Intermediates Adsorption Engineering of CO2 Electroreduction Reaction in Highly Selective Heterostructure Cu‐Based Electrocatalysts for CO Production

The challenge in the artificial CO₂ reduction to fuel is achieving high selective electrocatalysts. Here, a highly selective Cu₂O/CuO heterostructure electrocatalyst is developed for CO₂ electroreduction. The Cu₂O/CuO nanowires modified by Ni nanoparticles exhibit superior catalytic performance with high faradic efficiency (95% for CO). Theoretical and experimental analyses show that the hybridization of Cu₂O/CuO nanowires and Ni nanoparticles can not only adjust the d‐band center of electrocatalysts to enhance the intrinsic catalytic activity but also improve the adsorption of COOH* intermediates and suppress the hydrogen evolution reaction to promote the CO conversion efficiency during CO₂ reduction reaction. An in situ Raman spectroscopic study further confirms the existence of COOH* species and the engineering intermediates adsorption. This work offers new insights for facile designing of nonprecious transition metal compound heterostructure for CO₂ reduction reaction through adjusting the reaction pathway.     

Effects of nitrogen on interspecific competition between two cell-size cyanobacteria: Microcystis aeruginosa and Synechococcus sp.

Micro-cyanobacteria and pico-cyanobacteria coexist in many lakes throughout the world. Their distinct cell sizes and nutrient utilization strategies may lead to dominance of one over the other at varying nutrient levels. In this study, Microcystis aeruginosa and Synechococcus sp. were chosen as representative organisms of micro- and pico-cyanobacteria, respectively. A series of nitrate and ammonia conditions (0.02, 0.1, 0.5, and 2.5 mg N L⁻¹) were designed in mono- or co-cultured systems, respectively. Growth rates of the two species were calculated and fitted by the Monod and Logistic equations. Furthermore, the interspecific competition was analyzed using the Lotka–Volterra model. In mono-cultures, the two cyanobacteria displayed faster growth rates in ammonia than in nitrate. Meanwhile, Synechococcus sp. showed faster growth rates compared to M. aeruginosa in lower N groups (≤ 0.5 mg N L⁻¹). However, in the highest nitrate treatment (2.5 mg N L⁻¹), M. aeruginosa achieved much higher biomass and faster growth rates than Synechococcus sp.. In co-cultures, Synechococcus sp. dominated in the lowest N treatment (0.02 mg N L⁻¹), but M. aeruginosa dominated under the highest nitrate condition (2.5 mg N L⁻¹). Based on the analysis of Raman spectra of living cells in mono-cultures, nitrate (2.5 mg N L⁻¹) upgraded the pigmentary contents of M. aeruginosa better than ammonia (2.5 mg N L⁻¹), but nitrogen in different forms showed little effects on the pigments of Synechococcus sp.. Findings from this study can provide valuable information to predict cyanobacterial community succession and aquatic ecosystem stability.     

基于固态基底的SERS免疫检测新方法研究

目的:通过引入新型表面增强拉曼散射(SERS)检测探针(Au-DTNB-Tyr NPs)和金标银染技术,建立基于固态硅片基底的SERS免疫检测新技术。方法:羊抗人IgM-HRP作为检测抗体,在硅片基底上检测不同浓度的人IgM,HRP催化SERS检测探针沉积,利用金标银染技术增强SERS信号。结果:所建立的SERS免疫检测新方法检测人IgM的检测限为10 pg/mL,且SERS信号强度与人IgM浓度具有良好的线性关系(R2=0.993)。结论:基于硅片基底的SERS免疫检测新技术可高灵敏地定量检测人IgM,为实现固态硅片基底对多种抗原的高通量集成化检测奠定了基础。     

Label‐free grading and staging of urothelial carcinoma through multimodal fibre‐probe spectroscopy

