Self-Healable Sandfish Scale-Inspired Scalable Triboelectric Layer for Hybrid Energy Harvesting in Desert Environment.

In deserts, sedimentation from frequent dust activities on solar cells poses a substantial technical challenge, reducing efficiency and necessitating advanced cost-inefficient cleaning mechanisms. Herein, a novel sandfish scale-inspired self-healing fluorinated copolymer-based triboelectric layer is directly incorporated on top of the polysilicon solar cell for sustained hybrid energy harvesting. The transparent biomimetic layer, with distinctive saw-tooth microstructured morphology, exhibits ultra-low sand adhesion and high abrasion-resistant properties, inhibits sedimentation deposition on solar cells, and concurrently harvests kinetic energy from wind-driven sand particles through triboelectric nanogenerator (TENG). The film exhibits a low friction coefficient (0.149), minimal sand adhesion force (27 nN), and a small wear area (327 µm2). In addition, over 2 months, a solar cell with the sandfish scale-inspired structure demonstrates only a 16% decline in maximum power output compared to the bare solar cell, which experiences a 60% decline. Further, the sandfish scale-based TENG device's electrical output is fully restored to its original value after a 6-h self-healing cycle and maintains consistent stable outputs. These results highlight the exceptional advantages of employing biomimetic self-healing materials as robust triboelectric layers, showcasing sustained device stability and durability for prolonged use in harsh desert environments, ultimately contributing to a low cost-of-electricity generation paradigm.

Quantifying and Decoupling Molecular Interactions of Ionic Liquids with Gold Electrodes.

This work combined gold colloid probe atomic force microscopy (AFM) with a quartz crystal microbalance (QCM) to accurately quantify the molecular interactions of fluorine-free phosphonium-based ionic liquids (ILs) with gold electrode surfaces. First, the interactions of ILs with the gold electrode per unit area (FA', N/m2) were obtained via the force-distance curves measured by gold probe AFM. Second, a QCM was employed to detect the IL amount to acquire the equilibrium number of IL molecules adsorbed onto the gold electrode per unit area (NIL, Num/m2). Finally, the quantified molecular interactions of ILs with the gold electrode (F0, nN/Num) were estimated. F0 is closely related to the IL composition, in which the IL with the same anion but a longer phosphonium cation exhibits a stronger molecular interaction. The changes in the quantified interactions of gold with different ILs are consistent with the interactions predicted by the extended Derjaguin-Landau-Verwey-Overbeek theory, and the van der Waals interaction was identified as the major contribution of the overall interaction. The quantified molecular interaction is expected to enable the direct experimental-derived interaction parameters for molecular simulations and provide the virtual design of novel ILs for energy storage applications.

Cation Chain Length of Nonhalogenated Ionic Liquids Matters in Enhancing SERS of Cytochrome c on Zr-Al-Co-O Nanotube Arrays.

Surface-enhanced Raman scattering (SERS) is a remarkably powerful analytical technique enabling trace-level detection of biological molecules. The interaction of a probe molecule with the SERS substrate shows important distinctions in the SERS spectra, providing inherent fingerprint information on the probe molecule. Herein, nonhalogenated phosphonium-based ionic liquids (ILs) containing cations with varying chain lengths were used as trace additives to amplify the interaction between the cytochrome c (Cyt c) and Zr-Al-Co-O (ZACO) nanotube arrays, strengthening the SERS signals. An increased enhancement factor (EF) by 2.5-41.2 times compared with the system without ILs was achieved. The improvement of the SERS sensitivity with the introduction of these ILs is strongly dependent on the cation chain length, in which the increasing magnitude of EF is more pronounced in the system with a longer alkyl chain length on the cation. Comparing the interaction forces measured by Cyt c-grafted atomic force microscopy (AFM) probes on ZACO substrates with those predicted by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, the van der Waals forces became increasingly dominant as the chain length of the cations increased, associated with stronger Cyt c-ZACO XDLVO interaction forces. The major contributing component, van der Waals force, stems from the longer cation chains of the IL, which act as a bridge to connect Cyt c and the ZACO substrate, promoting the anchoring of the Cyt c molecules onto the substrate, thereby benefiting SERS enhancement.

