Accurate Determination Research Articles

A novel application of inverse gas chromatography for estimating contact angles in porous media

HypothesisSurface wettability is a critical factor in multi-phase flow within porous media, a processes essential in various applications e.g. in the energy sector. Traditional methods for assessing wettability of porous media by contact angle measurements, such as sessile droplet and micro-CT techniques, are limited by interface pinning, sample size or resolution impacting precision and accuracy. We hypothesized that using smaller and unconstrained probes, specifically gas molecules, to retrieve interactions along a representative sample size via inverse gas chromatography (IGC) could provide a more accurate determination of contact angles. MethodWe propose a procedure to relate IGC results with macro-scale wettability descriptions, such as the Young equation. To test the effectiveness of IGC method, glass bead samples with varying wettability, modified through a silanization process, were prepared. Contact angles for a distilled water-air-sample system were measured using the sessile droplet method and micro-CT for comparative analysis. IGC was employed to determine the surface energy components of these samples, which were then used in the extended Young-Dupré equation to calculate the contact angles. FindingsThe contact angle ranges determined by IGC and micro-CT for untreated glass beads, the most hydrophilic samples, showed great alignment. This consistency is attributed to the chemical amorphous nature of the untreated beads reflected in the assumption that dispersive and specific energetic components of surface sites are uncorrelated, on which the proposed analysis is based. For treated samples, where the silanization process creates correlations between surface energetic components, the alignment between IGC and micro-CT results was less precise. This study successfully demonstrated that IGC, a molecular-scale probe-based technique, can effectively determine the contact angle range, a macroscopic property, for amorphous samples. Future work should incorporate correlations between energetic components of surface detected by IGC to extend this method's applicability to a wider material range.

New algorithm of three-phase equilibrium calculations for CO2-hydrocarbon-water systems

In this century, global warming caused by the accumulation of atmospheric carbon dioxide has become an essential concern. The industry has two main decarbonization options: CO2 capture for permanent storage in geological formations and CO2 utilization for enhancing oil recovery (EOR). Both methods require accurate reservoir simulation to correctly describe the fluids flowing process and design an optimal injection plan. However, existing reservoir simulation practices often neglect the interaction and dissolution of CO2 and hydrocarbon components in water, leading to inaccurate predictions. Neglecting CO2 dissolution in water undermines storage estimation for capture and results in unreliable EOR descriptions. Therefore, to address this, our study focuses on developing a reliable and accurate phase equilibrium calculation package for hydrocarbon-CO2-water three-phase systems, which meets the demanding efficiency and robustness criteria of reservoir simulation. In this paper, we first introduce the methodology of the three-phase equilibrium calculation algorithm, then illustrate the numerical techniques employed to improve computational efficiency and finally demonstrate superior robustness of this algorithm through comprehensive case studies. Our research contributes three key improvements. First, we have increased the reliability of phase behavior descriptions by considering the dissolution of CO2 and hydrocarbon components in water. Second, we have enhanced the robustness of the three-phase equilibrium calculations algorithm, enabling accurate determination of three-phase statuses and fluid behaviors where standard commercial software may fail. Third, our algorithm exhibits notable efficiency improvements, ensuring its suitability for three-phase compositional simulations. The findings of this research provide valuable insights into the accurate modeling of hydrocarbon-CO2-water three-phase systems and offer practical solutions for designing effective CO2 reduction strategies.

Robust Somatic Copy Number Estimation using Coarse-to-fine Segmentation

Introduction: Cancers routinely exhibit chromosomal instability that results in copy number variants (CNVs), namely changes in the abundance of genomic material. Unfortunately, the detection of these variants in cancer genomes is difficult. Methods: We present Ploidetect, a software package that effectively identifies CNVs within wholegenome sequenced tumors. Ploidetect utilizes a coarse-to-fine segmentation approach which yields highly contiguous segments while allowing for focal CNVs to be detected with high sensitivity. Results: We benchmark Ploidetect against popular CNV tools using synthetic data, cell line data, and real-world metastatic tumor data and demonstrate strong performance in all tests. We show that high quality CNVs from Ploidetect enable the identification of recurrent homozygous deletions and genes associated with chromosomal instability in a multi-cancer cohort of 687 patients. Using highly contiguous CNV calls afforded by Ploidetect, we also demonstrate the use of segment N50 as a novel metric for the measurement of chromosomal instability within tumor biopsies. Conclusion: We propose that the increasingly accurate determination of CNVs is critical for their productive study in cancer, and our work demonstrates advances made possible by progress in this regard.