Urothelial carcinoma (UC) is the most common bladder tumour. Proper treatment requires tumour resection for diagnosing its grade (aggressiveness) and stage (invasiveness). White‐light cystoscopy and histopathological examination are the gold standard procedures for clinical and histopathological diagnostics, respectively. However, cystoscopy is limited in terms of specificity, histology requires long tissue processing, both procedures rely on operator's experience. Multimodal optical spectroscopy can provide a powerful tool for detecting, staging and grading bladder tumours in a fast, reliable and label‐free modality. In this study, we collected fluorescence, Raman and reflectance spectra from 50 biopsies obtained from 32 patients undergoing transurethral resection of bladder tumour using a multimodal fibre‐probe. Principal component analysis allowed distinguishing normal from pathological tissues, as well as discriminating tumour stages and grades. Each individual spectroscopic technique provided high specificity and sensitivity in classifying all tissues; however, a multimodal approach resulted in a considerable increase in diagnostic accuracy (≥95%), which is of paramount importance for tumour grading and staging. The presented method offers the potential for being applied in cystoscopy and for providing an automated diagnosis of UC at the clinical level, with an improvement with respect to current state‐of‐the‐art procedures.      

Raman ChemLighter: Fiber optic Raman probe imaging in combination with augmented chemical reality

Raman spectroscopy using fiber optic probe combines non‐contacted and label‐free molecular fingerprinting with high mechanical flexibility for biomedical, clinical and industrial applications. Inherently, fiber optic Raman probes provide information from a single point only, and the acquisition of images is not straightforward. For many applications, it is highly crucial to determine the molecular distribution and provide imaging information of the sample. Here, we propose an approach for Raman imaging using a handheld fiber optic probe, which is built around computer vision–based assessment of positional information and simultaneous acquisition of spectroscopic information. By combining this implementation with real‐time data processing and analysis, it is possible to create not only fiber‐based Raman imaging but also an augmented chemical reality image of the molecular distribution of the sample surface in real‐time. We experimentally demonstrated that using our approach, it is possible to determine and to distinguish borders of different bimolecular compounds in a short time. Because the method can be transferred to other optical probes and other spectroscopic techniques, it is expected that the implementation will have a large impact for clinical, biomedical and industrial applications.      

Quantitative FRET measurement based on spectral unmixing of donor,acceptor and spontaneous excitation‐emission spectra

The spontaneous excitation‐emission (ExEm) spectrum is introduced to the quantitative mExEm‐spFRET methodology we recently developed as a spectral unmixing component for quantitative fluorescence resonance energy transfer measurement, named as SPEES‐FRET method. The spectral fingerprints of both donor and acceptor were measured in HepG2 cells with low autofluorescence separately expressing donor and acceptor, and the spontaneous spectral fingerprint of HEK293 cells with strong autofluoresence was measured from blank cells. SPEES‐FRET was performed on improved spectrometer‐microscope system to measure the FRET efficiency (E) and concentration ratio (R _C) of acceptor to donor vales of FRET tandem plasmids in HEK293 cells, and obtained stable and consistent results with the expected values. Moreover, SPEES‐FRET always obtained stable results for the bright and dim cells coexpressing Cerulean and Venus or Cyan Fluorescent Protein (CFP)‐Bax and Yellow fluorescent protein (YFP)‐Bax, and the E values between CFP‐Bax and YFP‐Bax were 0.02 for healthy cells and 0.14 for the staurosporine (STS)‐treated apoptotic cells. Collectively, SPEES‐FRET has very strong robustness against cellular autofluorescence, and thus is applicable to quantitative evaluation on the protein‐protein interaction in living cells with strong autofluoresence.      

