On the nature of two-photon transitions for a collection of molecules in a Fabry-Perot cavity.

We investigate the effect of a cavity on nonlinear two-photon transitions of a molecular system and we analyze how such an effect depends on the cavity quality factor, the field enhancement, and the possibility of dephasing. We find that the molecular response to strong light fields in a cavity with a variable quality factor can be understood as arising from a balance between (i) the ability of the cavity to enhance the field of an external probe and promote multiphoton transitions more easily and (ii) the fact that the strict selection rules on multiphoton transitions in a cavity support only one resonant frequency within the excitation range. Although our simulations use a classical level description of the radiation field (i.e., we solve Maxwell-Bloch or Maxwell-Liouville equations within the Ehrenfest approximation for the field-molecule interaction), based on experience with this level of approximation in the past studies of plasmonic and polaritonic systems, we believe that our results are valid over a wide range of external probing.

Asymmetric Synthesis of Arboduridine.

The first asymmetric total synthesis of the monoterpenoid indole alkaloid arboduridine has been accomplished. The tricyclic A/B/D ring system was constructed by an enantioselective Michael reaction followed by intramolecular nucleophilic addition. Intramolecular α-amination of a ketone forged the piperidine ring, while a Horner-Wadsworth-Emmons (HWE) reaction was used to form the pyrrolidine ring. A reduction cyclization cascade led to formation of the tetrahydrofuran ring.

Acoustic noise reduction for spiral MRI by gradient derating.

PURPOSE: To show that the acoustic noise of spiral MRI can be reduced by derating the gradients with minimal penalty to image quality and scan time, and to illustrate an algorithm for optimal choice of derating parameters. THEORY AND METHODS: Acoustic noise level was measured and compared for various values of maximum gradient amplitude and slew rate for T1 -weighted spin-echo spiral scans while maintaining image contrast, FOV and resolution, and readout time. A full gradient trajectory and a derated gradient (undersampled) trajectory were chosen for a volunteer scan followed by parallel imaging-aided reconstruction to illustrate comparable image SNR. Two auto-derating methods, which prioritize slew rate and gradient amplitude, respectively, were derived using analytical results from the WHIRLED PEAS variant of spiral waveforms and compared in their acoustic noise level under test use cases. RESULTS: Derating the gradients made the scan quieter by 16.6 dB(A) on average than a full gradient trajectory and required an undersampling factor R = 2 in order to maintain scan time, with no appreciable penalty in image SNR. Prioritizing reduced slew rate resulted in maximal loudness reduction. CONCLUSION: Scanner gradients can often be derated to reduce the acoustic noise for spiral MRI with minimal penalty in scan time and image quality with the help of parallel imaging. An automatic slew-priority derating method that maximizes loudness reduction is given.

Ecological management model for the improvement of soil fertility through the regulation of rare microbial taxa in tea (Camellia sinensis L.) plantation soils.

Agricultural management is essential to enhance soil ecosystem service function through optimizing soil physical conditions and improving nutrient supply, which is predominantly regulated by soil microorganisms. Several studies have focused on soil biodiversity and function in tea plantation systems. However, the effects of different agriculture managements on soil fertility and microbes remain poorly characterized, especially for what concerns perennial agroecosystems. In this study, 40 soil samples were collected from 10 tea plantation sites in China to explore the effects of ecological and conventional managements on soil fertility, as well as on microbial diversity, community composition, and co-occurrence network. Compared with conventional management, ecological management was found to significantly enhance soil fertility, microbial diversity, and microbial network complexity. Additionally, a significant difference in community composition was clearly observed under the two agriculture managements, especially for rare microbial taxa, whose relative abundance significantly increased under ecological management. Random forest modeling revealed that rare taxa (e.g., Rokubacteria and Mortierellomycota), rather than dominant microbial taxa (e.g., Proteobacteria and Ascomycota), were key variables for predicting soil fertility. This indicates that rare taxa might play a fundamental role in biological processes. Overall, our results suggest that ecological management is more efficient than conventional management in regulating rare microbial taxa and maintaining a good soil fertility in tea plantation systems.

Modeling nonadiabatic dynamics with degenerate electronic states, intersystem crossing, and spin separation: A key goal for chemical physics.

