Pattern changes of ecological product trade in countries along the Belt and Road.

The Belt and Road Initiative (BRI) was designed to promote economic and trade cooperation between countries along the Belt and Road (B&R), specifically by building an international trade network. Ecological resources are the basis for human survival. Countries along the B&R transform ecological resources into ecological products by production activities. These products can then be used for trade, thereby driving the countries' economic development. This study uses net primary productivity (NPP) as a unified measure of ecological products, and explores the pattern changes of ecological product trade in countries along the B&R, from 2013 to 2019 (from the BRI proposal to the outbreak of COVID-19). The purpose of the study is to reveal the impact of the BRI on the trade of ecological products. The results show that (1) the trade scale of ecological products in the B&R region has changed significantly. The total volume of traded ecological products increased from 2071.74 to 2631.00 TgC. This represented an increase of about 26.99%, or 7.41% higher than the global average. (2) The spatial distribution pattern of ecological product trade did not change significantly in countries along the B&R. However, the gravity centers of the total and net trade volume of ecological products moved 120.74 km to the northeast and 392.98 km to the southeast, respectively. (3) The trade structure of ecological products in the B&R region, six sub-regions, and most countries remained relatively stable. Only the proportion of the livestock products trade in Mongolia and the proportion of the forest products trade in Bhutan have increased significantly. This finding suggests that the strength and breadth of the construction of unimpeded trade in countries along the B&R still need to further strengthened, in order to accelerate the realization of the vision of the Green Silk Road.

Exploring adaptive approaches for social-ecological sustainability in the Belt and Road countries: From the perspective of ecological resource flow.

The countries along the Belt and Road (B&R) are characterized by fragile ecosystems and underdevelopment economy. International trade usually transferred the eco-environmental negative impacts to developing countries. How to avoid the conflict between economic development and eco-environmental protection is the primary concern of building the Green Silk Road. To discover the adaptive strategies for ensuring the sustainability of the social-ecosystem in countries along the B&R, this study analyzes the supply-consumption relationship of ecological resources by simulating the flow of net primary productivity between the ecosystem and the social system. The results show that: (1) The flow of ecological resources between agricultural and husbandry systems have effectively alleviated the local ecological pressure caused by animal husbandry in countries along the B&R. Animal husbandry in developed countries economize the local ecological resources by importing feed, while mitigating the grazing pressure by utilizing the local crop residues in underdeveloped agricultural countries. (2) International trade not only enables countries with insufficient ecological resources to meet their demands by importing ecological products and thus alleviate ecosystem pressure, but also promotes countries with sufficient ecological resources to transform their resource advantages into economic advantages by exporting without at the expense of ecological sustainability. (3) For underdeveloped countries, the dependence of economic development on ecological resources is at the expense of the living demands of residents, only if the economy could have leap-forward improvement the allocation of ecological resources within the social system would be inclined to living demands. These adaptive approaches not only provide the evidences of ecological-social sustainable development by promoting the reasonable flow and allocation of ecological resources, but also imply the necessary assistance for the underdeveloped countries to guarantee the basic human well-being in economic development.

The external dependence of ecological products: Spatial-temporal features and future predictions.

The instability of international trade can threaten the resource security of resource-importing countries, while international trade helps address spatial mismatches between regional populations, economies, and resources. Ecological products are the basis for human survival and development, in which agri-livestock products are especially sensitive to trade fluctuation and closely related to human well-being. The external dependence is an important indicator to reveal the external supply risk of regional resources. Scientific understanding the external dependence of ecological products can reveal the potential risks of trade fluctuations to human well-being and ecological sustainability. In this study, the global status and trend of countries' external dependence of agri-livestock ecological products are investigated. The results showed that nearly 80% (141) of countries relied on imports to meet ecological product demands in 2018, in which Asian-African-Latin countries accounted for about 78%, which indicated that the instability of international trade would threaten the ecological resource security in 80% of the world's countries, especially for underdeveloped countries. Even worse, 68% of countries are increasing their external dependence of ecological products. Even if the intensity of ecological resource exploitation reaches the maximum sustainable utilization level, 60% (113) of countries are expected to need imports for meeting their ecological product demands in 2050. Moreover, even considering the agricultural technological upgrade and the consumption transformation, more than 50% (94) of countries are still net importers of ecological products. Therefore, trade liberalization is still one of the important means to reduce resource security risks caused by trade instability. More notably, half of the countries in the world may sacrifice ecological sustainability to meet basic human well-being in the future under deglobalization.

