Optical Effect Modulation in Polarized Raman Spectroscopy of Transparent Layered α-MoO3.

Optical anisotropy, which is quantified by birefringence (Δn) and linear dichroism (Δk), can significantly modulate the angle-resolved polarized Raman spectroscopy (ARPRS) response of anisotropic layered materials (ALMs) by external interference. This work studies the separate modulation of birefringence on the ARPRS response and the intrinsic response by selecting transparent birefringent crystal α-MoO3 as an excellent platform. It is found that there are several anomalous ARPRS responses in α-MoO3 that cannot be reproduced by the real Raman tensor widely used in non-absorbing materials; however, they can be well explained by considering the birefringence-induced Raman selection rules. Moreover, the systematic thickness-dependent study indicates that birefringence modulates the ARPRS response to render an interference pattern; however, the amplitude of modulation is considerably lower than that by linear dichroism as occurred in black phosphorous. This weak modulation brings convenience to the crystal orientation determination of transparent ALMs. Combining the atomic vibrational pattern and bond polarizability model, the intrinsic ARPRS response of α-MoO3 is analyzed, giving the physical origins of the Raman anisotropy. This study employs α-MoO3 as an example, although it is generally applicable to all transparent birefringent ALMs.

A chemosensing approach for the colorimetric and spectroscopic detection of Cr3+, Cu2+, Fe3+, and Gd3+ metal ions.

Metal cations are present in domestic and industrial wastewater and have adverse effects on human and aqueous life. The present study describes the development of the molecular probe 9-anthracen-9-ylmethylene)hydrazineylidene)methyl)-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-8-ol (AMHMPQ) to detect Cr3+, Cu2+, Fe3+, and Gd3+ ions by using UV-visible, fluorescence, colorimetric and excitation-emission matrix (EEM) spectroscopy techniques. The interaction of Cr3+, Cu2+, Fe3+, and Gd3+ can be observed by the absorption maxima shift, turn-off, colour changes, and EEM shifts. In addition, fluorescence limits of detection 17.66 × 10-6 M, 6.44 × 10-9 M, 28.87 × 10-8 M, and 12.49 × 10-6 M in wide linear ranges, low limits of quantifications, high values of Stern-Volmer constant, Job's plot and Benesi-Hildebrand plot justify the 1:1 association affinity with association constants of 1.46 × 104 M-1, 1.86 × 107 M-1, 2.69 × 105 M-1, 2.13 × 104 M-1 for AMHMPQ-metal ions (Cr3+, Cu2+, Fe3+, and Gd3+ ions), respectively. Paper- and mask-based kits are developed to explore the utility of the designed chemosensor. Additionally, AMHMPQ acts as a reusable sensor for two, seven, two, and zero cycles for Cr3+, Cu2+, Fe3+, and Gd3+ ions, respectively, when checked with EDTA.

Fabricated Metal-Organic Frameworks (MOFs) as luminescent and electrochemical biosensors for cancer biomarkers detection.

In the health domain, a major challenge is the detection of diseases using rapid and cost-effective techniques. Most of the existing cancer detection methods show poor sensitivity and selectivity and are time consuming with high cost. To overcome this challenge, we analyzed porous fabricated metal-organic frameworks (MOFs) that have better structures and porosities for enhanced biomarker sensing. Here, we summarize the use of fabricated MOF luminescence and electrochemical sensors in devices for cancer biomarker detection. Various strategies of fabrication and the role of fabricated materials in sensing cancer biomarkers have been studied and described. The structural properties, sensing mechanisms, roles of noncovalent interactions, limits of detection, modeling, advantages, and limitations of MOF sensors have been well-discussed. The study presents an innovative technique to detect the cancer biomarkers by the use of luminescence and electrochemical MOF sensors. In addition, the potential association studies have been opening the way for personalized patient treatments and the development of new cancer-detecting devices.

Dynamically Long-Term Imaging of Cellular RNA by Fluorescent Carbon Dots with Surface Isoquinoline Moieties and Amines.

Cellular RNA dynamics are closely associated with a vast range of physiological processes that are mostly long-lasting. To uncover the association between RNA dynamics and these processes, fluorescent RNA probes with high specificity, photostability, and biocompatibility are compulsory. Herein, a series of fluorescent carbon dots (CDs) have been prepared by one-pot hydrothermal treatment of o-, m-, or p-phenylenediamines with triethylenetetramine. Only CDs derived from the meta precursor ( m-CDs) with excellent photostability and biocompatibility can specifically bind to cellular RNA, allowing successfully long-term (up to 3 days) monitoring of RNA dynamics during cell apoptosis, mitosis, and proliferation. This RNA affinity can be attributed to the isoquinoline moieties and amines on the surface of m-CDs, which can bind to RNA through π-π stacking and electrostatic bonding, respectively. The cellular internalization of m-CDs is time-, temperature-, ATP-, caveolar, and microtubule-dependent. Additionally, investigations on the in vivo behavior of m-CD suggest that they can be efficiently and rapidly excreted from the zebrafish larvae body after 48 h. Our results provide a powerful tool for clarifying complex relationships between RNA dynamics and basic biological processes, disease development, or drug interactions.

MIL-101(Cr) as matrix for sensitive detection of quercetin by matrix-assisted laser desorption/ionization mass spectrometry.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) has been proven as a useful and advanced technique in the identification of polymers and proteins. However, MALDI-TOF-MS still has the unavoidable drawback of self-signal interference with traditional organic matrices, which could suppress and overlap with the analyte signals in the low-mass region. In this work, MIL-101(Cr), a kind of metal-organic frameworks which possess high molecular weight, π-conjugated 3-D structure, coordinately unsaturated chromium sites (CUS) and strong absorption in the UV range, was employed to replace traditional organic matrices, and it was found that MIL-101(Cr) can dramatically eliminate the background peaks, showing high signal-to-noise level in the analysis of small molecules. As proof-of-concept, quercetin, daidzein, genistein and naringenin, members of flavonol family which widely exists in food and natural products, were successfully determined by utilizing MIL-101(Cr) as the surface-assisted matrix, and the detection of quercetin was sensitive with good salt tolerance and reproducibility. Under optimal conditions, the mass peak intensity exhibited good linear relationships in the range from 0.25µg/mL-7.00µg/mL for quercetin (R2=0.996) with detection limit 2.11ng/mL (3σ/k), making the identification of quercetin in sophora japonica successfully. With this strategy we have demonstrated the potentiality of MIL-101(Cr) nanomaterials as MALDI-MS matrix for the detection of small molecules.