Genetic characterization of 2 Ceutorhynchus (Coleoptera: Curculionidae) weevils with mitogenomes and insights into the phylogeny and evolution of related weevils.

The rape stem weevil (Ceutorhynchus asper Roel.) and its close relatives primarily breed on cruciferous plants and cause severe damage to rapeseed production. However, their genetic and molecular information is still scarce. Here, we generated mitogenomes for both C. asper and Ceutorhynchus albosuturalis. The lengths of the 2 mitochondrial genomes are 14,207 bp (C. asper) and 15,373 bp (C. albosuturalis), and both weevils exhibit identical numbers of protein-coding genes with the absence of trnI. A + T contents for both mitogenomes are high (80% and 79.9%, respectively). Haplotype and genetic distance analyses showed that the genetic differentiation of C. asper populations in northwestern China is low. Based on 5 datasets from mitogenomes, phylogenetic analyses with maximum-likelihood and Bayesian methods show that both species (C. asper and C. albosuturalis) fall in the CCCMS clade (Curculioninae, Conoderinae, Cossoninae, Molytinae, and Scolytinae) of Curculionidae and belong to clades H and I of the genus Ceutorhynchus, respectively. Larvae of the clade H weevils mainly are borers in petioles or stems of cruciferous plants, while larvae of the clade I weevils mainly inhabit the fruits of the same plants, suggesting that ecological niche specialization can play a critical role in the diversification of Ceutorhynchus species. This study generates baseline molecular and genetic information for future research of Ceutorhynchus-related taxa and provides insights into the phylogeny and evolution of Curculionidae.

Characteristic changes in blood routine and peripheral blood lymphocyte subpopulations in recipients of different types of rejection. / ä¸åŒç±»åž‹æŽ’æ–¥ååº”å—è€ è¡€å¸¸è§„åŠå¤–å‘¨è¡€æ·‹å·´ç»†èƒžäºšç¾¤ç‰¹å¾æ€§å˜åŒ–.

OBJECTIVES: Rejection remains the most important factor limiting the survival of transplanted kidneys. Although a pathological biopsy of the transplanted kidney is the gold standard for diagnosing rejection, its limitations prevent it from being used as a routine monitoring method. Recently, peripheral blood lymphocyte subpopulation testing has become an important means of assessing the body's immune system, however, its application value and strategy in the field of kidney transplantation need further exploration. Additionally, the development and utilization of routine test parameters are also important methods for exploring diagnostic strategies and predictive models for kidney transplant diseases. This study aims to explore the correlation between peripheral blood lymphocyte subpopulations and T cell-mediated rejection (TCMR) and antibody-mediated rejection (ABMR), as well as their diagnostic value, in conjunction with routine blood tests. METHODS: A total of 154 kidney transplant recipients, who met the inclusion and exclusion criteria and were treated at the Second Xiangya Hospital of Central South University from January to December, 2021, were selected as the study subjects. They were assigned into a stable group, a TCMR group, and an ABMR group, based on the occurrence and type of rejection. The basic and clinical data of these recipients were retrospectively analyzed and compared among the 3 groups. The transplant kidney function, routine blood tests, and peripheral blood lymphocyte subpopulation data of the TCMR group and the ABMR group before rejection treatment were compared with those of the stable group. RESULTS: The stable, TCMR group, and ABMR group showed no statistically significant differences in immunosuppressive maintenance regimens or sources of transplanted kidneys (all P>0.05). However, the post-transplant duration was significantly longer in the ABMR group compared with the stable group (P<0.001) and the TCMR group (P<0.05). Regarding kidney function, serum creatinine levels in the ABMR group were higher than in the stable group and the TCMR group (both P<0.01), with the TCMR group also showing higher levels than the stable group (P<0.01). Both TCMR and ABMR groups had significantly higher blood urea nitrogen levels than the stable group (P<0.01), with no statistically significant difference between TCMR and ABMR groups (P>0.05). The estimated glomerular filtration rate (eGFR) was lower in both TCMR and ABMR groups compared with the stable group (both P<0.01). In routine blood tests, the ABMR group had lower hemoglobin, red blood cell count, and platelet count than the stable group (all P<0.05). The TCMR group had higher neutrophil percentage (P<0.05) and count (P<0.05) than the stable group, and the ABMR group had a higher neutrophil percentage than the stable group (P<0.05). The eosinophil percentage and count in the TCMR group were lower than in the stable and ABMR groups (all P<0.05). Both TCMR and ABMR groups had lower basophil percentage and count, as well as lower lymphocyte percentage and count, compared with the stable group (all P<0.05). There were no significant differences in monocyte percentage and count among the 3 groups (all P>0.05). In lymphocyte subpopulations, the TCMR and ABMR groups had lower counts of CD45+ cells and T cells compared with the stable group (all P<0.05). The TCMR group also had lower counts of CD4+ T cells, NK cells, and B cells than the stable group (all P<0.05). There were no significant differences in the T cell percentage, CD4+ T cell percentage, CD8+ T cell percentage and their counts, CD4+/CD8+ T cell ratio, NK cell percentage, and B cell percentage among the stable, TCMR, and ABMR groups (all P>0.05). CONCLUSIONS: The occurrence of rejection leads to impaired transplant kidney function, accompanied by characteristic changes in some parameters of routine blood tests and peripheral blood lymphocyte subpopulations in kidney transplant recipients. The different characteristics of changes in some parameters of routine blood tests and peripheral blood lymphocyte subpopulations during TCMR and ABMR may help predict and diagnose rejection and differentiate between TCMR and ABMR.

