Nonlinear Optical Properties of 2D Materials and their Applications.

2D materials are a subject of intense research in recent years owing to their exclusive photoelectric properties. With giant nonlinear susceptibility and perfect phase matching, 2D materials have marvelous nonlinear light-matter interactions. The nonlinear optical properties of 2D materials are of great significance to the design and analysis of applied materials and functional devices. Here, the fundamental of nonlinear optics (NLO) for 2D materials is introduced, and the methods for characterizing and measuring second-order and third-order nonlinear susceptibility of 2D materials are reviewed. Furthermore, the theoretical and experimental values of second-order susceptibility χ(2) and third-order susceptibility χ(3) are tabulated. Several applications and possible future research directions of second-harmonic generation (SHG) and third-harmonic generation (THG) for 2D materials are presented.

Sesquiterpenoids and Cytochalasins with Immunosuppressive Activity from Sonchus wightianus.

The plant species, Sonchus wightianus DC., was historically used in China for both medicinal and dietary uses. In present study, seven new guaiane sesquiterpenoids (1-7) and one cytochalasin (8), along with five known guaianes (9-13) and two known cytochalasins (14 and 15), were isolated from the whole plants of S. wightianus. These guaianes showed structural variations in the substituents at C-8 and/or C-15, and compounds 6 and 7 are two sesquiterpenoid glycoside derivatives. Their structures were determined by extensive analysis of spectroscopic, electronic circular dichroism, and X-ray diffraction data, and chemical method. Biological tests revealed that compounds 5 and 8 are potent and selective immunosuppressive reagents.

Temporal and vertical dynamics of carbon accumulation potential under grazing-excluded grasslands in China: The role of soil bulk density.

Despite the progress made in understanding relevant carbon dynamics under grazing exclusion, previous studies have underestimated the role of soil bulk density (BD), and its implications for potential accumulation of soil organic carbon (SOC), especially at regional scale over long term. In this study, we first constructed a database covering a vast majority of the grasslands in northwestern China based on 131 published literatures. A synthesis was then conducted by analyzing the experimental data to comprehensively investigate the mechanisms of vegetation recovery, carbon-nitrogen coupling, and the importance of changed soil BD in evaluating SOC sequestration potential. The results showed that although the recovery of vegetation height and cover were both critical for improving vegetation biomass, vegetation height required a longer recovery period. While the SOC accumulation was found to be greater in surface layers than deeper ones, it exhibited a reduced capacity for carbon sequestration and an increased risk of SOC loss. Grazing exclusion significantly reduced soil BD across different soil profiles, with the rate of change influenced by soil depth, time, geographical and climatic conditions. The potential for SOC accumulation in the top 30 cm of soil based on data of 2003-2022 was 0.78 Mg ha-1 yr-1 without considering BD effects, which was significantly underestimated compared to that of 1.16 Mg ha-1 yr-1 when BD changes were considered properly. This suggests that the efficiency of grazing exclusion in carbon sequestration and climate mitigation may have been previously underreported. Furthermore, mean annual precipitation represented the most relevant environmental factor that positively correlated to SOC accumulation, and a wetter climate may offer greater potential for carbon accumulation. Overall, this study implies grazing exclusion may play an even more critical role in carbon sequestration and climate change mitigation over long-term than previously recognized, which provides essential scientific evidence for implementing stepwise ecological restoration in grasslands.

Improved Luminous Efficiency of AgInS2 Quantum Dots and Zeolitic Imidazolate Framework-70 Composite for White Light Emitting Diode Applications.

