Spatial Pattern Evaluation of Rural Tourism via the Multifactor-Weighted Neural Network Model in the Big Data Era.

The exploration of the evaluation effect of rural tourism spatial pattern based on the multifactor-weighted neural network model in the era of big data aims to optimize the spatial layout of rural tourist attractions. There are plenty of problems such as improper site selection, layout dispersion, and market competition disorder of rural tourism caused by insufficient consideration of planning and tourist market. Hence, the multifactor model after simple weighting is combined with the neural network to construct a spatiotemporal convolution neural network model based on multifactor weighting here to solve these problems. Moreover, the simulation experiment is conducted on the spatial pattern of rural tourism in the Ningxia Hui Autonomous Region to verify the evaluation performance of the constructed model. The results show that the prediction accuracy of the model is 97.69%, which is at least 2.13% higher than that of the deep learning algorithm used by other scholars. Through the evaluation and analysis of the spatial pattern of rural tourist attractions, the spatial distribution of scenic spots in Ningxia has strong stability from 2009 to 2019. Meanwhile, the number of scenic spots in the seven plates has increased and the time cost of scenic spot accessibility has changed significantly. Besides, the change rate of the one-hour isochronous cycle reaches 41.67%. This indicates that the neural network model has high prediction accuracy in evaluating the spatial pattern of rural tourist attractions, which can provide experimental reference for the digital development of the spatial pattern of rural tourism.

Precise Identification of the Dimethyl Sulfoxide Triggered Tricarbonyldichlororuthenium(II) Dimer for Releasing CO.

Low concentrations of carbon monoxide (CO) can play vital roles in pharmacological and physiological functions in the human body. The transition-metal carbonyl complexes of the tricarbonyldichlororuthenium(II) dimer [Ru2(CO)6Cl4 (CORM-2)] were proposed as CO-releasing molecules (CORMs) to improve the delivery efficiency of CO for therapeutic effects. The accurate identification of final products for CORMs in solution and the detailed mechanisms of the release of CO were the essential prerequisite for its effective physiological application, which have been deficient. In this study, utilizing the cutting-edge two-dimensional (2D) IR spectroscopy, with the intrinsic vibrational modes and the coupling information on dynamics of intramolecular vibrational energy redistribution (IVR), the final products of A, B, C, and E are accurately identified when CORM-2 is dissolved in dimethyl sulfoxide (DMSO). Furthermore, with the clues on intermolecular interaction and chemical exchange dynamics between different products, the transformations between different products are also directly characterized for the first time. These findings challenge the results from the classic 1D spectroscopic pattern, and they evidently demonstrated that the release of CO from CORM-2 in DMSO was slow and complicated with multiple reaction pathways. Combining with DFT simulations, the detailed mechanisms of release of CO for CORM-2 dissolved in DMSO are schematically proposed, which can significantly contribute to its drug optimization and pharmacological as well as physiological applications.

A Genetically Encoded Two-Dimensional Infrared Probe for Enzyme Active-Site Dynamics.

While two-dimensional infrared (2D-IR) spectroscopy is uniquely suitable for monitoring femtosecond (fs) to picosecond (ps) water dynamics around static protein structures, its utility for probing enzyme active-site dynamics is limited due to the lack of site-specific 2D-IR probes. We demonstrate the genetic incorporation of a novel 2D-IR probe, m-azido-L-tyrosine (N3Y) in the active-site of DddK, an iron-dependent enzyme that catalyzes the conversion of dimethylsulfoniopropionate to dimethylsulphide. Our results show that both the oxidation of active-site iron to FeIII , and the addition of denaturation reagents, result in significant decrease in enzyme activity and active-site water motion confinement. As tyrosine residues play important roles, including as general acids and bases, and electron transfer agents in many key enzymes, the genetically encoded 2D-IR probe N3Y should be broadly applicable to investigate how the enzyme active-site motions at the fs-ps time scale direct reaction pathways to facilitating specific chemical reactions.

Large-Scale Thin CsPbBr3 Single-Crystal Film Grown on Sapphire via Chemical Vapor Deposition: Toward Laser Array Application.

Single-crystal perovskites with excellent photophysical properties are considered to be ideal materials for optoelectronic devices, such as lasers, light-emitting diodes and photodetectors. However, the growth of large-scale perovskite single-crystal films (SCFs) with high optical gain by vapor-phase epitaxy remains challenging. Herein, we demonstrated a facile method to fabricate large-scale thin CsPbBr3 SCFs (∼300 nm) on the c-plane sapphire substrate. High temperature is found to be the key parameter to control low reactant concentration and sufficient surface diffusion length for the growth of continuous CsPbBr3 SCFs. Through the comprehensive study of the carrier dynamics, we clarify that the trapped-related exciton recombination has the main effect under low carrier density, while the recombination of excitons and free carriers coexist until free carriers plays the dominate role with increasing carrier density. Furthermore, an extremely low-threshold (∼8 µJ cm-2) amplified spontaneous emission was achieved at room temperature due to the high optical gain up to 1255 cm-1 at a pump power of 20 times threshold (∼20 Pth). A microdisk array was prepared using a focused ion beam etching method, and a single-mode laser was achieved on a 3 µm diameter disk with the threshold of 1.6 µJ cm-2. Our experimental results not only present a versatile method to fabricate large-scale SCFs of CsPbBr3 but also supply an arena to boost the optoelectronic applications of CsPbBr3 with high performance.

Identifying and Modulating Accidental Fermi Resonance: 2D IR and DFT Study of 4-Azido-l-phenylalanine.

