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Time‐Dependent Cation Selectivity of Titanium Carbide MXene in Aqueous Solution
Electrochemical ion separation is a promising technology to recover valuable ionic species from water. Pseudocapacitive materials, especially 2D materials, are up-and-coming electrodes for electrochemical ion separation. For implementation, it is essential to understand the interplay of the intrinsic preference of a specific ion (by charge/size), kinetic ion preference (by mobility), and crystal structure changes. Ti3C2Tz MXene is chosen here to investigate its selective behavior toward alkali and alkaline earth cations. Utilizing an online inductively coupled plasma system, it is found that Ti3C2Tz shows a time-dependent selectivity feature. In the early stage of charging (up to about 50 min), K+ is preferred, while ultimately Ca2+ and Mg2+ uptake dominate; this unique phenomenon is related to dehydration energy barriers and the ion exchange effect between divalent and monovalent cations. Given the wide variety of MXenes, this work opens the door to a new avenue where selective ion-separation with MXene can be further engineered and optimized.
Dielectrophoresis: An Approach to Increase Sensitivity, Reduce Response Time and to Suppress Nonspecific Binding in Biosensors?
The performance of receptor-based biosensors is often limited by either diffusion of the analyte causing unreasonable long assay times or a lack of specificity limiting the sensitivity due to the noise of nonspecific binding. Alternating current (AC) electrokinetics and its effect on biosensing is an increasing field of research dedicated to address this issue and can improve mass transfer of the analyte by electrothermal effects, electroosmosis, or dielectrophoresis (DEP). Accordingly, several works have shown improved sensitivity and lowered assay times by order of magnitude thanks to the improved mass transfer with these techniques. To realize high sensitivity in real samples with realistic sample matrix avoiding nonspecific binding is critical and the improved mass transfer should ideally be specific to the target analyte. In this paper we cover recent approaches to combine biosensors with DEP, which is the AC kinetic approach with the highest selectivity. We conclude that while associated with many challenges, for several applications the approach could be beneficial, especially if more work is dedicated to minimizing nonspecific bindings, for which DEP offers interesting perspectives.
Melt Electrowriting of Scaffolds with a Porosity Gradient to Mimic the Matrix Structure of the Human Trabecular Meshwork
The permeability of the Human Trabecular Meshwork (HTM) regulates eye pressure via a porosity gradient across its thickness modulated by stacked layers of matrix fibrils and cells. Changes in HTM porosity are associated with increases in intraocular pressure and the progress of diseases like glaucoma. Engineered HTMs could help to understand the structure-function relation in natural tissues, and lead to new regenerative solutions. Here, melt electrowriting (MEW) is explored as a biofabrication technique to produce fibrillar, porous scaffolds that mimic the multilayer, gradient structure of native HTM. Poly(caprolactone) constructs with a height of 125-500 μm and fiber diameters of 10-12 μm are printed. Scaffolds with a tensile modulus between 5.6 and 13 MPa, and a static compression modulus in the range of 6-360 kPa are obtained by varying the scaffolds design, i.e., density and orientation of the fibers and number of stacked layers. Primary HTM cells attach to the scaffolds, proliferate, and form a confluent layer within 8-14 days, depending on the scaffold design. High cell viability and cell morphology close to that in the native tissue are observed. The present work demonstrates the utility of MEW to reconstruct complex morphological features of natural tissues.
Analysis of complex drugs by comprehensive two-dimensional gas chromatography and high-resolution mass spectrometry: detailed chemical description of the active pharmaceutical ingredient sodium bituminosulfonate and its process intermediates
The European pharmacopeia provides analytical methods for the chemical characterization of active pharmaceutical ingredients (APIs). However, the complexity of some APIs exceeds the limitations of the currently prevailing physicochemical methods. Sodium bituminosulfonate (SBS) is described by the collection of key parameters of generalizing criteria such as dry matter, sulfur and sodium content, and neutrality, but techniques to unravel the complexity on a molecular level are lacking. We present a study based on online derivatization with tetramethylammonium hydroxide in combination with comprehensive two-dimensional gas chromatography coupled to an electron ionization high-resolution time-of-flight mass spectrometer (GC × GC-HR-ToF–MS) for the chemical description of SBS as well as its process intermediates. The application of GC × GC allowed the comprehensive description of the chemical components in the API and the process intermediates for the first time. Furthermore, it was possible to classify peaks regarding their elemental and structural composition based on accurate mass information, elution behavior, and mass fragmentation pattern. This work demonstrates not only the general applicability, advantages but also limitations of GC × GC for the characterization of APIs for complex drugs. Graphical Abstract: [Figure not available: see fulltext.]