A Practical Risk Classification of Early Recurrence in Hepatocellular Carcinoma Patients with Microvascular invasion after Hepatectomy: A Decision Tree Analysis.

PURPOSE: This study was designed to establish risk classifications for early recurrence in hepatocellular carcinoma (HCC) patients with microvascular invasion (MVI) after hepatectomy. METHODS: The data of 563 HCC patients with MVI after hepatectomy from two hospitals were retrospectively reviewed. Kaplan-Meier curves and Cox proportional hazards regression models were used to analyse early recurrence. The risk classification for early recurrence was established by using classification and regression tree (CART) analysis and validated by using two independent validation cohorts from two hospitals. RESULTS: Multivariate analysis revealed that four indices, namely, infection of chronic viral hepatitis, MVI classification, tumour size, and serum alpha-fetoprotein (AFP), were independent prognostic factors for early recurrence in HCC patients with MVI. By CART analysis, MVI classification and serum AFP became the nodes of a decision tree and 3-stratification classifications that satisfactorily determined the risk of early recurrence were established. The area under the time-dependent receiver operating characteristic curve (AUC) values of the classification for early recurrence at 0.5, 1.0, and 2.0 years were 0.75, 0.73, and 0.71, respectively, which were all significantly higher than three common classic HCC stages (BCLC stage, Chinese stage, and TNM stage). The calibration curves showed good agreement between predictions by classification for early recurrence and actual survival outcomes. These prediction results also were confirmed in the independent internal and external validation cohorts. CONCLUSIONS: The 3 stratification classifications enabled satisfactory risk evaluation of early recurrence in HCC patients with MVI after hepatectomy.

The Nanoscale Wetting Parameter and Its Role in Interfacial Phenomena: Phase Transitions in Nanopores.

Through analysis of the statistical mechanical equations for a thin adsorbed film (gas, liquid, or solid) on a solid substrate or confined within a pore, it is possible to express the equilibrium thermodynamic properties of the film as a function of just two dimensionless parameters: a nanoscale wetting parameter, αw, and pore width, H*. The wetting parameter, αw, is defined in terms of molecular parameters for the adsorbed film and substrate and so is applicable at the nanoscale and for films of any phase. The main assumptions in the treatment are that (a) the substrate structure is not significantly affected by the adsorbed layer and (b) the diameter of the adsorbate molecules is not very small compared to the spacing of atoms in the solid substrate. We show that different surface geometries of the substrate (e.g., slit, cylindrical, and spherical pores) and various models of wall heterogeneity can be accounted for through a well-defined correction to the wetting parameter; no new dimensionless variables are introduced. Experimental measurements are reported for contact angles for various liquids on several planar substrates and are shown to be closely correlated with the nanoscale wetting parameter. We apply this approach to phase separation in nanopores of various geometries. Molecular simulation results for the phase diagram in confinement, obtained by the flat histogram Monte Carlo method, are reported and are shown to be closely similar to experimental results for capillary condensation, melting, and the triple point. The value of the wetting parameter, αw, is shown to determine the qualitative behavior (e.g., increase vs decrease in the melting temperature, capillary condensation vs evaporation), whereas the pore width determines the magnitude of the confinement effect. The triple point temperature and pressure for the confined phase are always lower than those for the bulk phase for all cases studied.