The application of multiple quantum dots (QDs) in the field of white light emitting diodes (WLEDs) is still an important challenge due to their low luminous efficiency and quenching phenomenon. In this paper, we prepared AgInS2 QDs/zeolitic imidazolate framework-70 (AIS/ZIF-70) composite by a microwave hydrothermal method. Owing to the high porosity and stability of ZIF-70, it could effectively prevent quenching issues due to the aggregation of QDs. Since the ZIF-70 and QDs were chemically bonded, the formation of the ZnS layer could effectively passivate the surface defect and thus the quantum yield reached 21.49 % in aqueous solution. The luminous efficiency (LE) of the assembled AIS/ZIF-based WLED was reinforced by 6.8 times with a molar ratio of AgIn/Zn=18, i. e. at 5.26 % molar fraction of ZIF-70. Moreover, the color rendering index (CRI) and correlated color temperature (CCT) of AIS/ZIF-based WLED were 84.3 and 3631 K, respectively, indicating its potential application in solid-state lighting.

Total Synthesis of (±)-Spiroaxillarone A.

Spiroaxillarone A, a novel and unique spirocyclic dinaphthalene natural product with significant antimalarial activity, was regioselectively synthesized from tetrahydrocurcumin in five steps with an overall 10% yield. Key features of the synthesis involved an oxidized free radical cycloaddition to build the spiro ring central skeleton and an oxidized dehydrogenation to introduce two double bonds via enol silicon ether from diketones.

Exploring the influence of human mobility factors and spread prediction on early COVID-19 in the USA.

BACKGROUND: COVID-19 is still spreading rapidly around the world. In this context, how to accurately predict the turning point, duration and final scale of the epidemic in different countries, regions or cities is key to enabling decision makers and public health departments to formulate intervention measures and deploy resources. METHODS: Based on COVID-19 surveillance data and human mobility data, this study predicts the epidemic trends of national and state regional administrative units in the United States from July 27, 2020, to January 22, 2021, by constructing a SIRD model considering the factors of "lockdown" and "riot". RESULTS: (1) The spread of the epidemic in the USA has the characteristics of geographical proximity. (2) During the lockdown period, there was a strong correlation between the number of COVID-19 infected cases and residents' activities in recreational areas such as parks. (3) The turning point (the point of time in which active infected cases peak) of the early epidemic in the USA was predicted to occur in September. (4) Among the 10 states experiencing the most severe epidemic, New York, New Jersey, Massachusetts, Texas, Illinois, Pennsylvania and California are all predicted to meet the turning point in a concentrated period from July to September, while the turning point in Georgia is forecast to occur in December. No turning points in Florida and Arizona were foreseen for the forecast period, with the number of infected cases still set to be growing rapidly. CONCLUSIONS: The model was found accurately to predict the future trend of the epidemic and can be applied to other countries. It is worth noting that in the early stage there is no vaccine or approved pharmaceutical intervention for this disease, making the fight against the pandemic reliant on non-pharmaceutical interventions. Therefore, reducing mobility, focusing on personal protection and increasing social distance remain still the most effective measures to date.

Total Synthesis of Nominal ent-Chlorabietol B.

The nominal enantiomer of chlorabietol B was regio- and stereoselectively synthesized from (-)-abietic acid in 13 steps. Key features of the synthesis involved an oxidative [3+2] cycloaddition to install the dihydrobenzofuran moiety and an Aldol reaction, followed by elimination and reduction steps to introduce the long chain with three cis double bonds. However, obvious differences in the NMR spectra of the synthetic and natural samples suggested that the proposed structure of chlorabietol B should be revised carefully.

Structural Elucidation and Total Synthesis of Three 9-Norlignans from Curculigo capitulata.

Capitulactones A-C, three unprecedented 9-norlignans featuring a unique 3,5-dihydrofuro[2,3- d]oxepin-7(2 H)-one scaffold, were isolated from the roots of Curculigo capitulata. Their structures with absolute configurations were unambiguously established by a combination of spectroscopic data, ECD analysis, and total synthesis. Biomimetic total syntheses of three pairs of the corresponding enantiomers were achieved in 9-10 steps with overall yields of 14.8, 12.7, and 10.3%, respectively. Notably, the unique scaffold of the common western hemisphere of the molecules was constructed by using the oxidation-reduction strategy from benzodihydrofuran.