Optical Spectrometry to Determine Nutrient Concentrations and other Physicochemical Parameters in Liquid Organic Manures: A Review
Nutrient concentrations in livestock manures and biogas digestates show a huge variability due to disparities in animal husbandry systems concerning animal species, feed composition, etc. Therefore, a nutrient estimation based on recommendation tables is not reliable when the exact chemical composition is needed. The alternative, to analyse representative fertilizer samples in a standard laboratory, is too time-and cost-intensive to be an accepted routine method for farmers. However, precise knowledge about the actual nutrient concentrations in liquid organic fertilizers is a prerequisite to ensure optimal nutrient supply for growing crops and on the other hand to avoid environmental problems caused by overfertilization. Therefore, spectrometric methods receive increasing attention as fast and low-cost alternatives. This review summarizes the present state of research based on optical spectrometry used at laboratory and field scale for predicting several parameters of liquid organic manures. It emphasizes three categories: (1) physicochemical parameters, e.g., dry matter, pH, and electrical conductivity; (2) main plant nutrients, i.e., total nitrogen, ammonium nitrogen, phosphorus, potassium, magnesium, calcium, and sulfur; and (3) micronutrients, i.e., manganese, iron, copper, and zinc. Furthermore, the commonly used sample preparation techniques, spectrometer types, measuring modes, and chemometric methods are presented. The primarily promising scientific results of the last 30 years contributed to the fact that near-infrared spectrometry (NIRS) was established in commercial laboratories as an alternative method to wet chemical standard methods. Furthermore, companies developed technical setups using NIRS for on-line applications of liquid organic manures. Thus, NIRS seems to have evolved to a competitive measurement procedure, although parts of this technique still need to be improved to ensure sufficient accuracy, especially in quality management.
Combined In Vitro Toxicity and Immunogenicity of Cold Plasma and Pulsed Electric Fields
In modern oncology, therapies are based on combining monotherapies to overcome treatment resistance and increase therapy precision. The application of microsecond-pulsed electric fields (PEF) is approved to enhance local chemotherapeutic drug uptake within combination electrochemotherapy regimens. Reactive oxygen species (ROS) have been implicated in anticancer effects, and cold physical plasma produces vast amounts of ROS, which have recently been shown to benefit head and neck cancer patients. PEF and cold plasma technology have been linked to immunogenic cell death (ICD) induction, a regulated cell death accompanied by sterile inflammation that promotes antitumor immunity. To this end, we investigated the combined effect of both treatments regarding their intracellular ROS accumulation, toxicity, ICD-related marker expression, and optimal exposure sequence in a leukemia model cell line. The combination treatment substantially increased ROS and intracellular glutathione levels, leading to additive cytotoxic effects accompanied by a significantly increased expression of ICD markers, such as the eat-me signal calreticulin (CRT). Preconditioned treatment with cold plasma followed by PEF exposure was the most potent treatment sequence. The results indicate additive effects of cold plasma and PEF, motivating further studies in skin and breast tumor models for the future improvement of ECT in such patients.
Effect of Fans’ Placement on the Indoor Thermal Environment of Typical Tunnel-Ventilated Multi-Floor Pig Buildings Using Numerical Simulation
An increasing number of large pig farms are being built in multi-floor pig buildings (MFPBs) in China. Currently, the ventilation system of MFPB varies greatly and lacks common standards. This work aims to compare the ventilation performance of three popular MFPB types with different placement of fans using the Computational Fluid Dynamics (CFD) technique. After being validated with field-measured data, the CFD models were extended to simulate the air velocity, air temperature, humidity, and effective temperature of the three MFPBs. The simulation results showed that the ventilation rate of the building with outflowing openings in the endwall and fans installed on the top of the shaft was approximately 25% less than the two buildings with fans installed on each floor. The ventilation rate of each floor increased from the first to the top floor for both buildings with a shaft, while no significant difference was observed in the building without a shaft. Increasing the shaft’s width could mitigate the variation in the ventilation rate of each floor. The effective temperature distribution at the animal level was consistent with the air velocity distribution. Therefore, in terms of the indoor environmental condition, the fans were recommended to be installed separately on each floor.
