Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics.

The dynamics, orientational anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO2), and lithium nitrate (LiNO3), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. The 2D IR, NMR, and viscosity results show that LiNO2 exhibits longer correlation times, lower diffusivity, and nearly 4 times greater viscosity compared to those of the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion network interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO2 and LiNO3 solutions show significantly weakened chemical interactions between the lithium cations and the methyl thiocyanate when compared with those of the lithium halide salts.

Nutrient Composition and Flavor Profile of Crucian Carp Soup Utilizing Fish Residues through Comminution and Pressure-Conduction Treatment.

In conventional fish soup processing, valuable aquatic resources like fish skins, bones, and scales are often squandered. This study was aimed at investigating if comminution combined with pressure-conduction treatment has the potential to enhance the reutilization of cooking residues. The different blending ratios of original soup (OS), made from the initial cooking of fish, and residue soup (RS), produced from processed leftover fish parts, were alternatively investigated to satisfy the new product development. Comminution combined with pressure-conduction treatment significantly increased the nutrient contents of calcium, soluble proteins and total solids in crucian carp soup (p < 0.05). With the increase in RS ratio, the decomposition of inosine monophosphate (IMP) and free amino acids was accelerated, but the accumulation of aromatic compounds was promoted simultaneously. In addition, the Maillard reaction may lead to a reduction in aldehydes, causing a diminution in the characteristic flavor of fish soup, while the formation of 1-octen-3-ol can enhance the earthiness of the fish soup. The electronic tongue test results and the sensory results showed that the blend ratio of OS and RS at 7:3 had a more significant umami and fish aroma (p < 0.05). Under this condition, the mixed soup has better nutritional values and flavor characteristics.

Facet-dependent dispersion and aggregation of aqueous hematite nanoparticles.

Nanoparticle aggregates in solution controls surface reactivity and function. Complete dispersion often requires additive sorbents to impart a net repulsive interaction between particles. Facet engineering of nanocrystals offers an alternative approach to produce monodisperse suspensions simply based on facet-specific interaction with solvent molecules. Here, we measure the dispersion/aggregation of three morphologies of hematite (α-Fe2O3) nanoparticles in varied aqueous solutions using ex situ electron microscopy and in situ small-angle x-ray scattering. We demonstrate a unique tendency of (104) hematite nanoparticles to maintain a monodisperse state across a wide range of solution conditions not observed with (001)- and (116)-dominated particles. Density functional theory calculations reveal an inert, densely hydrogen-bonded first water layer on the (104) facet that favors interparticle dispersion. Results validate the notion that nanoparticle dispersions can be controlled through morphology for specific solvents, which may help in the development of various nanoparticle applications that rely on their interfacial area to be highly accessible in stable suspensions.

Konjac glucomannan-assisted fabrication of stable emulsion-based oleogels constructed with pea protein isolate and its application in surimi gels.

Konjac glucomannan (KGM) is widely used as a stabilizer for the structuring of highly unsaturated oils. This study aimed to investigate the changes in structure and functional properties of soybean oil - based oleogels (emulsion template method) prepared with different amounts of KGM-modified pea isolate protein (PPI). The findings revealed that the oleogels formed three - dimensional networks through van der Waals interactions and hydrogen bonding between the stretched PPI and KGM. As the amount of KGM increased, the oil droplets were more uniformly dispersed within the continuous PPI - KGM rigid network, especially when the ratio of PPI to KGM was 4:1. This formulation also showed the highest thixotropy (73.2 %) and the best oil binding capacity (94 %). Cryo - SEM revealed that the oleogel - prepared surimi gels successfully enclosed oil droplets in a dense matrix through a dual stabilization mechanism. Additionally, the incorporation of oleogels significantly improved the textural properties of surimi in comparison to directly adding oil.

Development of Shark Single Domain Antibodies Specific for Human α-Fetoprotein and the Multimerization Strategy in Serum Detection.