Programmable Interactions of Cellulose Acetate with Octadecyltrichlorosilane-Functionalized SiO2 Nanoparticles.

It is significant to understand the interfacial interactions involved between the cellulose acetate (CA) and dispersed nanomaterials, in which the enhanced interaction improves the mechanical behavior of CA. In this work, the amendments of CA with SiO2 nanoparticles have been found to be endowed by grafting varying concentrations (0, 3, 5, and 6%) of octadecyltrichlorosilane (OTS). Aided by SiO2 colloid probe atomic force microscopy (AFM with a probe diameter of 20 µm), the adhesion force between CA and SiO2 is found to be programmable by tuning OTS concentrations functionalized onto SiO2 surfaces. The adhesion forces of 5% OTS-functionalized SiO2 with CA are the strongest, followed by the ones of 0, 3, and 6% OTS, resulting in a smoother and denser morphology on the film with 5% OTS. The AFM-measured approaching force-distance curves have been further compared to predictions by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, in which the XDLVO force is summed as the Liftshitz-van der Waals force (FLW), the electrostatic double-layer force (FEL), and the acid-base interaction force (FAB). FLW and FEL do not change significantly with OTS concentrations functionalized onto SiO2. However, FAB is sensitive to the functionalized OTS concentration onto SiO2 and significantly contributes to the interaction force of the composite films with 5% OTS, promoting the formation of a smooth and dense surface feature with a considerable mechanical performance demonstrated by load-displacement curves from a nanoindenter. This is highly encouraging and suggests that nanomaterials can be incorporated into CA to effectively improve their mechanical compatibility by programming the interaction between the CA matrix and nanomaterials.

Effect of Electrode Surface Chemistry on Ion Structuring of Imidazolium Ionic Liquids.

Surface chemistry plays a critical role in the ion structuring of ionic liquids (ILs) at the interfaces of electrodes and controls the overall energy storage performance of the system. Herein, we functionalized the gold (Au) colloid probe of an atomic force microscope with -COOH and -NH2 groups to explore the effect of different surface chemical properties on the ion structuring of an IL. Aided by colloid-probe atomic force microscopy (AFM), the ion structuring of an imidazolium IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6], abbreviated as BP hereafter), on the Au electrode surface and the ion response to the change in the surface chemistry are investigated. AFM morphologies, contact angles, and approaching force-distance curves of the BP IL on the functionalized Au surfaces exhibited that the IL forms a more obvious layering structure on the -COOH-terminated Au surface (Au-COOH), while it forms heterogeneous and aggregating droplets on the -NH2 surface (Au-NH2). The formed uniform and aggregation-free ion layers in the vicinity of the Au-COOH surface are due to the π-π+ stacking interaction between the delocalized π+ electrons from the imidazolium ring in the IL [BMIM]+ cation and the localized π electrons from the sp2 carbon on the -COOH group. The in situ observation of nano-friction and torsional resonance frequency at the IL-electrode interfaces further demonstrated the ion structuring of the IL at Au-COOH, which results in a more sensitive electrochemical response associated with a faster capacitive process.

Magnetic resonance spectroscopy and liquid chromatography-mass spectrometry metabolomics study may differentiate pre-eclampsia from gestational hypertension.