Transferability of Model-Based Static Coefficient of Friction

The accurate determination of static coefficients of friction (COFs) is crucial in engineering design, yet standard reference values often show considerable variability. As a result, engineers frequently need to perform experimental COF measurements to ensure the reliable transferability of model-based COFs to real-world components. However, the effectiveness of cost-efficient laboratory tests, typically conducted on standardized samples, in reflecting actual component performance is often questioned as it is not trivial to transfer and scale the tribosystem. This study addresses this issue by conducting friction coefficient experiments on interference fits and flange connections, comparing the results with laboratory-based COF tests. The findings reveal a strong correlation when the tribological conditions of the real assembly are replicated in the lab. This research offers a method to enhance the accuracy and transferability of COF values from lab tests to practical applications, providing engineers with a more reliable approach to friction testing.

Reference-based image super-resolution of hyperspectral and red-green-blue image for determination of wheat kernel quality using deep learning networks

In the process of cultivation and harvest, wheat kernel quality is highly susceptible to various factors, such as disease, mildew, atrophy and impurities, and detection of kernel quality is essential to avoid hazard proliferation, facilitate product grading, and ensure food safety. Possessing abundant image and spectral characteristics, hyperspectral imaging (HSI) has gained impressive achievements in kernel quality analysis, but its low spatial resolution limits its detection accuracy. In this study, reference-based image super-resolution (RefSR) of HSI and Red-Green-Blue image was adopted to improve resolution to determine wheat kernel quality using deep learning networks. Firstly, RefSR was conducted by the improved transformer network with dual-branch feature extraction and weighted fusion operation and achieved excellent RefSR with significant resolution improvement, peak signal to noise ratio of 35.521 and structural similarity index of 0.97, outweighing the existing state-of-the-art networks. Then, the reflectance images (RIs) of effective wavelengths (EWs) from generated HSI images were combined with the residual network with a spatial, channel attention and multi-scale residual to determine wheat kernel quality. Precise analysis was achieved with the accuracy in calibration, validation and prediction sets of 100.00%, 95.26% and 92.78%. RefSR provides a novel and efficient approach for obtaining HSI images of high spatial resolution and facilitates the application of HSI in analysis of crop kernels. RIs of several sporadic EWs can be easily acquired and processed, achieving field and rapid kernel detection. Therefore, the proposed method furnishes the efficient, accurate and applicable determination of wheat kernel quality.

Chiroptical Sensing of Amines With Isatins.

Isatins are extensively researched compounds with diverse applications, particularly as synthetic precursors in pharmaceutical developments. However, their use as optical probes for enantioselective sensing of chiral amines has not been explored to date. Herein, we present a novel chiroptical assay with an optimized isatin that generates strong, red-shifted circular dichroism (CD) signals at approximately 380 nm upon ketimine formation with chiral amines. The intensity of the induced CD signal increases linearly with the enantiomeric excess of the analyte and thus allows quantitative chirality analysis. The general usefulness of this approach is demonstrated with a broad range of aliphatic and aromatic chiral amines, and by accurate determination of the enantiomeric composition of 10 samples.

Determination of the REV size for heterogeneous rocks with different grain sizes: Deep learning and numerical approaches

Accurate determination of the representative elementary volume (REV) size plays a pivotal role in analysing the mechanical properties and failure processes of heterogeneous rocks in complex engineering environments. In this study, a novel microstructure modelling strategy (NMMS) for determining the REV size is proposed by combining deep learning and an improved phase-field method (PFM). Micro- and macroscale experiments are systematically conducted to determine the real microstructural characteristics and mechanical properties of heterogeneous rocks with different grain sizes. On the basis of this experimental evidence, geometric models of different sizes were reconstructed through deep learning to avoid the limitations of human-based methods, and an improved PFM was used for numerical calculations. These models were then employed to perform numerical tests under uniaxial loading conditions, and the coefficient of variation was introduced to determine the REV size of heterogeneous rocks with different grain sizes. The research findings indicate that the final REV size is the maximum value of the REVs defined by the evaluation properties within an acceptable coefficient of variation. At a criterion of 5% for the coefficient of variation, the REV sizes are 60 mm×60 mm, 70 mm×70 mm, and 90 mm×90 mm for fine-medium-grained (FMG), medium-grained (MG), and coarse-grained (CG) rocks, respectively. Furthermore, the REV determined by the NMMS was applied to investigate the effects of microstructure on macromechanical properties and damage evolution under triaxial loading conditions. The numerical results show that the NMMS can accurately predict the macromechanical properties and microcracking patterns of heterogeneous rocks, especially the intracrystalline cracks in feldspar, the interfacial cracks in gravel, and the “voids” of cracks in biotite. This research can provide some basic references for the optimal choice of the REV size of heterogeneous rocks.