Sensitive detection of cancer biomarkers can contribute to the timely diagnosis and treatment of diseases. In this study, the whitespotted bamboo sharks were immunized with human α-fetoprotein (AFP), and a phage-displayed variable new antigen receptor (VNAR) single domain antibody library was constructed. Then four unique VNARs (VNAR1, VNAR11, VNAR21, and VNAR25) against AFP were isolated from the library by biopanning for the first time. All of the sequences belong to type II of VNAR, and the VNAR11 was much different from the rest of the three sequences. Then VNAR1 and VNAR11 were selected to fuse with the C4-binding protein α chain (C4bpα) sequence and efficiently expressed in the Escherichia coli system. Furthermore, a VNAR-C4bpα-mediated sandwich chemiluminescence immunoassay (VSCLIA) was developed for the detection of AFP in human serum samples. After optimization, the VSCLIA showed a limit of detection of 0.74 ng/mL with good selectivity and accuracy. Moreover, the results of clinical serum samples detected by the VSCLIA were confirmed by an automatic immunoanalyzer in the hospital, indicating its practical application in actual samples. In conclusion, the novel antibody element VNAR exhibits great potential for immunodiagnosis, and this study also provides a new direction and experimental basis for AFP detection.

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

Lateral Flow Immunochromatographic Assay for Competitive Detection of Crustacean Allergen Tropomyosin Using Phage-Displayed Shark Single-Domain Antibody.

The common food allergy crustacean tropomyosin (TM) poses a significant food safety challenge, which requires rapid and sensitive methods for screening TM in food. Herein, the variable new antigen receptor (VNAR) single-domain antibodies specific for the crustacean TM were isolated from a naïve phage-displayed shark VNAR library. Subsequently, a lateral flow immunochromatographic assay (LFIA) based on the gold nanoparticle-labeled phage-displayed shark VNAR (AuNPs@PSV) probe was developed for the detection of TM in food. The AuNPs@PSV-LFIA took 15 min for one test and had a visual limit of detection (vLOD) of 0.1 µg/mL and an instrumental LOD of 0.02 µg/mL. Good selectivity, accuracy, precision, and stability were confirmed for the AuNPs@PSV-LFIA. Moreover, the test results of 21 commercially available food products consisted of the allergen labels and were validated by a commercial ELISA kit. Therefore, this work demonstrated the great potential of VNAR for detecting TM in food by LFIA.

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions.

Understanding the dissolution of boehmite in highly alkaline solutions is important to processing complex nuclear waste stored at the Hanford (WA) and Savannah River (SC) sites in the United States. Here, we report the adsorption of model carboxylates on boehmite nanoplates in alkaline solutions and their effects on boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate occurred at pH 13, with adsorption decreasing linearly to 3 M NaOH. Classical molecular dynamics simulations suggest that the adsorption of oxalate dianions onto the boehmite surface under high pH can occur through either inner- or outer-sphere complexation mechanisms depending on adsorption sites. However, both adsorption models indicate relatively weak binding, with an energy preference of 1.26 to 2.10 kcal/mol. By preloading boehmite nanoplates with oxalate or acetate, we observed suppression of dissolution rates by 23 or 10%, respectively, compared to pure solids. Scanning electron microscopy and transmission electron microscopy characterizations revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. We conclude that preadsorbed carboxylates can persist on boehmite surfaces, decreasing the density of dissolution-active sites and thereby adding extrinsic controls on dissolution rates.

Fast Attack Detection for Cyber-Physical Systems Using Dynamic Data Encryption.

To defend the cyber-physical system (CPSs) from cyber-attacks, this work proposes an unified intrusion detection mechanism which is capable to fast hunt various types of attacks. Focusing on securing the data transmission, a novel dynamic data encryption scheme is developed and historical system data is used to dynamically update a secret key involved in the encryption. The core idea of the dynamic data encryption scheme is to establish a dynamic relationship between original data, secret key, ciphertext and its decrypted value, and in particular, this dynamic relationship will be destroyed once an attack occurs, which can be used to detect attacks. Then, based on dynamic data encryption, a unified fast attack detection method is proposed to detect different attacks, including replay, false data injection (FDI), zero-dynamics, and setpoint attacks. Extensive comparison studies are conducted by using the power system and flight control system. It is verified that the proposed method can immediately trigger the alarm as soon as attacks are launched while the conventional χ2 detection could only capture the attacks after the estimation residual goes over the predetermined threshold. Furthermore, the proposed method does not degrade the system performance. Last but not the least, the proposed dynamic encryption scheme turns to normal operation mode as the attacks stop.

Directing polymorph specific calcium carbonate formation with de novo protein templates.