Impacts of a Specific Cyclooxygenase-2 Inhibitor on Pressure Overload-Induced Myocardial Hypertrophy in Rats.

OBJECTIVE: The aim of this study was to observe the impacts of the specific cyclooxygenase-2 inhibitor celecoxib on cardiac structures, functions, and inflammatory factors during the process of pressure overload-induced myocardial hypertrophy. METHODS: Twenty-four male Sprague Dawley rats were randomly divided into 3 groups: the sham operation group, the surgery group, and the celecoxib group. The model was established according to the abdominal aortic coarctation method. RESULTS: At 16 weeks, rats in the celecoxib group were fed a celecoxib-mixed diet (10 mg/kg) for 8 consecutive weeks. At week 24 after model establishment, the cardiac structures and functions were observed; changes in the levels of tumor necrosis factor (TNF)-α, transforming growth factor (TGF)-ß, prostaglandin E2 (PGE2), C-reactive protein (CRP), and uric acid (UA) were detected; and the contents of Smad1/2/3 proteins (Smad1, Smad2, and Smad3)  were determined. Left ventricular mass index, the heart weight/body weight ratio, and TNF-α, TGF-ß, PGE2, CRP, and UA levels of the celecoxib group were all significantly decreased relative to those of the surgery group (P < .05); moreover, the cardiac functions were significantly improved compared to those of the surgery group (P < .05). CONCLUSIONS: These results show that inflammatory factors are involved in the myocardial hypertrophy process and that celecoxib may reverse myocardial hypertrophy through a variety of pathways.

Room-Temperature Ionic-Liquid-Assisted Microwave Preparation of Tunable Photoluminescent Copper-Indium-Zinc-Sulfide Quantum Dots.

A facile approach towards photoluminescent (PL) Cu-In-Zn-S quantum dots (CIZS QDs) has been developed, comprising microwave treatment with the assist of room-temperature ionic liquid (RTIL). Because of its high polarizability, RTIL served as a microwave absorbent, which resulted in the increase of the instantaneous nucleation rate and the rapid synthesis of CIZS QDs at low temperature. Moreover, the surface decoration of QDs with RTIL can passivate the surface defects greatly. The PL intensity of the CIZS QDs depends on the anion species, alkyl chain length of the RTIL, and the metal element ratios of the QDs. On the basis of the variable PL peak position and extended luminescence lifetime of the CIZS QDs, the superior emission behavior of the QDs was confirmed by surface etching with fluoride produced by the hydrolysis of RTIL 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4 ). Moreover, the intermediate alkyl chain length of the RTIL can avoid aggregation, which results in the construction of CIZS QDs with homogenous size distribution. The shape-controlled CIZS QDs show a broadened tunable emission peak from 677 to 579 nm compared with that of QDs prepared by a conventional one-pot method by mixing the raw materials. CIZS QDs also exhibit a high quantum yield (QY) of 24.1 % after coating with a ZnS shell. This method is expected to be a useful technique for the rapid synthesis of multiple QDs with a wider range of emission wavelengths and higher QY for a variety of applications.

Biomimetic Synthesis of Isorosmanol and Przewalskin A.

Przewalskin A, a novel C23 terpenoid with anti-HIV-1 activity from Salvia przewalskii Maxim, was formed in 10 steps via isorosmanol from (+)-carnosic acid. The synthetic strategy was inspired primarily by the biogenetic hypothesis and was enabled by epoxidation, epoxide ring opening, and lactonization in one pot to prepare the 11,12-dimethoxy isorosmanol, and bismuthonium ylide-induced ring expansion of o-quinone to construct the 2-acyl-3-hydroxytropone.

Whey Acidic Protein/Four-Disulfide Core Domain 21 Regulate Sepsis Pathogenesis in a Mouse Model and a Macrophage Cell Line via the Stat3/Toll-Like Receptor 4 (TLR4) Signaling Pathway.