We examine the many open questions that arise for nonadiabatic dynamics in the presence of degenerate electronic states, e.g., for singlet-to-triplet intersystem crossing where a minimal Hamiltonian must include four states (two of which are always degenerate). In such circumstances, the standard surface hopping approach is not sufficient as the algorithm does not include Berry force. Yet, we hypothesize that such a Berry force may be crucial as far as creating chiral induced spin separation, which is now a burgeoning field of study. Thus, this Perspective highlights the fact that if one can generate a robust and accurate semiclassical approach for the case of degenerate states, one will take a big step forward toward merging chemical physics with spintronics.

A "backtracking" correction for the fewest switches surface hopping algorithm.

We propose a "backtracking" mechanism within Tully's fewest switches surface hopping (FSSH) algorithm, whereby whenever one detects consecutive (double) hops during a short period of time, one simply rewinds the dynamics backward in time. In doing so, one reduces the number of hopping events and comes closer to a truly fewest switches surface hopping approach with independent trajectories. With this algorithmic change, we demonstrate that surface hopping can be reasonably accurate for nuclear dynamics in a multidimensional configuration space with a complex-valued (i.e., not real-valued) electronic Hamiltonian; without this adjustment, surface hopping often fails. The added computational cost is marginal. Future research will be needed to assess whether or not this backtracking correction can improve the accuracy of a typical FSSH calculation with a real-valued electronic Hamiltonian (that ignores spin).

On the proper derivation of the Floquet-based quantum classical Liouville equation and surface hopping describing a molecule or material subject to an external field.

We investigate different approaches to derive the proper Floquet-based quantum-classical Liouville equation (F-QCLE) for laser-driven electron-nuclear dynamics. The first approach projects the operator form of the standard QCLE onto the diabatic Floquet basis and then transforms to the adiabatic representation. The second approach directly projects the QCLE onto the Floquet adiabatic basis. Both approaches yield a form that is similar to the usual QCLE with two modifications: (1) The electronic degrees of freedom are expanded to infinite dimension and (2) the nuclear motion follows Floquet quasi-energy surfaces. However, the second approach includes an additional cross derivative force due to the dual dependence on time and nuclear motion of the Floquet adiabatic states. Our analysis and numerical tests indicate that this cross derivative force is a fictitious artifact, suggesting that one cannot safely exchange the order of Floquet state projection with adiabatic transformation. Our results are in accord with similar findings by Izmaylov et al., [J. Chem. Phys. 140, 084104 (2014)] who found that transforming to the adiabatic representation must always be the last operation applied, although now we have extended this result to a time-dependent Hamiltonian. This paper and the proper derivation of the F-QCLE should lay the basis for further improvements of Floquet surface hopping.

Numerical research on partially coherent flat-topped beam propagation through atmospheric turbulence along a slant path.

In this paper, we investigate the propagation of partially coherent flat-topped (PCFT) beams through atmospheric turbulence along a slant path. Using wave optics simulation (WOS), we calculated the on-axis intensity of PCFT beams in both vacuum and turbulence links, finding that PCFT beams will self-focus during propagation and that the beam coherence length has a significant impact on this focusing phenomenon. The effects of the zenith angle and the source coherence length on the scintillation index and mean signal-to-noise ratio (SNR) are analyzed. Furthermore, taking into consideration the limitation of available devices, we examined the impacts of source coherence time and detector integration time on the performance of PCFT beams in slant links. WOS results indicate as much as an extra 2 dB SNR gain from PCFT beams in short links in comparison with Gaussian Schell-model beams.

Research on partially coherent flat-topped vortex hollow beam propagation in turbulent atmosphere.

In this paper, the aperture averaged scintillation, mean signal-to-noise ratio (SNR), and average bit error rate (BER) for the partially coherent flat-topped vortex hollow beams propagating in turbulent atmosphere are evaluated. The variation of the aperture averaged scintillation against the coherence length of the beams and size of the receiver aperture is studied. It is also found that the aperture averaged scintillation increases with the topological charge of the partially coherent flat-topped vortex hollow beams. The partially coherent flat-topped vortex hollow beam with the smaller beam order has advantage to resist the effect of the turbulence. We also investigated the variation of the mean SNR and average BER against the coherence length.

Numerical investigation of flat-topped vortex hollow beams and Bessel beams propagating in a turbulent atmosphere.