Ultrafast conformational dynamics of Rydberg-excited N-methyl piperidine.

We have observed the ultrafast conformational dynamics of electronically excited N-methyl piperidine (NMP) using time-resolved Rydberg fingerprint spectroscopy. Optical excitation at various wavelengths ranging from 212 nm to 229 nm leads to the 3s or 3p Rydberg states and induces coherent oscillatory motions with periods of about 700 fs. These coherent motions survive the internal conversion from 3p to 3s but then dephase on a time scale of a few oscillations. Intramolecular vibrational energy redistribution on a picosecond time scale leads to an equilibrium between two conformeric structures that are separated in binding energy by 0.09 eV. Model calculations using the DFT-SIC method are in excellent agreement with the experiments and identify the conformers as the chair and twist structures of NMP. The analysis of the equilibrium parameters at long time delays as a function of excitation wavelength allows for the extraction of thermodynamic parameters for the conformeric transformation. We derive an enthalpy of the chair to twist reaction in the 3s excited state of 62 meV with an entropy of 19.70 J mol-1 K-1. An activation energy of 276 meV is also obtained with a kinetic model.

Transient Symmetry Controls Photo Dynamics near Conical Intersections.

Excited-state chemistry lacks generalized symmetry rules. With many femtochemistry studies focused on individual cases, it is hard to build up the same level of chemical intuition for excited states as that for ground states. Here, we unravel the degrees of freedom involved in ultrafast internal conversion (IC) by mapping the vibrational coherence of the initial wavepacket and the dependence on molecular symmetry in various cyclic tertiary amines. Molecular symmetry plays an important role in the preservation of vibrational coherence in the transit from one electronic state to another. We show here that it is sufficient for the molecule to simply have the possibility of a more symmetric structure to achieve the preservation of vibrational coherence. It can be transient and still lead to preservation. This finding provides an additional angle on how symmetry influences electronic transitions and an additional piece to the puzzle of establishing symmetry-based selection rules for excited-state processes.

Risk of Global External Cereals Supply under the Background of the COVID-19 Pandemic: Based on the Perspective of Trade Network.

International food trade is an integral part of the food system, and the COVID-19 pandemic has exposed the fragility of external food supplies. Based on the perspective of cereals trade networks (CTN), the pandemic risk is combined with the trade intensity between countries, and an assessment model of cereals external supply risk is constructed that includes external dependence index (EDI), import concentration, and risk of COVID-19 from import countries index (RICI). The results show that: (1) the global main CTN have typical scale-free characteristics, and seven communities are detected under the influence of the core countries; (2) about 60%, 50%, and 70% of countries face risks of medium and above (high and very high) external dependence, concentration of imports, and COVID-19 in the country of origin, respectively. Under the influence of the pandemic, the risk of global external cereal supply index (RECSI) has increased by 65%, and the USA-CAN communities show the highest risk index; (3) the countries with a very high risk are mainly the Pacific island countries and the Latin American and African countries. In addition, Japan, Mexico, South Korea, and 80% of the net food-importing developing countries are at high or very high RECSI levels. Approximately 50% of countries belong to the compound risk type, and many export countries belong to the RICI risk type; (4) global external food supply is subjected to multiple potential threats such as trade interruption, "price crisis", and "payment dilemma". The geographical proximity of community members and the geographical proximity of the pandemic risk is superimposed, increasing the regional risk of external food supply; and (5) this study confirms that the food-exporting countries should avoid the adoption of food export restriction measures and can prevent potential external supply risks from the dimensions of maintaining global food liquidity and promoting diversification of import sources. We believe that our assessment model of cereals external supply risk comprises a useful method for investigations regarding the international CTN or global food crisis under the background of the pandemic.