Surface analysis of sheep menisci after meniscectomy via infrared attenuated total reflection spectroscopy

Menisci are very important fibrocartilaginous tissue, which maintain biomechanical functions and physiological stabilization of knee joint. Meniscectomy is known as a surgery to recover partial functions from acute meniscus tears. However, the late consequences of total or partial meniscectomy include signs of osteoarthritis and even ligament instability. Infrared attenuated total reflection (IR‐ATR) spectroscopy is a very useful technique, which can reveal molecular characteristics via the analysis of vibrational bands. The present study has employed IR‐ATR spectroscopy to investigate sheep menisci samples after meniscectomy in a label‐free fashion. Several differences of peak absorbance change and peak shift were observed between the native healthy samples and the meniscectomy samples in distinct IR wavenumber regions, such as amide I band, amide II band, C‐H bending band as well as the sugar band region. Combining the results from the collagen protein IR spectra, it can be speculated that six months after meniscectomy collagen fibrils on the incision lose its ordered arrangement and a decrease in the triple helical structure of collagen fibril is observed. In addition, the collagen fibrils and proteoglycan content might also be slight varied after meniscectomy.      

Integration of diffraction phase microscopy and Raman imaging for label‐free morpho‐molecular assessment of live cells

Label‐free quantitative imaging is highly desirable for studying live cells by extracting pathophysiological information without perturbing cell functions. Here, we demonstrate a novel label‐free multimodal optical imaging system with the capability of providing comprehensive morphological and molecular attributes of live cells. Our morpho‐molecular microscopy (3M) system draws on the combined strength of quantitative phase microscopy (QPM) and Raman microscopy to probe the morphological features and molecular fingerprinting characteristics of each cell under observation. While the commonr‐path geometry of our QPM system allows for highly sensitive phase measurement, the Raman microscopy is equipped with dual excitation wavelengths and utilizes the same detection and dispersion system, making it a distinctive multi‐wavelength system with a small footprint. We demonstrate the applicability of the 3M system by investigating nucleated and nonnucleated cells. This integrated label‐free platform has a promising potential in preclinical research, as well as in clinical diagnosis in the near future.      

The potential of biobanked liquid based cytology samples for cervical cancer screening using Raman spectroscopy

Patient samples are unique and often irreplaceable. This allows biobanks to be a valuable source of material. The aim of this study was to assess the ability of Raman spectroscopy to screen for histologically confirmed cases of Cervical Intraepithelial neoplasia (CIN) using biobanked liquid based cytology (LBC) samples. Two temperatures for long term storage were assessed; 80°C and ?25°C. The utility of Raman spectroscopy for the detection of CIN was compared for fresh LBC samples and biobanked LBC samples. Two groups of samples were used for the study with one group associated with disease (CIN 3) and the other associated with no disease (cytology negative). The data indicates that samples stored at ?80°C are not suitable for assessment by Raman spectroscopy due to a lack of cellular material and the presence of cellular debris. However, the technology can be applied to fresh LBC samples and those stored at ?25°C and is, moreover, effective in the discrimination of negative samples from those where CIN 3 has been confirmed. Pooled fresh and biobanked samples are also amenable to the technology and achieve a similar sensitivity and specificity for CIN 3. This study demonstrates that cervical cytology samples stored within biobanks at temperatures that preclude cell lysis can act as a useful resource for Raman spectroscopy and will facilitate research and translational studies in this area.      

Inline noninvasive Raman monitoring and feedback control of glucose concentration during ethanol fermentation

Raman spectroscopy as a process analytical technology tool was implemented for the monitoring and control of ethanol fermentation carried out with Saccharomyces cerevisiae. The need for the optimization of bioprocesses such as ethanol production, to increase product yield, enhanced the development of control strategies. The control system developed by the authors utilized noninvasive Raman measurements to avoid possible sterilization problems. Real-time data analysis was applied using partial least squares regression (PLS) method. With the aid of spectral pretreatment and multivariate data analysis, the monitoring of glucose and ethanol concentration was successful during yeast fermentation with the prediction error of 4.42 g/L for glucose and 2.40 g/L for ethanol. By Raman spectroscopy-based feedback control, the glucose concentration was maintained at 100 g/L by the automatic feeding of concentrated glucose solution. The control of glucose concentration during fed-batch fermentation resulted in increased ethanol production. Ethanol yield of 86% was achieved compared to the batch fermentation when 75 % yield was obtained. The results show that the use of Raman spectroscopy for the monitoring and control of yeast fermentation is a promising way to enhance process understanding and achieve consistently high production yield.