OBJECTIVE: To investigate the findings of magnetic resonance imaging (MRI), magnetic resonance spectroscopy (MRS), and serum metabolomics for differentiating pre-eclampsia (PE) from gestational hypertension (GH). METHODS: This prospective study enrolled 176 subjects including a primary cohort with healthy non-pregnant women (HN, n = 35), healthy pregnant women (HP, n = 20), GH (n = 27), and PE (n = 39) and a validation cohort with HP (n = 22), GH (n = 22), and PE (n = 11). T1 signal intensity index (T1SI), apparent diffusion coefficient (ADC) value, and the metabolites on MRS were compared. The differentiating performances of single and combined MRI and MRS parameters for PE were evaluated. Serum liquid chromatography-mass spectrometry (LC-MS) metabolomics was investigated by sparse projection to latent structures discriminant analysis. RESULTS: Increased T1SI, lactate/creatine (Lac/Cr), and glutamine and glutamate (Glx)/Cr and decreased ADC value and myo-inositol (mI)/Cr in basal ganglia were found in PE patients. T1SI, ADC, Lac/Cr, Glx/Cr, and mI/Cr yielded an area under the curves (AUC) of 0.90, 0.80, 0.94, 0.96, and 0.94 in the primary cohort, and of 0.87, 0.81, 0.91, 0.84, and 0.83 in the validation cohort, respectively. A combination of Lac/Cr, Glx/Cr, and mI/Cr yielded the highest AUC of 0.98 in the primary cohort and 0.97 in the validation cohort. Serum metabolomics analysis showed 12 differential metabolites, which are involved in pyruvate metabolism, alanine metabolism, glycolysis, gluconeogenesis, and glutamate metabolism. CONCLUSIONS: MRS is expected to be a noninvasive and effective tool for monitoring GH patients to avoid the development of PE. KEY POINTS: • Increased T1SI and decreased ADC value in the basal ganglia were found in PE patients than in GH patients. • Increased Lac/Cr and Glx/Cr, and decreased mI/Cr in the basal ganglia were found in PE patients than in GH patients. • LC-MS metabolomics showed that the major differential metabolic pathways between PE and GH were pyruvate metabolism, alanine metabolism, glycolysis, gluconeogenesis, and glutamate metabolism.

Value and prognostic factors of repeat hepatectomy for recurrent colorectal liver metastasis.

BACKGROUND: More than 50% of patients with colorectal cancer develop liver metastases. Hepatectomy is the preferred treatment for resectable liver metastases. This review provides a perspective on the utility and relevant prognostic factors of repeat hepatectomy in recurrent colorectal liver metastasis (CRLM). DATA SOURCES: The keywords "recurrent colorectal liver metastases", "recurrent hepatic metastases from colorectal cancer", "liver metastases of colorectal cancer", "repeat hepatectomy", "repeat hepatic resection", "second hepatic resection", and "prognostic factors" were used to retrieve articles published in the PubMed database up to August 2020. Additional articles were identified by a manual search of references from key articles. RESULTS: Despite improvements in surgical methods and perioperative chemotherapy, recurrence remains common in 37%-68% of patients. Standards or guidelines for the treatment of recurrent liver metastases are lacking. Repeat hepatectomy appears to be the best option for patients with resectable metastases. The commonly reported prognostic factors after repeat hepatectomy were R0 resection, carcinoembryonic antigen level, the presence of extrahepatic disease, a short disease-free interval between initial and repeat hepatectomy, the number (> 1) and size (≥ 5 cm) of hepatic lesions, requiring blood transfusion, and no adjuvant chemotherapy after initial hepatectomy. The median overall survival after repeat hepatectomy ranged from 19.3 to 62 months, and the 5-year overall survival ranged from 21% to 73%. Chemotherapy can act as a test for the biological behavior of tumors with the goal of avoiding unnecessary surgery, and a multimodal approach involving aggressive chemotherapy and repeat hepatectomy might be the treatment of choice for patients with early recurrent CRLM. CONCLUSIONS: Repeat hepatectomy is a relatively safe and effective treatment for resectable recurrent CRLM. The presence or absence of prognostic factors might facilitate patient selection to improve short- and long-term outcomes.

Genome assembly of the Chinese maize elite inbred line RP125 and its EMS mutant collection provide new resources for maize genetics research and crop improvement.