Effect of heat stress, determination of temperature-humidity index

Relevance. Increased values of temperature and relative humidity of the external environment lead to negative consequences for the animal body, forcing the thermoregulation processes to be turned on. These mechanisms allow the animal organism to adapt to new environmental conditions at the expense of productivity. In these cases heat stress is observed. It is established that its manifestation is observed after 17 hours and there is a possible decrease in productivity by 35–40%. To identify the effect of heat stress, accurate determination of temperature-humidity index (THI) is necessary.Methods. The materials and methods contain the most common formulas for determining the temperature and humidity index. The equipment and software package used for the research are presented.Results. A graph of the results of South Korean studies is presented to compare the effects of heat stress on productivity. The results and discussions display a modernized formula for determining the heat stress index and figures showing the level of heat stress at different temperature and relative humidity levels.

The chemical evolution of the Milky Way thin disk using solar twins

In this study we address whether the age--metallicity relation (AMR) deviates from the expected trend of metallicity increasing smoothly with age. We also show the presence (or absence) of two populations, as recently claimed using a relatively small dataset. Moreover, we studied the Milky Way thin disk's chemical evolution using solar twins, including the effect of radial migration and accretion events. In particular, we exploited high-resolution spectroscopy of a large sample of solar twins in tandem with an accurate age determination to investigate the Milky Way thin disk age--metallicity relationship. Additionally, we derived the stars' birth radius and studied the chemical evolution of the thin disk. We discovered that statistical and selection biases can lead to a misinterpretation of the observational data. An accurate accounting of all the uncertainties led us to detect no separation in the AMR into different populations for solar twins around the Sun ($-0.3 < Fe/H < 0.3$ dex). This lead us to the conclusion that the thin disk was formed relatively smoothly. For the main scenario of the Milky Way thin disk formation, we suggest that the main mechanism for reaching today's chemical composition around the Sun is radial migration with the possible contribution of well-known accretion events such as Gaia -Enceladus/Sausage (GES) and Sagittarius (Sgr).

Integrating 19F Distance Restraints for Accurate Protein Structure Determination by Magic Angle Spinning NMR Spectroscopy.

Traditional protein structure determination by magic angle spinning (MAS) solid-state NMR spectroscopy primarily relies on interatomic distances up to 8 Å, extracted from 13C-, 15N-, and 1H-based dipolar-based correlation experiments. Here, we show that 19F fast (60 kHz) MAS NMR spectroscopy can supply additional, longer distances. Using 4F-Trp,U-13C,15N crystalline Oscillatoria agardhii agglutinin (OAA), we demonstrate that judiciously designed 2D and 3D 19F-based dipolar correlation experiments such as (H)CF, (H)CHF, and FF can yield interatomic distances in the 8-16 Å range. Incorporation of fluorine-based restraints into structure calculation improved the precision of Trp side chain conformations as well as regions in the protein around the fluorine containing residues, with notable improvements observed for residues in proximity to the Trp pairs (W10/W17 and W77/W84) in the carbohydrate-binding loops, which lacked sufficient long-range 13C-13C distance restraints. Our work highlights the use of fluorine and 19F fast MAS NMR spectroscopy as a powerful structural biology tool.