In this paper, the aperture averaged scintillation, mean signal-to-noise ratio (SNR), and average bit error rate (BER) for both flat-topped vortex hollow beams and Bessel beams propagating in a turbulent atmosphere are evaluated. Investigations are also made illustrating the variation of aperture averaged scintillation, mean SNR, and average BER against the beam type, propagation distance, and size of the receiver aperture. Compared with the flat-topped vortex hollow beams, the Bessel beams have a smaller aperture averaged scintillation, higher mean SNR, and lower average BER when the receiver aperture is relatively small under the same conditions.

Comparative exomics of Phalaris cultivars under salt stress.

BACKGROUND: Reed canary grass (Phalaris arundinacea) is an economically important forage and bioenergy grass of the temperate regions of the world. Despite its economic importance, it is lacking in public genomic data. We explore comparative exomics of the grass cultivars in the context of response to salt exposure. The limited data set poses challenges to the computational pipeline. METHODS: As a prerequisite for the comparative study, we generate the Phalaris reference transcriptome sequence, one of the first steps in addressing the issue of paucity of processed genomic data in this species. In addition, the differential expression (DE) and active-but-stable genes for salt stress conditions were analyzed by a novel method that was experimentally verified on human RNA-seq data. For the comparative exomics, we focus on the DE and stable genic regions, with respect to salt stress, of the genome. RESULTS AND CONCLUSIONS: In our comparative study, we find that phylogeny of the DE and stable genic regions of the Phalaris cultivars are distinct. At the same time we find the phylogeny of the entire expressed reference transcriptome matches the phylogeny of only the stable genes. Thus the behavior of the different cultivars is distinguished by the salt stress response. This is also reflected in the genomic distinctions in the DE genic regions. These observations have important implications in the choice of cultivars, and their breeding, for bio-energy fuels. Further, we identified genes that are representative of DE under salt stress and could provide vital clues in our understanding of the stress handling mechanisms in general.

Graphene TiO2 nanocomposites with high photocatalytic activity for the degradation of sodium pentachlorophenol.

A series of graphene-TiO2 photocatalysts was synthesized by doping TiO2 with graphene oxide via hydrothermal treatment. The photocatalytic capability of the catalysts under ultraviolet irradiation was evaluated in terms of sodium pentachlorophenol (PCP-Na) decomposition and mineralization. The structural and physicochemical properties of these nanocomposites were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy, scanning electron microscopy, Ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectra, and Fourier-transform infrared spectroscopy. The graphene-TiO2 nanocomposites exhibited higher photocatalytic efficiency than commercial P25 for the degradation of PCP-Na, and 63.4% to 82.9% of the total organic carbon was fully mineralized. The improved photocatalytic activity may be attributed to the accelerated interfacial electron-transfer process and the significantly prolonged lifetime of electron-hole pairs imparted by graphene sheets in the nanocomposites. However, excessive graphene and the inhomogeneous aggregation of TiO2 nanoparticles may decrease photodegradation efficiency.

Construction of charge-reversible coordination-crosslinked spherical nucleic acids to deliver dual anti-cancer genes and ferroptosis payloads.

Spherical nucleic acids (SNAs) are nanostructures with the DNA arranged radially on the surface, thus allowing specific binding with cancer cells expressing high levels of scavenger receptor-A to enhance cellular uptake. However, conventional carriers for SNAs are cytotoxic, not degradable and difficult to deliver multiple payloads. In this study, we developed charge-reversible coordination-crosslinked SNAs to deliver dual anti-cancer genes and ferroptosis payload for anti-cancer purposes. To this end, we modified poly(lactic acid) (PLA) with functionalized side chains to allow its binding with antisense oligonucleotides (ASOs) and siRNA, annealed two single-stranded RNAs to obtain double-stranded RNA, and introduced a polyethylene glycol (PEG) shell to enhance the circulation time. Additionally, the ferroptosis payload imidazole was coordinated with iron ions as a core-crosslinked group to enhance the stability of SNAs and efficiency to kill cancer cells. We demonstrated that this novel nanocomplex efficiently internalized and killed CT-26 cells in vitro. In vivo data confirmed that the dual gene delivery system successfully targeted CT-26 tumors in tumor-bearing BALB/c mice, and exhibited strong tumor suppression ability, without inducing adverse toxic effects. Taken together, our dual gene therapy system offered an enhanced anti-tumor solution by simultaneously delivering dual anti-cancer genes and ferroptosis payload in tumor microenvironment.

Assessing heavy metal pollution in sediments from the northern margin of Chinese mangrove areas: Sources, ecological risks, and health impacts.

