Jiangjohns4163

In the static regime, the coefficient of static friction, defined by the maximum pinning force of a droplet, is proportional to the contact angle hysteresis, whereas in the kinetic regime, the coefficient of kinetic friction is proportional to the difference in dynamic advancing and receding contact angles. We show the consistency between the droplet form of Amontons' first and second laws and an equation derived by Furmidge. We use these liquid-solid Amontons' laws to describe literature data and report friction coefficients for various liquid-solid systems. The conceptual framework reported here should provide insight into the design of superhydrophobic, slippery liquid-infused porous surfaces (SLIPS) and other surfaces designed to control droplet motion.Design of a suitable photoswitchable chiral cation-binding cage for the synthesis of optically active aminals was established using the azobenzene-BINOL hybrid oligoethylene glycol (ABOEG) through E/Z isomerization of the azobenzene unit. Under photoirradiation, both the catalytic activity and enantioselectivity of the generating (Z)-ABOEG are enhanced, in contrast to that of (E)-ABOEG, which can be attributed to the geometrically distinct coordination behavior between the metal cation and the oligoethylene glycols.Characteristic gene selection and tumor classification of gene expression data play major roles in genomic research. Due to the characteristics of a small sample size and high dimensionality of gene expression data, it is a common practice to perform dimensionality reduction prior to the use of machine learning-based methods to analyze the expression data. In this context, classical principal component analysis (PCA) and its improved versions have been widely used. Recently, methods based on supervised discriminative sparse PCA have been developed to improve the performance of data dimensionality reduction. However, such methods still have limitations most of them have not taken into consideration the improvement of robustness to outliers and noise, label information, sparsity, as well as capturing intrinsic geometrical structures in one objective function. To address this drawback, in this study, we propose a novel PCA-based method, known as the robust Laplacian supervised discriminative sparse PCA, termed RLSDSPCA, which enforces the L2,1 norm on the error function and incorporates the graph Laplacian into supervised discriminative sparse PCA. To evaluate the efficacy of the proposed RLSDSPCA, we applied it to the problems of characteristic gene selection and tumor classification problems using gene expression data. The results demonstrate that the proposed RLSDSPCA method, when used in combination with other related methods, can effectively identify new pathogenic genes associated with diseases. In addition, RLSDSPCA has also achieved the best performance compared with the state-of-the-art methods on tumor classification in terms of major performance metrics. The codes and data sets used in the study are freely available at http//csbio.njust.edu.cn/bioinf/rlsdspca/.Alcohols and carboxylic acids are among the most commercially abundant, synthetically versatile, and operationally convenient functional groups in organic chemistry. Under visible light photoredox catalysis, these native synthetic handles readily undergo radical activation, and the resulting open-shell intermediates can subsequently participate in transition metal catalysis. In this report, we describe the C(sp3)-C(sp3) cross-coupling of alcohols and carboxylic acids through the dual combination of N-heterocyclic carbene (NHC)-mediated deoxygenation and hypervalent iodine-mediated decarboxylation. This mild and practical Ni-catalyzed radical-coupling protocol was employed to prepare a wide array of alkyl-alkyl cross-coupled products, including highly congested quaternary carbon centers from the corresponding tertiary alcohols or tertiary carboxylic acids. We demonstrate the synthetic applications of this methodology to alcohol C1-alkylation and formal homologation, as well as to the late-stage functionalization of drugs, natural products, and biomolecules.Ni 2,2'-bipyridine (bpy) complexes are commonly employed photoredox catalysts of bond-forming reactions in organic chemistry. However, the mechanisms by which they operate are still under investigation. One potential mode of catalysis is via entry into Ni(I)/Ni(III) cycles, which can be made possible by light-induced, excited-state Ni(II)-C bond homolysis. Here, we report experimental and computational analyses of a library of Ni(II)-bpy aryl halide complexes, Ni(Rbpy)(R'Ph)Cl (R = MeO, t-Bu, H, MeOOC; R' = CH3, H, OMe, F, CF3), to illuminate the mechanism of excited-state bond homolysis. At given excitation wavelengths, photochemical homolysis rate constants span 2 orders of magnitude across these structures and correlate linearly with Hammett parameters of both bpy and aryl ligands, reflecting structural control over key metal-to-ligand charge-transfer (MLCT) and ligand-to-metal charge-transfer (LMCT) excited-state potential energy surfaces (PESs). Temperature- and wavelength-dependent investigations reveal moderate excited-state barriers (ΔH‡ ∼ 4 kcal mol-1) and a minimum energy excitation threshold (∼55 kcal mol-1, 525 nm), respectively. Correlations to electronic structure calculations further support a mechanism in which repulsive triplet excited-state PESs featuring a critical aryl-to-Ni LMCT lead to bond rupture. Structural control over excited-state PESs provides a rational approach to utilize photonic energy and leverage excited-state bond homolysis processes in synthetic chemistry.Spectral induced polarization (SIP) has the potential for monitoring reactive processes in the subsurface. While strong SIP responses have been measured in response to calcite precipitation, their origin and mechanism remain debated. Here we present a novel geo-electrical millifluidic setup designed to observe microscale reactive transport processes while performing SIP measurements. We induced calcite precipitation by injecting two reactive solutions into a porous medium, which led to