BACKGROUND Whey acidic protein/four-disulfide core domain 21 (Wfdc21), also known as Lnc-DC, it has been reported to be correlated with immune response. However, the role of Wfdc21 in the pathogenesis of sepsis is still unknown. In the present study, we aimed to investigate the role of Wfdc21 in the pathogenesis of sepsis. MATERIAL AND METHODS The cecal ligation and puncture (CLP)-induced sepsis model was established in Balb/c mice. Animals were euthanized 4, 8, 16, or 24 h after CLP. The glycogen distribution in the kidney and liver was checked by Periodic acid-Schiff (PAS) staining. Changes in the serum interleukin-1ß (IL-1ß) and tumor necrosis factor-α (TNF-α) concentrations were monitored with ELISA, and Wdfc21 expression was determined by qPCR. Mouse macrophage-like RAW264.7 cells were treated with different doses of lipopolysaccharide (LPS) from Escherichia coli to mimic sepsis in vitro. Western blot analysis was performed to confirm whether LPS-induced in vitro sepsis was correlated with the involvement of the Stat3/TLR4 signaling pathway. In addition, RAW 264.7 cells were infected with lentiviruses containing Wfdc21 shRNA to further confirm the role of Wfdc21 in the pathogenesis of sepsis. RESULTS We found that Wfdc21 level was elevated in the CLP-induced animal model and LPS-treated RAW264.7 cells. Furthermore, the downregulation of Wfdc21 modulated the concentration of pro-inflammatory factors in LPS-treated macrophages, such as IL-1ß and TNF-α, in LPS-treated macrophages. This regulatory effect was mediated through the Stat3/TLR4 signaling pathway, since Wfdc21 can regulate p-Stat3 and TLR4 levels in LPS-treated macrophages. CONCLUSIONS Wfdc21 plays a critical role in the pathogenesis of sepsis and may provide a therapeutic target for sepsis treatment.

TMSI-promoted vinylogous Michael addition of siloxyfuran to 2-substituted chromones: a general approach for the total synthesis of chromanone lactone natural products.

A concise and facile synthetic protocol for the construction of the 2-γ-lactone chromanone skeleton has been achieved through a TMSI-promoted diastereoselective vinylogous Michael addition of siloxyfuran to 2-substituted chromones. The applicability of this method is demonstrated through the rapid access to the total syntheses of (±)-microdiplodiasone, (±)-lachnone C, and (±)-gonytolides C and G.

Cu(II) /TEMPO-promoted one-pot synthesis of highly substituted pyrimidines from amino acid esters.

A novel, Cu(OAc)2/TEMPO promoted one-step approach for the preparation of fully substituted pyrimidines from readily available amino acid esters has been described. In this reaction, the amino acid esters act as the only N-C sources for the construction of corresponding pyrimidines. The mechanism of this process includes oxidative dehydrogenation, the generation of an imine radical, and a formal [3+3] cycloaddition. This methodology proves to be a high atom-economic and straightforward strategy for the synthesis of pyrimidines and diverse substrates which are substituted by various functional groups have been afforded in moderate to good yield.

Total synthesis of (±)-przewalskin B.

A concise total synthesis of przewalskin B was accomplished from readily available diene 7. Key features of the synthesis involved a Diels-Alder reaction to install the A ring, a Claisen-Johnson rearrangement to establish the spiro-quaternary center, and a ring-closing metathesis (RCM) of a sterically crowded system to construct the cyclic enone moiety.

Cu/Mn co-oxidized cyclization for the synthesis of highly substituted pyrrole derivatives from amino acid esters: a strategy for the biomimetic syntheses of lycogarubin C and chromopyrrolic acid.

