Nanoscale chemical characterization of materials and interfaces by tip-enhanced Raman spectroscopy.

Materials and their interfaces are the core for the development of a large variety of fields, including catalysis, energy storage and conversion. In this case, tip-enhanced Raman spectroscopy (TERS), which combines scanning probe microscopy with plasmon-enhanced Raman spectroscopy, is a powerful technique that can simultaneously obtain the morphological information and chemical fingerprint of target samples at nanometer spatial resolution. It is an ideal tool for the nanoscale chemical characterization of materials and interfaces, correlating their structures with chemical performances. In this review, we begin with a brief introduction to the nanoscale characterization of materials and interfaces, followed by a detailed discussion on the recent theoretical understanding and technical improvements of TERS, including the origin of enhancement, TERS instruments, TERS tips and the application of algorithms in TERS. Subsequently, we list the key experimental issues that need to be addressed to conduct successful TERS measurements. Next, we focus on the recent progress of TERS in the study of various materials, especially the novel low-dimensional materials, and the progresses of TERS in studying different interfaces, including both solid-gas and solid-liquid interfaces. Finally, we provide an outlook on the future developments of TERS in the study of materials and interfaces.

Neural Encoding for Spatial Release from Informational Masking and its Correlation with Behavioral Metrics.

The central auditory system encompasses two primary functions: identification and localization. Spatial release from masking (SRM) highlights speech recognition in competing noise and improves the listening experience when a spatial cue is introduced between noise and target speech. This assessment focuses on the integrity of auditory function and holds clinical significance. However, infants or pre-lingual subjects sometimes provide less reliable results. This study investigates the value of cortical auditory evoked potentials (CAEPs) onset and acoustic change complex (ACC) as an objective measurement of SRM. Thirty normal-hearing young adults (11 males) were recruited. We found the spatial separation of signals and noise (±90 degrees symmetrically) resulted in a signal-to-noise ratio (SNR) improvement of 9.00 ± 1.71 dB behaviorally. It significantly enhanced cortical processing at all SNR levels, shortened CAEPs latencies, and increased amplitudes, resulting in a greater number of measurable peaks for ACC. SRM showed mild to moderate correlations with the differences between the two conditions in CAEP measures. The regression model combining N1'-P2' amplitude at 5 dB SNR (R2 = 0.26), P1 amplitude at 0 dB SNR (R2 = 0.14), and P1 latency at -5 dB SNR (R2 = 0.15), explained 45.3% of the variance in SRM. Our study demonstrates that introducing spatial cues can improve speech perception and enhance central auditory processing in normal-hearing young adults. CAEPs may contribute to predictions about SRM and hold potential for practical application.

Micro Reference Electrode with an Ultrathin Ionic Path.

Reference electrode (RE) plays the core role in accurate potential control in electrochemistry. However, nanoresolved electrochemical characterization techniques still suffer from unstable potential control of pseudo-REs, because the commercial RE is too large to be used in the tiny electrochemical cell, and thus only pseudo-RE can be used. Therefore, microsized RE with a stable potential is urgently required to push the nanoresolved electrochemical measurements to a new level of accuracy and precision, but it is quite challenging to reproducibly fabricate such a micro RE until now. Here, we revisited the working mechanism of the metal-junction RE and clearly revealed the role of the ionic path between the metal wire and the borosilicate glass capillary to maintain a stable potential of RE. Based on this understanding, we developed a method to fabricate micro ultrastable-RE, where a reproducible ultrathin ionic path can form by dissolving a sandwiched sacrificial layer between the Pt wire and the capillary for the ion transfer. The potential of this new micro RE was almost the same as that of the commercial Ag/AgCl electrode, while the size is much smaller. Different from commercial REs that must be stored in the inner electrolyte, the new RE could be directly stored in air for more than one year without potential drift. Eventually, we successfully applied the micro RE in the electrochemical tip-enhanced Raman spectroscopy (EC-TERS) measurement to precisely control the potential of the working electrode, which makes it possible to compare the results from different laboratories and techniques to better understand the electrochemical interface at the nanoscale.