Maize is an important crop worldwide, as well as a valuable model with vast genetic diversity. Accurate genome and annotation information for a wide range of inbred lines would provide valuable resources for crop improvement and pan-genome characterization. In this study, we generated a high-quality de novo genome assembly (contig N50 of 15.43 Mb) of the Chinese elite inbred line RP125 using Nanopore long-read sequencing and Hi-C scaffolding, which yield highly contiguous, chromosome-length scaffolds. Global comparison of the RP125 genome with those of B73, W22, and Mo17 revealed a large number of structural variations. To create new germplasm for maize research and crop improvement, we carried out an EMS mutagenesis screen on RP125. In total, we obtained 5818 independent M2 families, with 946 mutants showing heritable phenotypes. Taking advantage of the high-quality RP125 genome, we successfully cloned 10 mutants from the EMS library, including the novel kernel mutant qk1 (quekou: "missing a small part" in Chinese), which exhibited partial loss of endosperm and a starch accumulation defect. QK1 encodes a predicted metal tolerance protein, which is specifically required for Fe transport. Increased accumulation of Fe and reactive oxygen species as well as ferroptosis-like cell death were detected in qk1 endosperm. Our study provides the community with a high-quality genome sequence and a large collection of mutant germplasm.

Novel Intrinsic Self-Healing Poly-Silicone-Urea with Super-Low Ice Adhesion Strength.

Accumulation of snow and ice often causes problems and even dangerous situations for both industry and the general population. Passive de-icing technologies, e.g., hydrophobic, liquid-infused bionic surfaces, have attracted more and more attention compared with active de-icing technologies, e.g., electric heating, hot air heating, due to the passive de-icing technology's lower energy consumption and sustainability footprint. Using passive de-icing coatings seems to be one of the most promising solutions. However, the previously reported de-icing coatings suffer from high ice adhesion strength or short service life caused by wear. An intrinsic self-healing material based on poly-silicone-urea is developed in this work to address these problems. The material is prepared by introducing dynamic disulfide bonds into the hard phase of the polymer. Experimental results indicate that this poly-silicone-urea has a self-healing efficiency of close to 99%. More interestingly, it is found that the coating prepared from this poly-silicone-urea has a super low ice adhesion force, only 7 ± 1 kPa, which is almost the lowest value compared with previous intrinsic self-healing de-/anti-icing reports. This material can maintain low ice adhesion strength after healing. This intrinsic self-healing poly-silicone-urea can meet several practical applications, opening the door for future sustainable anti-/de-icing technologies.

In vivo detection of dysregulated choline metabolism in paclitaxel-resistant ovarian cancers with proton magnetic resonance spectroscopy.

BACKGROUND: Chemoresistance gradually develops during treatment of epithelial ovarian cancer (EOC). Metabolic alterations, especially in vivo easily detectable metabolites in paclitaxel (PTX)-resistant EOC remain unclear. METHODS: Xenograft models of the PTX-sensitive and PTX-resistant EOCs were built. Using a combination of in vivo proton-magnetic resonance spectroscopy (1H-MRS), metabolomics and proteomics, we investigated the in vivo metabolites and dysregulated metabolic pathways in the PTX-resistant EOC. Furthermore, we analyzed the RNA expression to validate the key enzymes in the dysregulated metabolic pathway. RESULTS: On in vivo 1H-MRS, the ratio of (glycerophosphocholine + phosphocholine) to (creatine + phosphocreatine) ((GPC + PC) to (Cr + PCr))(i.e. Cho/Cr) in the PTX-resistant tumors (1.64 [0.69, 4.18]) was significantly higher than that in the PTX-sensitive tumors (0.33 [0.10, 1.13]) (P = 0.04). Forty-five ex vivo metabolites were identified to be significantly different between the PTX-sensitive and PTX-resistant tumors, with the majority involved of lipids and lipid-like molecules. Spearman's correlation coefficient analysis indicated in vivo and ex vivo metabolic characteristics were highly consistent, exhibiting the highest positive correlation between in vivo GPC + PC and ex vivo GPC (r = 0.885, P < 0.001). These metabolic data suggested that abnormal choline concentrations were the results from the dysregulated glycerophospholipid metabolism, especially choline metabolism. The proteomics data indicated that the expressions of key enzymes glycerophosphocholine phosphodiesterase 1 (GPCPD1) and glycerophosphodiester phosphodiesterase 1 (GDE1) were significantly lower in the PTX-resistant tumors compared to the PTX-sensitive tumors (both P < 0.01). Decreased expressions of GPCPD1 and GDE1 in choline metabolism led to an increased GPC levels in the PTX-resistant EOCs, which was observed as an elevated total choline (tCho) on in vivo 1H-MRS. CONCLUSIONS: These findings suggested that dysregulated choline metabolism was associated with PTX-resistance in EOCs and the elevated tCho on in vivo 1H-MRS could be as an indicator for the PTX-resistance in EOCs.