highly localized precipitates at the mixing interface. Strikingly, the amplitude of the SIP response increased by 340% during the last 7% increase in precipitate volume. Furthermore, while the peak frequency in SIP response varied spatially over 1 order of magnitude, the crystal size range was similar along the front, contradicting assumptions in the classical grain polarization model. We argue that the SIP response of calcite precipitation in such mixing fronts is governed by Maxwell-Wagner polarization due to the establishment of a precipitate wall. Numerical simulations of the electric field suggested that spatial variation in peak frequency was related to the macroscopic shape of the front. These findings provide new insights into the SIP response of calcite precipitation and highlight the potential of geoelectrical millifluidics for understanding and modeling electrical signatures of reactive transport processes.Chromatography is a classical technique for protein separation. However, the chromatography column is filled with tightly packed separation materials and requires an additional pressurizing pump to propel the flow of fluidic samples, largely restraining their applications. Here, we combine heterostructured porous particles with paper strips, realizing spontaneous separation of similarly sized proteins. The interconnected nanofibrous structure and good hydrophility of paper strips enable the spontaneous flow of the liquid sample, and the heterostructured porous particles provide versatile tools for protein separation via electrostatic interaction. The fabricated paper strips are inexpensive, user-friendly, and disposable and exhibit good separation performance. This work may offer a new avenue for fabricating on-site bioseparation tools and purifying various biomacromolecules.In this work, we present a quantum mechanics/molecular mechanics (QM/MM) approach for the computation of solid-state nuclear magnetic resonance (SS-NMR) shielding constants (SCs) for molecular crystals. Besides applying standard-DFT functionals like GGAs (PBE), meta-GGAs (TPSS), and hybrids (B3LYP), we apply a double-hybrid (DSD-PBEP86) functional as well as MP2, using the domain-based local pair natural orbital (DLPNO) formalism, to calculate the NMR SCs of six amino acid crystals. All the electronic structure methods used exhibit good correlation of the NMR shieldings with respect to experimental chemical shifts for both 1H and 13C. We also find that local electronic structure is much more important than the long-range electrostatic effects for these systems, implying that cluster approaches using all-electron/Gaussian basis set methods might offer great potential for predictive computations of solid-state NMR parameters for organic solids.Chemical recycling is one of the most promising technologies that could contribute to circular economy targets by providing solutions to plastic waste; however, it is still at an early stage of development. In this work, we describe the first light-driven, acid-catalyzed protocol for chemical recycling of polystyrene waste to valuable chemicals under 1 bar of O2. Requiring no photosensitizers and only mild reaction conditions, the protocol is operationally simple and has also been demonstrated in a flow system. Electron paramagnetic resonance (EPR) investigations and density functional theory (DFT) calculations indicate that singlet oxygen is involved as the reactive oxygen species in this degradation process, which abstracts a hydrogen atom from a tertiary C-H bond, leading to hydroperoxidation and subsequent C-C bond cracking events via a radical process. Notably, our study indicates that an adduct of polystyrene and an acid catalyst might be formed in situ, which could act as a photosensitizer to initiate the formation of singlet oxygen. In addition, the oxidized polystyrene polymer may play a role in the production of singlet oxygen under light.Aggregation-induced enhancement (AIE) in the photoluminescence quantum yield (PLQY) from 12.5 to 51% in the N,N-dimethylformamide (DMF)-stabilized Au nanocluster (AuNC) system is reported here. The self-assembling of AuNC has been achieved via hydrogen bonding interaction, which is further utilized in designing the AuNC_DCM system for realizing a Förster resonance energy transfer (FRET)-based white LED (WLED), having CIE coordinates of (0.35, 0.29). The solution-processed fabrication strategy used, has given us the liberty to optimize its components for optimal full-spectrum light output. The CIE coordinates of the designed WLED have been improved further to (0.33, 0.32), with a high color rendering index of 93 and correlated color temperature of 5620 K by incorporating a green emitter, namely nitrogen-doped graphene quantum dots (NGQD), in the AuNC_DCM system. The excellent spectral quality of the as-designed WLED and the repeatability of the proposed fabrication method will make the developed AuNCs_DCM FRET conjugate useful in practical photonic applications.The photophysical and electrochemical properties of a new class of fluorinated benzonitrile compounds substituted with mixed phenoxazine and carbazole units have been investigated. When absorbing in a large range of the UV-vis spectrum due to both localized and charge-transfer absorptions, these compounds show dual broad emission in solution and intense emission in PMMA films, with photoluminescence quantum yields changing from a few percent in solution to 18% in a more rigid environment. The compounds also exhibit thermally activated delayed fluorescence demonstrated by the role of oxygen in the quenching of delayed fluorescence and by time-resolved luminescence studies, with an efficiency directly related to the number of phenoxazine substituents. selleck chemical Electrochemistry reveals dramatic changes in the reduction mechanisms according to the number of remaining fluorine atoms on the benzonitrile core. All these results demonstrate how it is possible to tune the photophysical and electrochemical properties of easily synthesizable derivatives by controlling the nature and relative number of the substituents on a simple aromatic platform.