Azido-modified aromatic amino acids have been used as powerful infrared probes for the site-specific detection of proteins because of their large transition dipole strengths. However, their complex absorption profiles hinder their wider application. The complicated absorption profile of 4-azido-l-phenylalanine (pN3Phe) in isopropanol was identified and attributed to accidental Fermi resonances (FRs) by means of linear absorption and two-dimensional (2D) IR spectroscopies. The 2D IR results of pN3Phe in H2O and D2O further demonstrate that the FRs are distinctively influenced by the hydrogen-bonding environment. Under the influence of FRs, the 2D IR shape is distorted, indicating that pN3Phe is not a good candidate in spectral diffusion studies. A three-state model and first-principles calculations were used to analyze unperturbed energy levels, unveiling the FRs between the azide asymmetric stretching band and two combination bands. Furthermore, the anharmonic frequency calculations suggest that changing the substitution position of the azide group from para to meta can effectively modulate the FRs by reducing the coupling strength. This work provides a deep understanding of the FRs in azido-modified aromatic amino acids and sheds light on the modification of azido-modified amino acids for wider utilization as vibrational probes.

Measuring the carrier dynamics of photocatalyst micrograins using the Christiansen effect.

The optical measurement of photocatalyst materials is subject to Mie scattering when the particle size is comparable to the wavelength of the probe light. A novel approach was developed to deal with this scattering problem in the transient spectroscopy of photocatalyst micrograins using the Christiansen effect because the probe light in the vicinity of the Christiansen frequency can be transmitted. Scattering theory was used to analyze the transient spectra of micrograins and estimate the extinction coefficient at the Christiansen frequency. The Drude-Lorentz model was used to calculate the complex refractive index considering the contributions from both phonons and free carriers. We found that the net photogenerated carrier density was linearly correlated with the absorbance at the Christiansen frequency. With the parameters obtained from Raman scattering measurements, the absolute net carrier density was also determined. We further demonstrated the versatility of this method by applying it to the photogenerated carrier dynamics of intrinsic 6H-SiC grains. The transient broadband mid-IR spectra were measured by the pump-probe technique, and the transient absolute net carrier density was estimated. The carrier relaxation dynamics was fitted with three components with lifetime constants that agreed well with those obtained for SiC by transient broadband THz conductivity spectroscopy. We predict that this method could be extended to other photocatalytic materials with suitable probe frequencies.

Influence of Water in the Photogeneration and Properties of a Bifunctional Quinone Methide.

Quinone methides (QM) are crucial reactive species in molecular biology and organic chemistry, with little known regarding the mechanism(s) for the generation of short-lived reactive QM intermediates from relevant precursors in aqueous solutions. In this study, several time-resolved spectroscopy methods were used to directly examine the photophysics and photochemical pathways of 1,1'-(2,2'-dihydroxy-1,1'-binaphthyl-6,6'-diyl)bis(N,N,N-trimethylmethanaminium) bromide (BQMP-b) from initial photoexcitation to the generation of the key reactive binol QM intermediate (BQM) in aqueous solution. The fluorescence of BQMP-b is effectively quenched with a small amount of water, which suggests an excited state intramolecular proton transfer (ESIPT) occurs. The kinetics isotope effects observed in femtosecond and nanosecond time-resolved transient absorption experiments provide evidence for the participation of water molecules in the BQMP-b singlet excited state ESIPT process and in the subsequent -HNMe3+ group release and ground state intramolecular proton transfer that give rise to production of the reactive BQM intermediate. Nanosecond time-resolved resonance Raman (ns-TR3) measurements were also employed to investigate the structure and properties of several intermediates, including the key reactive BQM in aqueous solution. The ns-TR3 and density functional theory (DFT) computational results were compared, and this indicates the binol moiety and water molecules both have important roles in the characteristics and structure of the key reactive BQM intermediate produced from BQMP-b. The results presented here also provide new benchmark characterization of bifunctional quinone methide intermediates that can be utilized to guide direct time-resolved spectroscopic study of the alkylation and interstrand cross-linking reactions of quinone methides with DNA in the future.

Enhanced invasion of metastatic cancer cells via extracellular matrix interface.

Cancer cell invasion is a major component of metastasis and is responsible for extensive cell diffusion into and major destruction of tissues. Cells exhibit complex invasion modes, including a variety of collective behaviors. This phenomenon results in the structural heterogeneity of the extracellular matrix (ECM) in tissues. Here, we systematically investigated the environmental heterogeneity facilitating tumor cell invasion via a combination of in vitro cell migration experiments and computer simulations. Specifically, we constructed an ECM microenvironment in a microfabricated biochip and successfully created a three-dimensional (3D) funnel-like matrigel interface inside. Scanning electron microscopy demonstrated that the interface was at the interior defects of the nano-scale molecular anisotropic orientation and the localized structural density variations in the matrigel. Our results, particularly the correlation of the collective migration pattern with the geometric features of the funnel-like interface, indicate that this heterogeneous in vitro ECM structure strongly guides and promotes aggressive cell invasion in the rigid matrigel space. A cellular automaton model was proposed based on our experimental observations, and the associated quantitative analysis indicated that cell invasion was initiated and controlled by several mechanisms, including microenvironment heterogeneity, long-range cell-cell homotype and gradient-driven directional cellular migration. Our work shows the feasibility of constructing a complex and heterogeneous in vitro 3D ECM microenvironment that mimics the in vivo environment. Moreover, our results indicate that ECM heterogeneity is essential in controlling collective cell invasive behaviors and therefore determining metastasis efficiency.