Selective Separation of Highly Similar Proteins on Ionic Liquid-Loaded Mesoporous TiO2.

Separating proteins from their mixtures is an important process in a great variety of applications, but it faces difficult challenges as soon as the proteins are simultaneously of similar sizes and carry comparable net charges. To develop both efficient and sustainable strategies for the selective separation of similar proteins and to understand the underlying molecular mechanisms to enable the separation are crucial. In this work, we propose a novel strategy where the cholinium-based amino acid [Cho][Pro] ionic liquid (IL) is used as the trace additive and loaded physically on a mesoporous TiO2 surface for separating two similar proteins (lysozyme and cytochrome c). The observed selective adsorption behavior is explained by the hydration properties of the [Cho][Pro] loaded on the TiO2 surface and their partially dissociated ions under different pH conditions. As the pH is increased from 5.0 to 9.8, the degree of hydration of IL ions also increases, gradually weakening the interaction strength of the proteins with the substrates, more for lysozymes, leading to their effective separation. These findings were further used to guide the detection of the retention behavior of a binary mixture of proteins in high-performance liquid chromatography, where the introduction of ILs did effectively separate the two similar proteins. Our results should further stimulate the use of ILs in the separation of proteins with a high degree of mutual similarity.

Immobilizing Ionic Liquids onto Functionalized Surfaces for Sensing Volatile Organic Compounds.

Herein, a highly sensitive volatile organic compound (VOC) gas sensor is demonstrated using immobilized ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate, onto surfaces functionalized by the quaternary ammonium group -N+R, -COOH, and -NH2, i.e., N+-IL, COOH-IL, and NH2-IL, respectively. These functional groups ensure highly tunable interactions between the IL and surfaces, efficiently modulating the electrical resistance of the immobilized IL upon exposure to acetone and toluene. The immobilized IL to both acetone and toluene displays significant electronic resistance changes at a concentration of 150 ppm, falling in the order NH2-IL > N+-IL > COOH-IL for acetone while COOH-IL > NH2-IL > N+-IL for toluene. A better gaseous sensing ability is achieved in COOH-IL for toluene than acetone, while this does not hold in the case of NH2-IL and N+-IL surfaces because of the completely different ion structuring of the IL at these functionalized surfaces. The accelerated ion mobility in the IL that is immobilized onto functionalized surfaces is also responsible for the strong gaseous sensing response, which is demonstrated further by the atomic force microscopy-measured smaller friction coefficient. This is highly encouraging and suggests that ILs can be immobilized by a network formed by surface functionalization to easily and cheaply detect VOCs at ppm concentrations.

Microstructural probing of phosphonium-based ionic liquids on a gold electrode using colloid probe AFM.

Atomic force microscopy (AFM) with a gold colloid probe modeled as the electrode surface is employed to directly capture the contact resonance frequency of two phosphonium-based ionic liquids (ILs) containing a common anion [BScB]- and differently lengthened cations ([P6,6,6,14]+ and [P4,4,4,8]+). The comparative interfacial studies are performed by creating IL films on the surface of gold, followed by measuring the wettability, thickness of the films, adhesion forces, surface morphology and AFM-probed contact resonance frequency. In addition, the cyclic voltammetry and impedance spectroscopy measurements of the neat ILs are measured on the surface of the gold electrode. The IL with longer cation alkyl chains exhibits a well-defined thin film on the electrode surface and enhanced the capacitance than the shorter chain IL. The AFM contact resonance frequency and force curves reveal that the longer IL prefers to form stiffer ion layers at the gold electrode surface, suggesting the "…anion-anion-cation-cation…" bilayer structure, in contrast, the shorter-chain IL forms the softer cation-anion alternating structure, i.e., "…anion-cation-anion-cation…".

Molecular interactions of ionic liquids with SiO2 surfaces determined from colloid probe atomic force microscopy.