With the rapid economic development of coastal cities, the discharge of substantial amounts of heavy metal pollutants poses a serious hazard to mangroves; however, the potential sources of heavy metals and the resulting health risks are not fully understood. In this study, we analyzed the contents, sources, and ecological and health risks of heavy metal contamination in mangrove sediments from the northern margin of China. The accumulation of heavy metals in mangroves was primarily driven by five potential sources, namely agricultural (33.5 %), natural sources (21.3 %), industrial (19.1 %), aquaculture (14.3 %), and traffic (11.8 %). The assessment of health risks using a probabilistic approach demonstrated that noncarcinogenic risks were within acceptable limits for all populations. It was worth noting that both noncarcinogenic and carcinogenic risks were greater in children than in adults. Analysis of source-oriented health risks revealed that agricultural sources and As and Cd were priority sources and elements of pollution requiring attention.

Two-month ketogenic diet alters systemic and brain metabolism in middle-aged female mice.

The ketogenic diet (KD) is a very low-carbohydrate, high-fat diet that reduces glucose catabolism and enhances ß-oxidation and ketogenesis. While research in female rodents is limited, research in male rodents suggests that ketogenic interventions initiated at midlife may slow age-related cognitive decline, as well as preserve muscle mass and physical function later in life. This study aimed to investigate the effects of a KD on global metabolic changes in middle-aged females to inform potential mechanisms behind the anti-aging effects of this diet in an understudied sex. Targeted 1H-NMR metabolomics was conducted on serum, the liver, the kidney, and the gastrocnemius muscle, as well as the cortex and the hippocampal brain regions in 16-month-old female mice after a 2-month KD. Analysis of the serum and liver metabolome revealed that the 2-month KD resulted in increased concentrations of fatty acid catabolism metabolites, as well as system-wide elevations in ketones, consistent with the ketogenic phenotype. Metabolites involved in the glucose-alanine cycle were altered in the gastrocnemius muscle, serum and the liver. Other tissue-specific alterations were detected, including distinct effects on hepatic and renal one-carbon metabolism, as well as region specific differences in metabolism across hippocampal and cortical parts of the brain. Alterations to hippocampal metabolites involved in myelinogenesis could relate to the potential beneficial effects of a KD on memory.

A novel index for vegetation drought assessment based on plant water metabolism and balance under vegetation restoration on the Loess Plateau.

Vegetation is vital to the ecosystem, contributing to the global carbon balance, but susceptible to the impacts of climate change. Monitoring vegetation drought remains challenging due to the lack of widely accepted drought indices. This study focused on vegetation, and simulated the vegetation suitable water demand and soil available water supply (calculated by Remote-sensing-based Water Balance Assessment Tool model). The standardized Vegetation Water deficit Index (SVWDI) was established by calculating the vegetation water deficit, which reflects the response of vegetation to drought. We examined the spatiotemporal evolution of vegetation drought on the Loess Plateau and evaluated the applicability of standardized vegetation water deficit index. Our findings revealed that the standardized vegetation water deficit index demonstrated an overall upward trend across different time scales from 1991 to 2020. Drought conditions were concentrated in the first 20 years of the study period, but vegetation drought on the Loess Plateau has been alleviated in the past decade. Moreover, as the time scale extended, the trend of SVWDI generally decreased, with approximately 49.50 % (1-month scale), 46.66 % (3-month scale), 47.08 % (12-month scale), and 32.16 % (24-month scale) of the grid areas experiencing increased SVWDI. The correlation between SVWDI and tree-ring width index (TRWI) performed well under all precipitation gradients, but the Palmer drought severity index (PDSI) was only highly correlated with TRWI in regions with low precipitation. In terms of the relationship with vegetation health, SVWDI demonstrated the highest correlation with the normalized difference vegetation index (NDVI) across different time scales, followed by PDSI and standardized precipitation evapotranspiration index (SPEI). This study provides insights into the evolution of vegetation drought in response to climate change. The findings can guide initiatives such as returning farmland to forest and grassland on the Loess Plateau to aid climate change adaptation strategies.

Conductive catalysis by subsurface transition metals.