Ultrafast X-ray scattering offers a structural view of excited-state charge transfer.

Intramolecular charge transfer and the associated changes in molecular structure in N,N'-dimethylpiperazine are tracked using femtosecond gas-phase X-ray scattering. The molecules are optically excited to the 3p state at 200 nm. Following rapid relaxation to the 3s state, distinct charge-localized and charge-delocalized species related by charge transfer are observed. The experiment determines the molecular structure of the two species, with the redistribution of electron density accounted for by a scattering correction factor. The initially dominant charge-localized state has a weakened carbon-carbon bond and reorients one methyl group compared with the ground state. Subsequent charge transfer to the charge-delocalized state elongates the carbon-carbon bond further, creating an extended 1.634 Å bond, and also reorients the second methyl group. At the same time, the bond lengths between the nitrogen and the ring-carbon atoms contract from an average of 1.505 to 1.465 Å. The experiment determines the overall charge transfer time constant for approaching the equilibrium between charge-localized and charge-delocalized species to 3.0 ps.

Strong-field induced fragmentation and isomerization of toluene probed by ultrafast femtosecond electron diffraction and mass spectrometry.

We investigate the fragmentation and isomerization of toluene molecules induced by strong-field ionization with a femtosecond near-infrared laser pulse. Momentum-resolved coincidence time-of-flight ion mass spectrometry is used to determine the relative yield of different ionic products and fragmentation channels as a function of laser intensity. Ultrafast electron diffraction is used to capture the structure of the ions formed on a picosecond time scale by comparing the diffraction signal with theoretical predictions. Through the combination of the two measurements and theory, we are able to determine the main fragmentation channels and to distinguish between ions with identical mass but different structures. In addition, our diffraction measurements show that the independent atom model, which is widely used to analyze electron diffraction patterns, is not a good approximation for diffraction from ions. We show that the diffraction data is in very good agreement with ab initio scattering calculations.

Observation of the molecular response to light upon photoexcitation.

When a molecule interacts with light, its electrons can absorb energy from the electromagnetic field by rapidly rearranging their positions. This constitutes the first step of photochemical and photophysical processes that include primary events in human vision and photosynthesis. Here, we report the direct measurement of the initial redistribution of electron density when the molecule 1,3-cyclohexadiene (CHD) is optically excited. Our experiments exploit the intense, ultrashort hard x-ray pulses of the Linac Coherent Light Source (LCLS) to map the change in electron density using ultrafast x-ray scattering. The nature of the excited electronic state is identified with excellent spatial resolution and in good agreement with theoretical predictions. The excited state electron density distributions are thus amenable to direct experimental observation.

A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene.

We explore the photo-induced kinetics of 1,3-cyclohexadiene upon excitation at 200 nm to the 3p state by ultrafast time-resolved, gas-phase x-ray scattering using the Linac Coherent Light Source. Analysis of the scattering anisotropy reveals that the excitation leads to the 3px and 3py Rydberg electronic states, which relax to the ground state with a time constant of 208 ± 11 fs. In contrast to the well-studied 266 nm excitation, at 200 nm the majority of the molecules (76 ± 3%) relax to vibrationally hot cyclohexadiene in the ground electronic state. A subsequent reaction on the ground electronic state surface leads from the hot cyclohexadiene to 1,3,5-hexatriene, with rates for the forward and backward reactions of 174 ± 13 and 355 ± 45 ps, respectively. The scattering pattern of the final hexatriene product reveals a thermal distribution of rotamers about the carbon-carbon single bonds.

Scattering off molecules far from equilibrium.