Ionic liquids (ILs) interact strongly with many different types of solid surfaces in a wide range of applications, e.g. lubrication, energy storage and conversion, etc. However, due to the nearly immeasurable large number of potential ILs available, identifying the appropriate ILs for specific solid interfaces with desirable properties is a challenge. Theoretical studies are highly useful for effective development of design and applications of these complex molecular systems. However, obtaining reliable force field models and interaction parameters is highly demanding. In this work, we apply a new methodology by deriving the interaction parameters directly from the experimental data, determined by colloid probe atomic force microscopy (CP-AFM). The reliability of the derived interaction parameters is tested by performing molecular dynamics simulations to calculate translational self-diffusion coefficients and comparing them with those obtained from NMR diffusometry.

A multi center real world observation to evaluate the efficacy of cryotherapy versus local hyperthermia for the treatment of plane warts.

Most plane warts are recalcitrant to treatment. Both cryotherapy and local hyperthermia have been applied to treat plane warts. However, no direct comparative study on their respective efficacy and safety has ever been performed. To assess the efficacy and safety of local hyperthermia at 43 ± 1°C versus liquid nitrogen cryotherapy for plane warts. Sequential patients with plane warts entered the study, either receiving cryotherapy or local hyperthermia therapy at the discretion of the patients and the recommendations of consultants. Cryotherapy with liquid nitrogen was delivered in two sessions 2 weeks apart, while local hyperthermia was delivered on three consecutive days, plus two similar treatments 10 ± 3 days later. The temperature over the treated skin surface was set at 43 ± 1°C for 30 min in each session. The primary outcome was the clearance rates of the lesions 6 months after treatment. Among the 194 participants enrolled, 183 were included in the analysis at 6 months. Local hyperthermia and cryotherapy achieved clearance rates of 35.56% (48/135) and 31.25% (15/48), respectively (p = 0.724); recurrence rates of 16.67% (8/48) and 53.33% (8/15) (p = 0.01); and adverse events rates of 20.74% (28/135) and 83.33% (40/48), respectively (p < 0.001). Cryotherapy had a higher pain score (p < 0.001) and a longer healing time (p < 0.001). Local hyperthermia at 43°C and cryotherapy had similar efficacy for plane warts. Local hyperthermia had a safer profile than cryotherapy but it required more treatment visits during a treatment course. More patients preferred local hyperthermia due to its treatment friendly nature.

Radiologic Imaging Modalities for Colorectal Cancer.

BACKGROUND: Studies reported various diagnostic value of radiologic imaging modalities for diagnosis and management of colorectal cancer (CRC). AIMS: To summary the diagnosis and management of CRC using computed tomography colonography (CTC), magnetic resonance colonography (MRC), and positron emission tomography (PET)/computed tomography (CT). METHODS: Comprehensive literature searches were conducted in PubMed, EmBase, and the Cochrane library for studies published before April 2021. The diagnostic performance of CTC, MRC, and PET/CT for CRC was summarized. RESULTS: A total of 54 studies (17 studies for CTC, 8 studies for MRC, and 29 studies for PET/CT) were selected for final analysis. The sensitivity and specificity for CTC ranged from 27 to 100%, 88 to 100%, respectively, and the pooled sensitivity and specificity for CTC were 0.97 (95% CI 0.88-0.99) and 0.99 (95% CI 0.99-1.00). The sensitivity and specificity for MRC ranged from 48 to 100%, 60 to 100%, respectively, and the pooled sensitivity and specificity for MRC were 0.98 (95% C: 0.77-1.00) and 0.94 (95% CI 0.84-0.98). The sensitivity and specificity for PET/CT ranged from 84 to 100%, 33 to 100%, respectively, and the pooled sensitivity and specificity for PET/CT were 0.94 (95% CI 0.92-0.96) and 0.94 (95% CI 0.90-0.97). The area under the receiver operating characteristic curve for CTC, MRC, and PET/CT was 1.00 (95% CI 0.99-1.00), 0.99 (95% CI 0.98-1.00), and 0.97 (0.95% CI 0.95-0.98), respectively. CONCLUSIONS: This study suggested both CTC and MRC with relative higher diagnostic value for diagnosing CRC, while PET/CT with higher diagnostic value in detecting local recurrence for patients with CRC.