Ocean alkalinity enhancement approaches and the predictability of runaway precipitation processes: results of an experimental study to determine critical alkalinity ranges for safe and sustainable application scenarios

Abstract. To ensure the safe and efficient application of ocean alkalinity enhancement (OAE), it is crucial to investigate its impacts on the carbonate system. While modeling studies reported a sequestration potential of 3–30 Gt carbon dioxide (CO2) per year (Oschlies et al., 2023), there has been a lack of empirical data to support the applicability of this technology in natural environments. Recent studies have described the effect of runaway carbonate precipitation in the context of OAE, showing that calcium carbonate (CaCO3) formation was triggered if certain Ωaragonite saturation thresholds were exceeded. This effect could potentially lead to a net loss of the initially added alkalinity, counteracting the whole concept of OAE. The related precipitation can adversely affect the carbon storage capacity and may in some cases result in CO2 emissions. Experiments at the Espeland marine biological station (Bergen, Norway) were conducted to systematically study the chemical consequences of OAE deployment. The experiments lasted for 20–25 d to monitor the temporal development of carbonate chemistry parameters after alkalinity addition and the subsequent triggered carbonate precipitation process. Identified uniform patterns before and during the triggered runaway process can be described by empirical functional relationships. For approaches equilibrated to the CO2 concentration of the atmosphere, total alkalinity (TA) levels of up to 6500 µmol kg−1 remained stable without loss of total alkalinity (TA) for up to 20 d. Higher implemented TA levels, up to 11 200 µmol kg−1, triggered runaway carbonate formation. Once triggered, the loss of alkalinity continued until the Ωaragonite values leveled out at 5.8–6.0, still resulting in a net gain of 3600–4850 µmol kg−1 in TA. The non-CO2-equilibrated approaches, however, only remained stable for TA additions of up to 1000 µmol kg−1. The systematic behavior of treatments exceeding this level allows us to predict the duration of transient stability and the quantity of TA loss after this period. Once triggered, the TA loss continued in the non-CO2-equilibrated approaches until Ωaragonite values of 2.5–5.0 were reached, in this case resulting in a net loss of TA. To prevent a net loss of TA, treated water must be diluted below the time-dependent critical levels of TA and Ωaragonite within the identified transient stability duration. Identified stability and loss patterns of added TA depend on local environmental conditions impacting the carbonate system, such as salinity, temperature, biological activity, and particle abundance. Incorporating such stability and loss patterns into ocean biogeochemical models, which are capable of resolving dilution processes of treated and untreated water parcels, would, from a geochemical perspective, facilitate the prediction of safe local application levels of OAE. This approach would also allow an accurate determination of the fate of added alkalinity and a more realistic carbon storage potential estimation compared to the assessments that neglect carbonate system responses to OAE.

Rapid Liquid Chromatography–Tandem Mass Spectrometry Method for Determination of Total and Free Testosterone in Human Serum and Its Application to Monitoring Biomarker Response of Elite Athletes

Total testosterone (TT) and free testosterone (FT) are important biochemical markers for anabolism of the human body, and can also serve as early screening indicators for overtraining syndrome (OTS). Presently, there is no fast and reliable serum TT and FT determination method in the field of sport science that can meet the requirements of sports research. Thus, a rapid and accurate determination method for serum TT and FT to fill the gap is needed urgently in sports training. Herein, a simple and reliable liquid chromatography–tandem mass spectrometry (LC-MS/MS) method for the simultaneous determination of TT and FT in serum was developed and fully validated, followed by the application of professional athletes in training monitoring. Efficient pretreatments based on only one-step liquid–liquid extraction (LLE) for TT and one-step LLE after a 20 min ultrafiltration for FT were adopted in this study, and the isotope internal standard of testosterone-13C3 was used to ensure the reliability of the whole procedure. A linear range of four orders of magnitude with 0.02–100 ng/mL can meet the concentration range requirement between a higher limit for male TT and a lower limit for female FT. The accuracy, precision, stability, and matrix effect were all within the limits of the guidelines. The serum TT and FT levels of 200 professional athletes (98 male athletes and 102 female athletes) were investigated by this method. Serum TT, FT, and FT/TT levels of professional athletes were significantly higher than the general population, and serum TT levels were significantly higher by LC-MS/MS than by a chemiluminescence immunoassay. In conclusion, the LC-MS/MS method for TT and FT measurement developed in this study is time-saving and easy to operate, which can be used as a reliable method for the determination of serum TT and FT in sports training, offering valuable information for monitoring anabolism of athletes and screening OTS in the early stage.