Biomolecules modulate inorganic crystallization to generate hierarchically structured biominerals, but the atomic structure of the organic-inorganic interfaces that regulate mineralization remain largely unknown. We hypothesized that heterogeneous nucleation of calcium carbonate could be achieved by a structured flat molecular template that pre-organizes calcium ions on its surface. To test this hypothesis, we design helical repeat proteins (DHRs) displaying regularly spaced carboxylate arrays on their surfaces and find that both protein monomers and protein-Ca2+ supramolecular assemblies directly nucleate nano-calcite with non-natural {110} or {202} faces while vaterite, which forms first in the absence of the proteins, is bypassed. These protein-stabilized nanocrystals then assemble by oriented attachment into calcite mesocrystals. We find further that nanocrystal size and polymorph can be tuned by varying the length and surface chemistry of the designed protein templates. Thus, bio-mineralization can be programmed using de novo protein design, providing a route to next-generation hybrid materials.

Multiparametric MRI for evaluation of pathological response to the neoadjuvant chemo-immunotherapy in resectable non-small-cell lung cancer.

OBJECTIVES: This study aimed to explore the predictive value of intravoxel incoherent motion diffusion-weighted imaging (IVIM-DWI) and diffusion kurtosis imaging (DKI) quantitative parameters for the response to neoadjuvant chemo-immunotherapy (NCIT) in resectable non-small-cell lung cancer (NSCLC) patients, so as to provide a basis for clinical individualized precision treatment. METHODS: Treatment naive locally advanced NSCLC patients who enrolled in 3 prospective, open-label, and single-arm clinical trials and received NCIT were retrospectively analyzed in this study. Functional MRI imaging was performed at baseline and following 3 weeks of treatment as an exploratory endpoint to evaluate treatment efficacy. Univariate and multivariate logistic regressions were used to identify independent predictive parameters for NCIT response. Prediction models were built with statistically significant quantitative parameters and their combinations. RESULTS: In total of 32 patients, 13 were classified as complete pathological response (pCR) and 19 were non-pCR. Post-NCIT ADC, ΔADC, and ΔD values in the pCR group were significantly higher than those in the non-pCR group, while the pre-NCIT D, post-NCIT Kapp, and ΔKapp were significantly lower than those in non-pCR group. Multivariate logistic regression analysis demonstrated that pre-NCIT D and post-NCIT Kapp values were independent predictors for NCIT response. The combined predictive model, which consisted of IVIM-DWI and DKI, showed the best prediction performance with AUC of 0.889. CONCLUSIONS: The pre-NCIT D, post-NCIT parameters (ADC and Kapp) and Δ parameters (ΔADC, ΔD, and ΔKapp) were effective biomarkers for predicting pathologic response, and pre-NCIT D and post-NCIT Kapp values were independent predictors of NCIT response for NSCLC patients. CLINICAL RELEVANCE STATEMENT: This exploratory study indicated that IVIM-DWI and DKI MRI imaging would predict pathologic response of neoadjuvant chemo-immunotherapy in locally advanced NSCLC patients at initial state and early treatment, which could help make clinical individualized treatment strategies. KEY POINTS: • Effective NCIT treatment resulted in increased ADC and D values for NSCLC patients. • The residual tumors in non-pCR group tend to have higher microstructural complexity and heterogeneity, as measured by Kapp. • Pre-NCIT D and post-NCIT Kapp values were independent predictors of NCIT response.

Global status of phenotypic pyrazinamide resistance in Mycobacterium tuberculosis clinical isolates: an updated systematic review and meta-analysis.

Pyrazinamide (PZA) is an essential first-line tuberculosis drug for its unique mechanism of action active against multidrug-resistant-TB (MDR-TB). Thus, the aim of updated meta-analysis was to estimate the PZA weighted pooled resistance (WPR) rate in M. tuberculosis isolates based on publication date and WHO regions. We systematically searched the related reports in PubMed, Scopus, and Embase (from January 2015 to July 2022). Statistical analyses were performed using STATA software. The 115 final reports in the analysis investigated phenotypic PZA resistance data. The WPR of PZA was 57% (95% CI 48-65%) in MDR-TB cases. According to the WHO regions, the higher WPRs of PZA were reported in the Western Pacific (32%; 95% CI 18-46%), South East Asian region (37%; 95% CI 31-43%), and the Eastern Mediterranean (78%; 95% CI 54-95%) among any-TB patients, high risk of MDR-TB patients, and MDR-TB patients, respectively. A negligible increase in the rate of PZA resistance were showed in MDR-TB cases (55% to 58%). The rate of PZA resistance has been rising in recent years among MDR-TB cases, underlines the essential for both standard and novel drug regimens development.