Pump-probe gas phase X-ray scattering experiments, enabled by the development of X-ray free electron lasers, have advanced to reveal scattering patterns of molecules far from their equilibrium geometry. While dynamic displacements reflecting the motion of wavepackets can probe deeply into the reaction dynamics, in many systems, the thermal excitation embedded in the molecules upon optical excitation and energy randomization can create systems that encompass structures far from the ground state geometry. For polyatomic molecular systems, large amplitude vibrational motions are associated with anharmonicity and shifts of interatomic distances, making analytical solutions using traditional harmonic approximations inapplicable. More generally, the interatomic distances in a polyatomic molecule are not independent and the traditional equations commonly used to interpret the data may give unphysical results. Here, we introduce a novel method based on molecular dynamic trajectories and illustrate it on two examples of hot, vibrating molecules at thermal equilibrium. When excited at 200 nm, 1,3-cyclohexadiene (CHD) relaxes on a subpicosecond time scale back to the reactant molecule, the dominant pathway, and to various forms of 1,3,5-hexatriene (HT). With internal energies of about 6 eV, the energy thermalizes quickly, leading to structure distributions that deviate significantly from their vibrationless equilibrium. The experimental and theoretical results are in excellent agreement and reveal that a significant contribution to the scattering signal arises from transition state structures near the inversion barrier of CHD. In HT, our analysis clarifies that previous inconsistent structural parameters determined by electron diffraction were artifacts that might have resulted from the use of inapplicable analytical equations.

Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation.

The coherence and dephasing of vibrational motions of molecules constitute an integral part of chemical dynamics, influence material properties and underpin schemes to control chemical reactions. Considerable progress has been made in understanding vibrational coherence through spectroscopic measurements, but precise, direct measurement of the structure of a vibrating excited-state polyatomic organic molecule has remained unworkable. Here, we measure the time-evolving molecular structure of optically excited N-methylmorpholine through scattering with ultrashort X-ray pulses. The scattering signals are corrected for the differences in electron density in the excited electronic state of the molecule in comparison to the ground state. The experiment maps the evolution of the molecular geometry with femtosecond resolution, showing coherent motion that survives electronic relaxation and seems to persist for longer than previously seen using other methods.

Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions.

Time-resolved pump-probe gas-phase X-ray scattering signals, extrapolated to zero momentum transfer, provide a measure of the number of electrons in a system, an effect that arises from the coherent addition of elastic scattering from the electrons. This allows to identify reactive transients and determine the chemical reaction kinetics without the need for extensive scattering simulations or complicated inversion of scattering data. We examine the photodissociation reaction of trimethylamine and identify two reaction paths upon excitation to the 3p state at 200 nm: a fast dissociation path out of the 3p state to the dimethyl amine radical (16.6±1.2 %) and a slower dissociation via internal conversion to the 3s state (83.4±1.2 %). The time constants for the two reactions are 640±130 fs and 74±6 ps, respectively. Additionally, it is found that the transient dimethyl amine radical has a N-C bond length of 1.45±0.02 Šand a C-N-C bond angle of 118°±4°.

Determining Orientations of Optical Transition Dipole Moments Using Ultrafast X-ray Scattering.

Identification of the initially prepared, optically active state remains a challenging problem in many studies of ultrafast photoinduced processes. We show that the initially excited electronic state can be determined using the anisotropic component of ultrafast time-resolved X-ray scattering signals. The concept is demonstrated using the time-dependent X-ray scattering of N-methyl morpholine in the gas phase upon excitation by a 200 nm linearly polarized optical pulse. Analysis of the angular dependence of the scattering signal near time zero renders the orientation of the transition dipole moment in the molecular frame and identifies the initially excited state as the 3p z Rydberg state, thus bypassing the need for further experimental studies to determine the starting point of the photoinduced dynamics and clarifying inconsistent computational results.

Assessing the ecological vulnerability of the upper reaches of the Minjiang River.