Development and characterisation of [18F]TTDP, a novel T cell immunoglobulin and ITIM domain tracer, in humanised mice and non-human primates.

PURPOSE: The T cell immunoglobulin and ITIM domain (TIGIT) blockade immunotherapy response is directly associated with individual differences of TIGIT expression on tumour-infiltrating lymphocytes (TILs) in tumour immune microenvironment (TIME) of non-small cell lung cancer (NSCLC). Here, we developed a TIGIT-targeted PET tracer to evaluate its feasibility in predicting immunotherapy efficacy, aiming to manage NSCLC patients accurately. METHODS: We synthesised a 18F-labeled TIGIT-targeted D-peptide, [18F]TTDP, and investigated the specificity of [18F]TTDP both to murine TIGIT and human TIGIT by a series of in vitro and in vivo assays. [18F]TTDP PET imaging was performed in humanised immune system (HIS) mice models bearing NSCLC patient-derived xenografts (PDXs) to evaluate the predictive value of FDA-approved combination immunotherapy of atezolizumab plus tiragolumab. Lastly, rhesus macaque was applied for [18F] TTDP PET to explore the tracer's in vivo distribution and translational potential in non-human primates. RESULTS: [18F]TTDP showed high specificity for both murine TIGIT and human TIGIT in vitro and in vivo. The HIS NSCLC PDX platform was successfully established for [18F]TTDP PET imaging, and tumour uptake of [18F]TTDP was significantly correlated with the TIGIT expression of TILs in the TIME. [18F]TTDP PET imaging, in predicting treatment response to the combination immunotherapy in NSCLC HIS-PDX models, showed a sensitivity of 83.33% and a specificity of 100%. In addition, [18F]TTDP PET also showed cross-species consistency of the tracer biodistribution between non-human primate and murine animals, and no adverse events were observed. CONCLUSION: The combined implementation of the [18F]TTDP and HIS-PDX model creates a state-of-the-art preclinical platform that will impact the identification and validation of TIGIT-targeted PET image-guided diagnosis, treatment response prediction, beneficial patient screening, novel immunotherapies, and ultimately the outcome of NSCLC patients. We first provided in vivo biodistribution of [18F]TTDP PET imaging in rhesus macaque, indicating its excellent translational potential in the clinic.

Halogen Engineering Strategy-Induced Color-Tunable Room Temperature Phosphorescence in Metal-Organic Halides.

Color-tunable room temperature phosphorescence (RTP) materials possess potential applications in multicolor imaging, multichannel anticounterfeiting, and information encryption. Herein, we synthesized two zero-dimensional cadmium-organic halides, (H-aepy)2CdX4 (referred to as CdX-aepy; X = Cl-, Br-; aepy = 3-(2-aminoethyl)pyridine), both of which exhibit long-lived excitation wavelength- and time-dependent RTP. Experimental and theoretical results suggest that the multicolor RTP can be ascribed to the coemission of pristine H-aepy ligands and halogen-affected H-aepys, supporting that suitably introducing halogens can be an efficient strategy for constructing multicolor RTP materials. Additionally, we also demonstrate that the two phosphors can be applied in multichannel anticounterfeiting and information encryption. This work reports two hybrids with color-tunable RTP, as well as provides new insight into the effect of halogens on the regulation of RTP.

External Fields Assisted Highly Efficient Oxygen Evolution Reaction of Confined 1T-VSe2 Ferromagnetic Nanoparticles.