An effective and concise approach to synthesis of tetrasubstituted pyrroles from readily available amino acid esters by the promotion of Cu(OAc)2 in conjunction with Mn(OAc)3 has been developed. This reaction proceeds through multiple dehydrogenations, deamination, and oxidative cyclization. This oxidized system tolerates substrates bearing various electron-donating or electron-withdrawing groups. With this methodology, several key intermediates of natural products have been effectively prepared, and the total syntheses of lycogarubin C and chromopyrrolic acid have been completed in high efficiency.

Asymmetric Total Syntheses of ent-Stachybotrin C and Its Congener.

The asymmetric total syntheses of ent-stachybotrin C and its congener have been accomplished through a convergent approach in the longest linear sequence of 12 steps from commercially available materials, respectively. Noteworthy transformation of the synthesis involved a cascade Knoevenagel condensation/Hantzsch ester reduction/epoxide ring-opening/transetherification to construct the core pyran ring with two adjacent stereocenters.

Stereochemical insights into enantioselective antiplasmodial lignanamides from the twigs and leaves of Solanum erianthum.

Stereochemical investigations on the twigs and leaves of Solanum erianthum afforded five pairs of lignanamide enantiomers and a previously undescribed phenolic amide (3). Particularly, two pairs of previously undescribed lignanamide racemates (1a/1b-2a/2b) represent the first case of natural products that feature an unreported 5/5-fused N/O-biheterocyclic core. Their structures, including the absolute configurations, were determined unambiguously by using spectroscopic analyses and electronic circular dichroism calculations. A speculative biogenetic pathway for 1-3 was proposed. Interestingly, these lignanamides exhibited enantioselective antiplasmodial activities against drug-sensitive Plasmodium falciparum 3D7 strain and chloroquine-resistant Plasmodium falciparum Dd2 strain, pointing out that chirality plays an important role in drug development.

Spatiotemporal evolution and influencing factors of China's economic development performance under carbon emission constraints.

BACKGROUND: China's high-quality economic development depends on achieving sustainable economic development, reaching peak carbon emissions, achieving carbon neutrality, and intensifying the development of an industrial and energy structure that saves resources and protects the environment. This study used the data envelopment analysis (DEA) model and the Malmquist productivity index to measure the economic development performance of mainland China under carbon emission constraints. Then, it described the spatiotemporal evolution of economic development performance and analyzed its influencing factors using the Tobit model. RESULTS: The results revealed that there were obvious differences in the trends of the static and dynamic performance of economic development. On the one hand, the static performance of economic development exhibited an upward trend from 2008 to 2020. Its distribution characteristics were dominant in the higher and high-level areas. On the other hand, the dynamic performance had a downward trend from 2008 to 2016 and then an upward trend from 2016 to 2020. In most provinces, the dynamic performance was no longer constrained by technological progress but rather by scale efficiency. It was found that the main factors influencing economic development performance were urbanization level, energy efficiency, vegetation coverage, and foreign investment, while other factors had no significant influence. CONCLUSIONS: This study suggests that China should improve its economic development performance by increasing the use of clean energy, promoting human-centered urbanization, increasing carbon absorption capacity, and absorbing more foreign capital in the future.

Total Synthesis of Guajavadimer A via Lewis Acid-Catalyzed Cascade Double Hetero-Diels-Alder Reactions.

The first total synthesis of guajavadimer A, a dimeric caryophyllene-derived meroterpenoid featuring an unprecedented 4-9-6-6-6-9-4-fused ring system, is reported. Key to the approach is the construction of the pyrano[4,3,2-de]chromene core via a cascade of double hetero-Diels-Alder reactions. Practically, a 4-substituted-2,6-dihydroxybenzaldehyde dimethyl acetal serves as an effective surrogate for ortho-quinone methide, which is generated from the corresponding aldehyde and trimethyl orthoformate, with ß-caryophyllene undergoing cycloaddition to generate pyrano[4,3,2-de]chromene derivatives with excellent regioselectivity and stereoselectivity in one pot under mild conditions.