The nature of catalysis has been hotly pursued for over a century, and current research is focused on understanding active centers and their electronic structures. Herein, the concept of conductive catalysis is proposed and verified by theoretical simulations and experimental observations. Metallic systems containing buried catalytically active transitional metals and exposed catalytically inert main group metals are constructed, and the electronic interaction between them via metallic bonding is disclosed. Through the electronic interaction, the catalytic properties of subsurface transitional metals (Pd or Rh) can be transferred to outermost main group metals (Al or Mg) for several important transformations like semi-hydrogenation, Suzuki-coupling and hydroformylation. The catalytic force is conductive, in analogy with the magnetic force and electrostatic force. The traditional definition of active centers is challenged by the concept of conductive catalysis and the electronic nature of catalysis is more easily understood. It might provide new opportunities for shielding traditional active centers against poisoning or leaching and allow for precise regulation of their catalytic properties by the conductive layer.

Metabolomic and physiological analysis of alfalfa (Medicago sativa L.) in response to saline and alkaline stress.

Alfalfa (Medicago sativa L.) is a leguminous forage widely grown worldwide. Saline and alkaline stress can affect its development and yield. To elucidate the physiological mechanisms of alfalfa in response to saline and alkaline stress, we investigated the growth and physiological and metabolomic changes in alfalfa under saline (100 mM NaCl) and alkaline (100 mM Na2CO3, NaHCO3) stress. At the same Na+ concentration, alkaline stress caused more damage than that caused by saline stress. A total of 65 and 124 metabolites were identified in response to saline and alkaline stress, respectively. Determination of gene expression, enzyme activity, substance content, and KEGG enrichment analysis in key pathways revealed that alfalfa responded to saline stress primarily by osmoregulation and TCA cycle enhancement. Flavonoid synthesis, TCA cycle, glutamate anabolism, jasmonate synthesis, and cell wall component synthesis increased as responses to alkaline stress. This study provides important resources for breeding saline-alkaline-resistant alfalfa.

Ketogenic diet and BHB rescue the fall of long-term potentiation in an Alzheimer's mouse model and stimulates synaptic plasticity pathway enzymes.

The Ketogenic Diet (KD) improves memory and longevity in aged C57BL/6 mice. We tested 7 months KD vs. control diet (CD) in the mouse Alzheimer's Disease (AD) model APP/PS1. KD significantly rescued Long-Term-Potentiation (LTP) to wild-type levels, not by changing Amyloid-ß (Aß) levels. KD's 'main actor' is thought to be Beta-Hydroxy-butyrate (BHB) whose levels rose significantly in KD vs. CD mice, and BHB itself significantly rescued LTP in APP/PS1 hippocampi. KD's 6 most significant pathways induced in brains by RNAseq all related to Synaptic Plasticity. KD induced significant increases in synaptic plasticity enzymes p-ERK and p-CREB in both sexes, and of brain-derived neurotrophic factor (BDNF) in APP/PS1 females. We suggest KD rescues LTP through BHB's enhancement of synaptic plasticity. LTP falls in Mild-Cognitive Impairment (MCI) of human AD. KD and BHB, because they are an approved diet and supplement respectively, may be most therapeutically and translationally relevant to the MCI phase of Alzheimer's Disease.

Branched-Chain Amino Acids Deficiency Promotes Diabetic Neuropathic Pain Through Upregulating LAT1 and Inhibiting Kv1.2 Channel.

Diabetic neuropathic pain (DNP), one of the most common complications of diabetes, is characterized by bilateral symmetrical distal limb pain and substantial morbidity. To compare the differences  is aimed at serum metabolite levels between 81 DNP and 73 T2DM patients without neuropathy and found that the levels of branched-chain amino acids (BCAA) are significantly lower in DNP patients than in T2DM patients. In high-fat diet/low-dose streptozotocin (HFD/STZ)-induced T2DM and leptin receptor-deficient diabetic (db/db) mouse models, it is verified that BCAA deficiency aggravated, whereas BCAA supplementation alleviated DNP symptoms. Mechanistically, using a combination of RNA sequencing of mouse dorsal root ganglion (DRG) tissues and label-free quantitative proteomic analysis of cultured cells, it is found that BCAA deficiency activated the expression of L-type amino acid transporter 1 (LAT1) through ATF4, which is reversed by BCAA supplementation. Abnormally upregulated LAT1 reduced Kv1.2 localization to the cell membrane, and inhibited Kv1.2 channels, thereby increasing neuronal excitability and causing neuropathy. Furthermore, intraperitoneal injection of the LAT1 inhibitor, BCH, alleviated DNP symptoms in mice, confirming that BCAA-deficiency-induced LAT1 activation contributes to the onset of DNP. These findings provide fresh insights into the metabolic differences between DNP and T2DM, and the development of approaches for the management of DNP.