. MAFLD was independently associated with an increased risk of CKD (odds ratio [OR]: 1.35, 95% CI: 1.09-1.67) and increased eGFR and UACR. Among the three MAFLD subtypes, only the T2DM subtype exhibited significant associations with increased risk of CKD (OR: 2.85, 95% CI: 2.24-3.63), as well as increased eGFR and UACR. Glycemic deterioration in MAFLD was dose-dependently associated with an increased risk of CKD (P-trend < 0.001). Achieved metabolic goals in MAFLD decreased the risk of CKD, eGFR, and UACR; MAFLD with 2 or 3 achieved metabolic goals was not significantly associated with the risk of CKD (OR: 0.81, 95% CI: 0.59-1.12) and albuminuria. Conclusion: MAFLD was independently associated with an increased risk of CKD, as well as increased eGFR and UACR. This association is strongly driven by T2DM status. Glycemic deterioration in MAFLD was dose-dependently associated with an increased risk of CKD. Achieved metabolic goals in MAFLD decreased the risk of CKD by reducing the risk of albuminuria.

Graphene-based electrochemical sensors for antibiotic detection in water, food and soil: A scientometric analysis in CiteSpace (2011-2021).

The residues of antibiotics in the environment pose a potential health hazard, so highly sensitive detection of antibiotics has always appealed to analytical chemists. With the widespread use of new low-dimensional materials, graphene-modified electrochemical sensors have emerged as an excellent candidate for highly sensitive detection of antibiotics. Graphene, its derivatives and its composites have been used in this field of exploration in the last decade. In this review, we have not only described the field using traditional summaries, but also used bibliometrics to quantify the development of the field. The literature between 2011 and 2021 was included in the analysis. Also, the sensing performance and detection targets of different sensors were compared. We were able to trace not only the flow of research themes, but also the future areas of development. Graphene is a material that has a high potential to be used on a large scale in the preparation of electrochemical sensors. How to design a sensor with selectivity and low cost is the key to bring this material from the laboratory to practical applications.

MoS2/WSe2 vdW Heterostructures Decorated with PbS Quantum Dots for the Development of High-Performance Photovoltaic and Broadband Photodiodes.

van der Waals heterostructures (vdWHs) overcoming the lattice and processing limitations of conventional heterostructures provide an opportunity to develop high-performance 2D vdWH solar cells and photodiodes. However, it is challenging to improve the sensitivity and response speed of 2D vdWH photovoltaic devices due to the low light absorption efficiency and electron/hole traps in heterointerfaces. Here, we design a PbS/MoS2/WSe2 heterostructure photodiode in which a light-sensitive PbS quantum dot (QD) layer combined with a MoS2/WSe2 heterostructure significantly enhances the photovoltaic response. The electron current in the heterostructure is increased by the effective collection of photogenerated electrons induced by PbS QDs. The device exhibits a broadband photovoltaic response from 405 to 1064 nm with a maximum responsivity of 0.76 A/W and a specific detectivity of 5.15 × 1011 Jones. In particular, the response speed is not limited by multiple electron traps in the PbS QDs/2D material heterointerface, and a fast rising/decaying time of 43/48 µs and a -3 dB cutoff frequency of over 10 kHz are achieved. The negative differential capacitance and frequency dependence of capacitance demonstrate the presence of interface states in the MoS2/WSe2 heterointerface that hamper the improvement of the response speed. The scheme to enhance photovoltaic performance without sacrificing response speed provides opportunities for the development of high-performance 2D vdWH optoelectronic devices.

Multimodal Nanoscopic Study of Atomic Diffusion and Related Localized Optoelectronic Response of WS2/MoS2 Lateral Heterojunctions.

The atomic diffusion in transition metal dichalcogenides (TMDs) van der Waals heterojunctions (HJs) strongly modifies their optoelectronic properties in the nanoscale. However, probing such localized properties challenges the spatial resolution and the sensitivity of a variety of analytic tools. Herein, a multimodal nanoscopy (based on tip enhanced Raman spectroscopy (TERS) and photoluminescence (TEPL)) combined with the Kelvin probe force microscopy (KPFM) method was used to probe such nanoscale localized optoelectronic properties induced by atomic diffusion. Chemical vapor deposition (CVD)-grown lateral bilayer (2L) WS2/MoS2 HJs were imaged with a spatial resolution better than 40 nm via TERS and TEPL mapping by using intrinsic Raman and photoluminescence (PL) peaks. The contact potential difference (CPD), capacitance, and PL variation in a nanoscale vicinity of the HJ interface can be correlated to the local stoichiometry variation determined by TERS. The diffusion coefficients of W and Mo were obtained to be ∼0.5 × 10-12 and ∼1 × 10-12 cm2/s, respectively, by using Fick's second law. The obtained results would be useful to further understand the localized optoelectronic response of the TMDs HJs.

Visualising structural modification of patterned graphene nanoribbons using tip-enhanced Raman spectroscopy.

Graphene nanoribbons (GNRs) fabricated using electron beam lithography are investigated using tip-enhanced Raman spectroscopy (TERS) with a spatial resolution of 5 nm under ambient conditions. High-resolution TERS imaging reveals a structurally modified 5-10 nm strip of disordered graphene at the edge of the GNRs. Furthermore, hyperspectral TERS imaging discovers the presence of nanoscale organic contaminants on the GNRs. These results pave the way for nanoscale chemical and structural characterisation of graphene-based devices using TERS.

Polymer-buried van der Waals magnets for promising wearable room-temperature spintronics.

The demand for high-performance spintronic devices has boosted intense research on the manipulation of magnetism in van der Waals (vdW) magnets. Despite great efforts, robust ferromagnetic transitions above room temperature still face significant hurdles. Strain engineering can reversibly regulate magnetic exchange, but the degree of regulation is still impractical for most magnetic applications. Hereby we employ a large-strain transferrer to produce tunable strains of up to 4.7%, which induces authentic room-temperature ferromagnetism in large-area Fe3GeTe2 nanoflakes with 20-fold improvement in magnetization. The record increment of the Curie temperature (TC) of well above 400 K originates from the strain-enhanced magnetic anisotropy and excellent magnetoelastic coupling. The correlation between the emerging ferromagnetism and Raman spectral evolution is also established, which complements well the TC phase diagram in a large-strain region. In addition, an unusual exchange bias effect with a vertical magnetization shift is tracked for the first time upon bending, which reveals the hidden competition between antiferromagnetic and ferromagnetic coupling. The reversible strain manipulation of single-domain ferromagnetic order in a single nanoflake further opens up a route to develop low-power wearable spintronic devices. The findings here provide vast opportunities to exploit the possibility of practical applications of more vdW magnets.