Pioneering simultaneous determination of breast cancer medications and metformin through sustainable micellar electrokinetic chromatographic method

The current study is the first report for the capillary electrophoretic simultaneous determination of five breast cancer medications, including febuxostat, quercetin, letrozole and doxorubicin in addition to metformin which is frequently co-administered with these drugs. The studied drugs are frequently purchased in different co-formulations used for breast cancer patients. A green micellar electrokinetic chromatographic (MEKC) method is proposed and optimized assisted by factorial design. The factors optimized include pH and concentration of buffer, surfactant concentration, as well as the applied voltage and injection time. The experimental results prove the optimum separation of the five drugs at pH 9.7 and buffer concentration of 10 mM with sodium dodecyl sulfate (SDS) concentration of 40 mM with +25 kV applied voltage. The developed method is validated considering linearity, precision, accuracy, and robustness adopting official guidelines. Good linearity is observed for all drugs, with correlation coefficients greater than 0.99. The range of percentage recoveries was from 98% to 102% with less than 2% relative standard deviation demonstrating the precision and accuracy of the established method. The study includes in-vitro assay of febuxostat, metformin, and doxorubicin in spiked human plasma. In addition, Accurate determination of the analytes under study in a variety of pharmaceutical dosage forms is accomplished by application of the proposed MEKC method. The greenness profile of the investigated method is confirmed using analytical eco-scale in addition to green analytical procedure index (GAPI) approaches.

Homojunction-Incorporated Oxygen Vacancy Functionalized Spherical TiO2 Nanocrystals for the Electrochemical Detection of Chemical Oxygen Demand.

Chemical oxygen demand (COD) is a critical criterion for the analytical assessment of the degree of organic contaminants in an aqueous system. Typically, toxic and expensive reagents are employed in standardized COD analysis methods, leading to secondary pollution. In this work, we developed a rapid electrochemical method for COD detection based on the oxidation of hydroxyl radicals for organics in water by using oxygen vacancy doped anatase/rutile-TiO2 nanoparticles as electrooxidation catalysts. Homojunction interface generated increasing oxygen vacancies for enhancing electron-transfer rate and accelerating H2O oxidation to substantially improve ·OH yield. Oxygen vacancy further increased the oxygen evolution potential of the material. Initially, glucose was chosen as a standard analyte to evaluate electrochemical responses, and water from urban wastewater treatment plants was assessed as real samples subsequently. Excellent analytical characteristics were achieved with the A/R-TiO2 sensor under the optimal conditions, exhibiting a linear range from 1 to 300 mg L-1 and detection limit of 0.1 mg L-1 COD. The estimated COD values obtained from the samples were highly consistent with those determined using the conventional standard dichromate method. We have presented a fast, cost-effective, and ecologically sustainable method that outperforms the standard COD analysis method and holds great potential for the accurate determination of COD and boasts high detection sensitivity and a broad linear range.

Analysis of Magnetization Dynamics in NiFe Thin Films with Growth-Induced Magnetic Anisotropies

We have used angled magnetron sputter deposition with and without sample rotation to control the magnetic anisotropy in 20 nm NiFe films. Ferromagnetic resonance spectroscopy, with data analysis using a Bayesian approach, is used to extract material parameters relating to the magnetic anisotropy. When the sample is rotated during growth, only shape anisotropy is present, but when the sample is held fixed, a strong uniaxial anisotropy emerges with in-plane easy axis along the azimuthal direction of the incident atom flux. When the film is deposited in two steps, with an in-plane rotation of 90 degrees between steps, the two orthogonal induced in-plane easy-axes effectively cancel. The analysis approach enables precise and accurate determination of material parameters from ferromagnetic resonance measurements; this demonstrates the ability to precisely control both the direction and strength of uniaxial magnetic anisotropy, which is important in magnetic thin-film device applications.

A Mobius transformation-based liftoff effect reduction method for crack classification and prediction in eddy current testing

In eddy current (EC) defect evaluation, accurate determination of the crack depth is crucial. The lift-off signal on the complex impedance plane is not necessarily horizontal and mostly arc-shaped, which makes it difficult to separate from crack signals, which can have various orientations depending on probe characteristics and frequencies. Phase rotation is normally used to align the lift-off signal to the real axis and defect signal is read from the imaginary axis. However, this approach proves challenging to separate lift-off and defect signals within the complex plane in many cases.To address this issue, this study proposes and implements a Mobius transformation that linearizes the arc-shaped lift-off signals on the complex plane, enabling more accurate extraction of crack signals unaffected by lift-off signal height. Furthermore, it is demonstrated through k-nearest neighbors (kNN) that the transformed crack signals can still be effectively quantified.