Management-induced changes in soil organic carbon on global croplands
Soil organic carbon (SOC), one of the largest terrestrial carbon (C) stocks on Earth, has been depleted by anthropogenic land cover change and agricultural management. However, the latter has so far not been well represented in global C stock assessments. While SOC models often simulate detailed biochemical processes that lead to the accumulation and decay of SOC, the management decisions driving these biophysical processes are still little investigated at the global scale. Here we develop a spatially explicit data set for agricultural management on cropland, considering crop production levels, residue returning rates, manure application, and the adoption of irrigation and tillage practices. We combine it with a reduced-complexity model based on the Intergovernmental Panel on Climate Change (IPCC) tier 2 method to create a half-degree resolution data set of SOC stocks and SOC stock changes for the first 30 cm of mineral soils. We estimate that, due to arable farming, soils have lost around 34.6 GtC relative to a counterfactual hypothetical natural state in 1975. Within the period 1975-2010, this SOC debt continued to expand by 5 GtC (0.14 GtCyr-1) to around 39.6 GtC. However, accounting for historical management led to 2.1 GtC fewer (0.06 GtCyr-1) emissions than under the assumption of constant management. We also find that management decisions have influenced the historical SOC trajectory most strongly by residue returning, indicating that SOC enhancement by biomass retention may be a promising negative emissions technique. The reduced-complexity SOC model may allow us to simulate management-induced SOC enhancement - also within computationally demanding integrated (land use) assessment modeling.
Surface Plasmon Resonance Sensitivity Enhancement Based on Protonated Polyaniline Films Doped by Aluminum Nitrate
Complex composite films based on polyaniline (PANI) doped hydrochloric acid (HCl) incorporated with aluminum nitrate (Al(NO3)3) on Au-layer were designed and synthesized as a surface plasmon resonance (SPR) sensing device. The physicochemical properties of (PANI-HCl)/Al(NO3)3 complex composite films were studied for various Al(NO3)3 concentrations (0, 2, 4, 8, 16, and 32 wt.%). The refractive index of the (PANI-HCl)/Al(NO3)3 complex composite films increased continuously as Al(NO3)3 concentrations increased. The electrical conductivity values increased from 5.10 µS/cm to 10.00 µS/cm as Al(NO3)3 concentration increased to 32 wt.%. The sensitivity of the SPR sensing device was investigated using a theoretical approach and experimental measurements. The theoretical system of SPR measurement confirmed that increasing Al(NO3)3 in (PANI-HCl)/Al(NO3)3 complex composite films enhanced the sensitivity from about 114.5 [Deg/RIU] for Au-layer to 159.0 [Deg/RIU] for Au-((PANI-HCl)/Al(NO3)3 (32 wt.%)). In addition, the signal-to-noise ratio for Au-layer was 3.95, which increased after coating by (PANI-HCl)/Al(NO3)3 (32 wt.%) complex composite layer to 8.82. Finally, we conclude that coating Au-layer by (PANI-HCl)/Al(NO3)3 complex composite films enhances the sensitivity of the SPR sensing device.
Simulating Cotton Growth and Productivity Using AquaCrop Model under Deficit Irrigation in a Semi-Arid Climate
AquaCrop is a water-driven model that simulates the effect of environment and management on crop production under deficit irrigation. The model was calibrated and validated using three databases and four irrigation treatments (i.e., 100%ET, 80%ET, 70%ET, and 50%ET). Model performance was evaluated by simulating canopy cover (CC), biomass accumulation, and water productivity (WP). Statistics of root mean square error (RMSE) and Willmott’s index of agreement (d) showed that model predictions are suitable for non-stressed and moderate stressed conditions. The results showed that the simulated biomass and yield were consistent with the measured values with a coefficient of determination (R2) of 0.976 and 0.950, respectively. RMSE and d-index values for canopy cover (CC) were 2.67% to 4.47% and 0.991% to 0.998% and for biomass were 0.088 to 0.666 ton/ha and 0.991 to 0.999 ton/ha, respectively. Prediction of simulated and measured biomass and final yield was acceptable with deviation ˂10%. The overall value of R2 for WP in terms of yield was 0.943. Treatment with 80% ET consumed 20% less water than the treatment with 100%ET and resulted in high WP in terms of yield (0.6 kg/m3) and biomass (1.74 kg/m3), respectively. The deviations were in the range of −2% to 11% in yield and −2% to 4% in biomass. It was concluded that AquaCrop is a useful tool in predicting the productivity of cotton under different irrigation scenarios.