Regulation of the Colour Change of 3D-Printed Mackerel Mince (Scomber scombrus) Based on Purple Potato Powder and Citric Acid.

The present study evaluates the effect of purple potato (PP) powder and citric acid (CA) on the regulation of the colour change of 3D (three-dimensional) printed mackerel mince (Scomber scombrus). In addition, the effects of PP and CA content on the 3D-printability and quality of mackerel mince were also investigated. The results showed that an increase in PP and CA concentrations gradually brightened the product colour and turned it pink. Furthermore, an increase in PP concentration and added CA reduced the fluidity and loss of water in mackerel mince. Proper PP and CA concentrations moderately increased the storage modulus (G'), loss modulus (G″), and yield stress of mackerel mince, making it suitable for 3D printing. At the same time, an increase in PP and CA concentrations enhanced the umami and sweet taste of mackerel mince but reduced the fishy and sour taste, and the degree of preference was within the acceptable range, except for PP1%-CA0%. It was found that, when the 3D-printing accuracy of mackerel-mince samples reached more than 97% and was acceptable, the optimal PP and CA concentrations for realizing the regulation of L*, a*, and b* were 1.00~3.00% and 0.09~0.32%, respectively.

Unprecedented Ferroelectricity and Ferromagnetism in a Cr2+ -Based Two-Dimensional Hybrid Perovskite.

Organic-inorganic hybrid perovskites (OIHPs) have gained tremendous interest for their rich functional properties. However, the coexistence of more than one of ferroelectricity, ferromagnetism and ferroelasticity has been rarely found in OIHPs. Herein, we report a two-dimensional Cr2+ -based OIHP, [3,3-difluorocyclobutylammonium]2 CrCl4 ([DFCBA]2 CrCl4 ), which shows both ferroelectricity and ferromagnetism. It undergoes a 4/mmmFm type ferroelectric phase transition at a temperature as high as 387 K and shows multiaxial ferroelectricity with a saturate polarization of 2.1 µC cm-2 . It acts as a soft ferromagnet with a Curie temperature of 32.6 K. This work throws light on the exploration of OIHPs with the coexistence of ferroelectricity and ferromagnetism for applications in future multifunctional smart devices.

Spin-Electric Coupling with Anisotropy-Induced Vanishment and Enhancement in Molecular Ferroelectrics.

Manipulating quantum properties by electric fields using spin-electric coupling (SEC) effects promises spatial addressability. While several studies about inorganic materials showing the SEC functionality have been reported, the vastly tunable crystal structures of molecular ferroelectrics provide a range of rationally designable materials yet to be exploited. In this work, Mn2+-doped molecular ferroelectrics are chosen to experimentally demonstrate the feasibility of achieving the quantum coherent SEC effect in molecular ferroelectrics for the first time. The electric field pulse applied between Hahn-echo pulses in electron paramagnetic resonance (EPR) experiments causes controllable phase shifts via manipulating of the zero-field splitting (ZFS) of the Mn(II) ions. Detailed investigations of the aMn crystal showed unexpected SEC vanishment and enhancement at different crystal orientations, which were elucidated by studying the spin Hamiltonian and magnetic anisotropy. With the enhanced SEC efficiency being achieved (0.68 Hz m/V), this work discovers an emerging material library of molecular ferroelectrics to implement coherent quantum control with selective and tunable SEC effects toward highly scalable quantum gates.

Insights into sorption speciation of uranium on phlogopite: Evidence from TRLFS and DFT calculation.

Knowledge of the sorption speciation of uranium at mineral/water interface is essential to construct reliable retention and migration models. In this work, the sorption speciation of U(VI) at the phlogopite/water interface was studied at trace concentrations by combining batch sorption, time-resolved luminescence spectroscopy, and theoretical calculation. Batch experiments showed that the sorption of U(VI) on phlogopite was strongly dependent on pH but weakly affected by ionic strength, implying that the inner-sphere surface complexation was mainly responsible for U(VI) sorption on phlogopite. The diverse luminescence spectral characteristics indicated the formation of multiple inner-sphere surface species at the phlogopite/water interface, whose abundances varied as a function of pH. A portion of U(VI) precipitated as uranyl oxyhydroxides such as metaschoepite and becquerelite at high pH. Density functional theory calculation revealed that the bidentate complex at the edge of phlogopite (≡AlO-MgO-UO2(H2O)3) was the most favorable sorption configuration for U(VI) at acidic condition. The increasing temperature enhanced the sorption of U(VI) on phlogopite without altering the sorption species, and such enhancement in U(VI) sorption was withdrawn once the temperature decreased. These findings are essential for understanding the immobilization mechanism of U(VI) in mica-rich granitic terrains at a molecular scale and building a reliable retention model.