Diagnostic Accuracy of Saliva-based Testing as a Vibrio Cholerae Surveillance Tool among naturally-infected patients.

Saliva, as a diagnostic medium, offers a promising alternative to blood by virtue of its non-invasive collection, which enhances patient compliance, especially in paediatric and geriatric populations. In this study, we assessed the utility of saliva as a non-invasive medium for measuring V. cholerae-specific serum antibodies in naturally infected individuals. We tested paired serum and saliva samples obtained from a total of 63 cholera patients enrolled in a cohort study. Vibriocidal antibodies assay (IgM/IgG) as markers for accurate determination was used to determine cholera specific antibody levels. Using receiver operating characteristics (ROC) curve, we found that the best cut-off that maximizes (sensitivity + specificity) is 10 titres. At this saliva titre, the sensitivity is 76.9% (95%CI: 60.9%, 87.7%) and specificity is 80.0% (95%CI: 56.6%, 92.5%). Using Spearman's correlation coefficient, we also found evidence of a positive correlation between Vibrio Cholerae saliva and serum antibodies (rho=0.66, p<0.001). In conclusion, saliva-based diagnostic cholera tests has high diagnostic accuracy, and would be advantageous, cheaper, and quicker for early diagnosis of severe cholera outcomes.

A NIR light activated self‐reporting carbon dots assembly as phototheranostics for tumor photodynamic therapy

AbstractPhotodynamic therapy (PDT) has emerged as a promising protocol for cancer therapy. However, real‐time monitoring of PDT progress and accurate determination of the optimal treatment timing remain challenges. In this work, we selected carbon dots (CDs) and new indocyanine green (IR820) as building units to fabricate a smart nanotheranostics (CDs‐IR820 assembly) with the characteristics of controlled release and real‐time imaging to solve the time gap between diagnosis and treatment. The fabricated CDs‐IR820 assembly locked the photosensitivity of the CDs and could degrade under 750 nm laser irradiation to achieve controlled release of the CDs, thus used for cell imaging and producing single oxygen under the white light. Besides, the released CDs could migrate from the mitochondria to the nucleus during the PDT process, indicating the cell activity, which facilitated the regulation of treatment parameters to achieve the precise PDT for cancer.

Investigating the influence of geometric configurations and loading modes on mixed mode I/II fracture characteristics of rocks: Part I-Numerical simulation

The influence of geometric configurations and loading modes is a bottleneck that restricts the accurate determination of rock fracture parameters and the precise understanding of fracture mechanisms. Therefore, the phase field method is employed to analyze the influences of specimen geometry and loading modes on the dimensionless stress intensity factors, peak load, fracture toughness, and crack initiation angle during the rock mixed mode I/II fracture process. Three new configurations of specimens are proposed to test rock mixed mode I/II fracture. The research results indicate that as the prefabricated crack inclination angle increases, the peak load of three-point bending type specimen increases, while the peak load of diametric-compression type specimen decreases. Moreover, the influence of geometric configurations on the fracture parameters of three-point bending specimens is greater than that of diametric-compression disk specimens. The research findings of this work can provide basic supporting data for the establishment of mixed mode I/II fracture testing standards.

Describing the Disulfide Bond: From the Density Functional Theory and Back through the "Lego Brick" Approach.

Selected molecular species containing the disulfide bond, RSSR, have been considered, these ranging from hydrogen disulfide, H2S2 (R = H), to diphenyl disulfide with R = C6H5. The aim of this work is two-fold: (i) to investigate different computational approaches in order to derive accurate equilibrium structures at an affordable cost, (ii) to employ the results from the first goal in order to benchmark cheaper methodologies rooted in the density functional theory. Among the strategies used for the accurate geometrical determinations, the semiexperimental approach has been exploited in combination with a reduced-dimensionality VPT2 model, without however obtaining satisfactory results. Instead, the so-called "Lego brick" approach turned out to be very effective despite the flexibility of the systems investigated. Concerning the second target of this work, the focus was mainly on the S-S bond and the structural parameters related to it. Among those tested, PBE0(-D3BJ), M06-2X(-D3) and DSD-PBEP86-D3BJ have been found to be the best-performing functionals.