As a clean and effective approach, the introduction of external magnetic fields to improve the performance of catalysts has attracted extensive attention. Owing to its room-temperature ferromagnetism, chemical stability, and earth abundance, VSe2 is expected to be a promising and cost-effective ferromagnetic electrocatalyst for the accomplishment of high-efficient spin-related OER kinetics. In this work, a facile pulsed laser deposition (PLD) method combined with rapid thermal annealing (RTA) treatment is used to successfully confine monodispersed 1T-VSe2 nanoparticles in amorphous carbon matrix. As expected, with external magnetic fields of 800 mT stimulation, the confined 1T-VSe2 nanoparticles exhibit highly efficient oxygen evolution reaction (OER) catalytic activity with an overpotential of 228 mV for 10 mA cm-2 and remarkable durability without deactivation after >100 h OER operation. The experimental results together with theoretical calculations illustrate that magnetic fields can facilitate the surface charge transfer dynamics of 1T-VSe2 , and modify the adsorption-free energy of *OOH, thus finally improving the intrinsic activity of the catalysts. This work realizes the application of ferromagnetic VSe2 electrocatalyst in highly efficient spin-dependent OER kinetics, which is expected to promote the application of transition metal chalcogenides (TMCs) in external magnetic field-assisted electrocatalysis.

Bloom-induced internal release controlling phosphorus dynamics in large shallow eutrophic Lake Taihu, China.

High phosphorus (P) concentrations are commonly observed in lakes during algal blooms despite massive efforts on external nutrient reduction. However, the knowledge about the relative contribution of internal P loading linked with algal blooms on lake phosphorus (P) dynamics remains limited. To quantify the effect of internal loading on P dynamics, we conducted extensive spatial and multi-frequency nutrient monitoring from 2016 to 2021 in Lake Taihu, a large shallow eutrophic lake in China, and its tributaries (2017-2021). The in-lake P stores (ILSP) and external loading were estimated and then internal P loading was quantified from the mass balance equation. The results showed that the in-lake total P stores (ILSTP) ranged from 398.5 to 1530.2 tons (t), and exhibited a dramatic intra- and inter-annual variability. The annual internal TP loading released from sediment ranged from 1054.3 to 1508.4 t, which was equivalent to 115.6% (TP loading) of the external inputs on average, and responsible for the fluctuations of ILSTP on a weekly scale. High-frequency observations exemplified that ILSTP increased by 136.4% during algal blooms in 2017, while by only 47.2% as a result of external loading after heavy precipitation in 2020. Our study demonstrated that both bloom-induced internal loading and storm-induced external loading are likely to run counter significantly to watershed nutrient reduction efforts in large shallow lakes. More importantly, bloom-induced internal loading is higher than storm-induced external loading over the short term. Given the positive feedback loop between internal P loadings and algal bloom in eutrophic lakes, which explains the significant fluctuation of P concentration while nitrogen concentration decreased. It is emphasized that internal loading and ecosystem restoration are unignorable in shallow lakes, particularly in the algal-dominated region.

Temporal dependence of chlorophyll a-nutrient relationships in Lake Taihu: Drivers and management implications.

Eutrophication and its associated algal blooms are principal environmental challenges confronting lakes worldwide. The empirical relationships between nutrient (total nitrogen, TN; total phosphorus, TP) and chlorophyll a (Chla) level are widely used as a theoretical basis for lake eutrophication management. Here, seasonal environmental variables and Chla from 2005 to 2020 in Chinese shallow eutrophic Lake Taihu were examined and Chla-nutrient equations in the entire period and annually from 2005 to 2020 were explored using 95% quantile regression model. The results showed robust linear relationships of logChla-logTN and logChla-logTP in the vast majority of cases. Based on Chla-nutrient equations in the entire study period, 0.69 mg/L TN and 52 µg/L TP are recommended as nutrient threshold in Lake Taihu. Furthermore, the results revealed increasing Chla sensitivity to nutrient for each study month (i.e. February, May, August, and November) from 2005 to 2020, whose drivers included increase in water temperature and water level, decrease in wind speed, mass ratio of nitrogen to phosphorus, and grazing effect. It is noteworthy that atmospheric stilling is likely to be the key climatic factor promoting annual peak Chla in Lake Taihu. For one, the deviations of the sub-index of Trophic State Index indicated that light is a critical limiting factor of summer Chla in Lake Taihu. For another, calmer water mainly due to atmospheric stilling decreased near 40% non-algal turbidity and a substantially increased buoyant cyanobacteria during the study period, improving phytoplankton "light niche". Thus, increasing algal sensitivity to nutrient occurred until the additional algal-turbidity induce further light limitations or the exhaustion of TN (or TP) cause nutrient limitation. Given atmospheric stilling is a global phenomenon, this study would affect future algal bloom mitigation efforts in shallow lakes as temperature is always the focus in the recent literatures on global climate change.