The upper reaches of the Minjiang River (URMR), located on the eastern edge of the Tibetan Plateau in southwestern China, are an important component of the ecological barrier of the Upper Yangtze River Basin. Climate change and human activities have increased the ecological sensitivity and vulnerability of the region, which may pose a threat to the ecological security of the Yangtze River Basin and have negative impacts on local social and economic development. In this study, we analyzed land use and cover change (LUCC) of the URMR between 2000 and 2010, and found that the total rate of LUCC was less than 0.50% during this period. In addition, net primary production (NPP) was employed to describe the changes in ecosystem sensitivity and vulnerability, and the results demonstrated that slightly and moderately sensitive and vulnerable zones occupied the largest area, distributed mainly in forest, shrub, and grassland ecosystems. However, compared with the period from 2000 to 2005, the ecological sensitivity and vulnerability showed a worsening trend in the period 2005-2010. Exploring the relationship between vulnerability/sensitivity and environmental factors, we found that sensitivity and vulnerability were positively correlated with precipitation (>700 mm) and aridity index (>36 mm/°C). The results highlight that the future ecological sensitivity and vulnerability of URMR should be further investigated, and that the LUCC induced by human activities and climate change have caused alteration of in ecosystem vulnerability.

Ratio-controlled synthesis of CuNi octahedra and nanocubes with enhanced catalytic activity.

Non-noble bimetallic nanocrystals (NCs) have been widely explored due to not only their low cost and abundant content in the Earth's crust but also their outstanding performance in catalytic reactions. However, controllable synthesis of non-noble alloys remains a significant challenge. Here we report a facile synthesis of CuNi octahedra and nanocubes with controllable shapes and tunable compositions. Its success relies on the use of borane morpholine as a reducing agent, which upon decomposition generates a burst of H2 molecules to induce rapid formation of the nuclei. Specifically, octahedra switched to nanocubes with an increased amount of borane morpholine. In addition, the ratio of CuNi NCs could be facilely tuned by changing the molar ratio of both precursors. The obtained CuNi NCs exhibited high activity in aldehyde-alkyne-amine coupling reactions, and their performance is strongly facet- and composition-dependent due to the competition of the surface energy (enhanced by increasing the percent of Ni) and active sites (derived from Cu atoms).

[Chemical Constituents from Shoot of Phyllostachys edulis (II)].

OBJECTIVE: To investigate the chemical constituents from the shoot of Phyllostachys edulis. METHODS: Normal-phase, reversed-phase silica gel, Sephadex LH-20 porous polymer gel column and HPLC chromatography were used for isolation. Spectroscopic methods (13C-NMR, 1H-NMR, DEPT and EI-MS) were used for identification. RESULTS: Eleven compounds were isolated and elucidated, which were skimmin(I), liquiritienin(II),1-(4-hydroxy-3-methoxyphenyl)-1-propanone(III), syringicaldehyde(IV), vanillin(V), isoliquiritigenin(VI), 4-hydroxybenzoic acid(VII), methyl p-hydroxy benzeneacetate (VIII), 5,7-dihydroxy-8-methoxyflavone (IX), daucosterol(X) and ß-sitosterol(X). CONCLUSION: All the compounds are obtained from this plant for the first time, and compounds VI, VIII and IX are firstly isolated from the plants of this genus.

[Experimental investigation of shear bond strength on orthodontic bonding on dental fluorosis after air abrading surface preparation technique].

OBJECTIVE: To find a way to having higher bond strength on mottled enamel. METHODS: Sixty mottled enamel first bicuspid teeth extracted from fifteen patients needing orthodontic force were prepared and divided into four groups. Group A was routine acid etched, group B was air abraded, group C was etched by clearfil liner self-etching primer, group D was air abraded and then etched by clearfil liner self-etching primer. Next the bond and resin were used. The shear bond strength was observed and compared. The data were analysed by SPSS 11.5 statistical package. RESULTS: The shear bonding strength of group A was (2.247 +/- 0.261) MPa, group B was (5.374 +/- 0.469) MPa, group C was (4.345 +/- 0.401) MPa, group D was (5.791 +/- 0.636) MPa. The strengths of four groups were significantly different (P < 0.01). The adhesive remnant index (ARI) scores of the four groups had no significant difference. CONCLUSION: In clinic, using air abrasion surface preparation technique is an acceptable way to enhancing the shear bond strength before sticking the orthodontic bonding on dental fluorosis.