Marine Bioactive Compounds as Nutraceutical and Functional Food Ingredients for Potential Oral Health.

Oral diseases have received considerable attention worldwide as one of the major global public health problems. The development of oral diseases is influenced by socioeconomic, physiological, traumatic, biological, dietary and hygienic practices factors. Currently, the main prevention strategy for oral diseases is to inhibit the growth of biofilm-producing plaque bacteria. Tooth brushing is the most common method of cleaning plaque, aided by mouthwash and sugar-free chewing gum in the daily routine. As the global nutraceutical market grows, marine bioactive compounds are becoming increasingly popular among consumers for their antibacterial, anti-inflammatory and antitumor properties. However, to date, few systematic summaries and studies on the application of marine bioactive compounds in oral health exist. This review provides a comprehensive overview of different marine-sourced bioactive compounds and their health benefits in dental caries, gingivitis, periodontitis, halitosis, oral cancer, and their potential use as functional food ingredients for oral health. In addition, limitations and challenges of the application of these active ingredients are discussed and some observations on current work and future trends are presented in the conclusion section.

Coexistence of magnetic and electric orderings in a divalent Cr2+-based multiaxial molecular ferroelectric.

Multiferroic materials have attracted great interest because of their underlying new science and promising applications in data storage and mutual control devices. However, they are still very rare and highly imperative to be developed. Here, we report an organic-inorganic hybrid perovskite trimethylchloromethylammonium chromium chloride (TMCM-CrCl3), showing the coexistence of magnetic and electric orderings. It displays a paraelectric-ferroelectric phase transition at 397 K with an Aizu notation of 6/mFm, and spin-canted antiferromagnetic ordering with a Néel temperature of 4.8 K. The ferroelectricity originates from the orientational ordering of TMCM cations, and the magnetism is from the [CrCl3]- framework. Remarkably, TMCM-CrCl3 is the first experimentally confirmed divalent Cr2+-based multiferroic material as far as we know. A new category of hybrid multiferroic materials is pointed out in this work, and more Cr2+-based multiferroic materials will be expectedly developed in the future.

Crystallization and Phase Transformations of Aluminum (Oxy)hydroxide Polymorphs in Caustic Aqueous Solution.

Gibbsite, bayerite, and boehmite are important aluminum (oxy)hydroxide minerals in nature and have been widely deployed in various industrial applications. They are also major components in caustic nuclear wastes stored at various U.S. locations. Knowledge of their crystallization and phase transformation processes contributes to understanding their occurrence and could help optimize waste treatment processes. While it has been reported that partial conversion of bayerite and gibbsite to boehmite occurs in basic solutions at elevated temperatures, systematic studies of factors affecting the phase transformation as well as the underlying reaction mechanisms are nonexistent, particularly in highly alkaline solutions. We explored the effects of sodium hydroxide concentrations (0.1-3 M), reaction temperatures (60-100 °C), and aluminum concentrations (0.1-1 M) on the crystallization and transformation of these aluminum (oxy)hydroxides. Detailed structural and morphological characterization by X-ray diffraction (XRD), scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) spectrometry revealed that these processes depend largely on the reaction temperature and the Al/OH- ratio. When 1 ≤ Al/OH- ≤ 2.5, the reactions favor formation of high-crystallinity precipitates, whereas at an Al/OH- ratio of ≥2.5 precipitation ceases unless the Al concentration is higher than 1 M. We identified pseudoboehmite, bayerite, and gibbsite as intermediate phases to bayerite, gibbsite and boehmite, respectively, all of which transform via dissolution-reprecipitation. Gibbsite transforms to boehmite in both acidic and weak caustic environments at temperatures above 80 °C. However, a "bar-shaped" gibbsite morphology dominates in highly caustic environments (3 M NaOH). The findings enable a robust basis for the selection of various solid phases by tuning the reaction conditions.