Elucidating phytoplankton limiting factors in lakes and reservoirs of the Chinese Eastern Plains ecoregion.

Knowledge of phytoplankton limiting factors is essential for cost-efficient lake eutrophication management. Herein, we propose a statistical framework to explore site-specific phytoplankton limiting factors and their dependence on water depth (WD) in 54 lakes in the Chinese Eastern Plains ecoregion. First, the maximal chlorophyll a (Chla) response to total N (TN) or P (TP), representing a region-specific "standard" model where phytoplankton were primarily N- or P-limited, was quantified using a 95% quantile regression. Second, site-specific limiting factors were identified using analogical residual analysis. N- or P-limitation was inferred if FractionTN (i.e. fraction of Chla observed and predicted by the "standard" model for a given TN) > 0.95 or FractionTP >0.95; if both FractionTN and FractionTP <0.95 in a specific environmental condition (e.g. high non-algal turbidity), light limitation was suggested. As a result, 5%, 7%, 4%, 36%, 16%, 2%, and 30% of the sampling sites were limited by N, P, N+P, light availability, rapid flushing, abundant macrophytes, and unmeasured factors, respectively. Bloom control suggestions in the short run are proposed considering these actual limiting factors. Furthermore, the maximal FractionTN or FractionTP response to WD was explored, reflecting the effect of WD on FractionTN (or FractionTP) without significant confounders. The results indicated that phytoplankton in the studied freshwaters would be potentially light-limited, N-limited, N+P-co-limited, or P-limited depending on WD (<1.8, 1.8-2.1, 2.1-5.2, or >5.2 m, respectively), because N will gradually become surplus with increasing WD, while at very shallow depths, strong sediment re-suspension induces light limitation. This finding implies that long-term nutrient management strategies in the studied freshwaters that have WDs of 0-2.1, 2.1-5.2, and >5.2 m can entail control of N, N+P, and P, respectively. This study provides essential information for formulating context-dependent bloom control for lakes in our study area and serves as a valuable reference for developing a cost-efficient eutrophication management framework for other regions.

New insights into eutrophication management: Importance of temperature and water residence time.

Eutrophication and harmful cyanobacterial blooms threaten water resources all over the world. There is a great controversy about controlling only phosphorus or controlling both nitrogen and phosphorus in the management of lake eutrophication. The primary argument against the dual nutrients control of eutrophication is that nitrogen fixation can compensate the nitrogen deficits. Thus, it is of great necessary to study the factors that can significantly affect the nitrogen fixation. Due to the difference of climate and human influence, the water quality of different lakes (such as water temperature, N:P ratio and water residence time) is also quite different. Numerous studies have reported that the low N:P ratio can intensify the nitrogen fixation capacities. However, the effects of temperature and water residence time on the nitrogen fixation remain unclear. Thus, 30 shallows freshwater lakes in the eastern plain of China were selected to measure dissolved N2 and Ar concentrations through N2: Ar method using a membrane inlet mass spectrometer to quantify the nitrogen fixation capacities and investigate whether the temperature and water residence time have a great impact on nitrogen fixation. The results have shown that the short lake water residence time can severely inhibit the nitrogen fixation capacities through inhibiting the growth of nitrogen-fixing cyanobacteria, changing the N:P ratio and resuspending the solids from sediments. Similarly, lakes with low water temperature also have a low nitrogen fixation capacity, suggesting that controlling nitrogen in such lakes is feasible if the growth of cyanobacteria is limited by nitrogen.