Deep eutectic solvent (DES)-assisted extraction of pectin from Ficus carica Linn. peel: optimization, partial structure characterization, functional and antioxidant activities.

BACKGROUND: The pectin from Ficus carica Linn. (fig) peels is a valuable and recyclable constituent that may bring huge economic benefits. To maximize the utilization of this resource, deep eutectic solvent (DES)-assisted extraction was applied to extract pectin from fig peels, and the extraction process was optimized with response surface methodology. RESULTS: When DES (choline chloride/oxalic acid = 1:1) content was 168.1 g kg-1 , extraction temperature was 79.8 °C, liquid-solid ratio was 23.3 mL g-1 , and extraction time was 120 min, the maximum yield of 239.6 g kg-1 was obtained, which was almost twice the extraction of hot water. DES-extracted fig peel pectin (D-FP) exhibited better nature than hot water-extracted fig peel pectin (W-FP) in terms of uronic acid content, particle size distribution, and solubility, but lower molecular weight and esterification degree. D-FP and W-FP had similar infrared spectra and thermodynamic peaks but differed in monosaccharide compositions. D-FP also showed good antioxidant capacities and exhibited better functional activities than W-FP. CONCLUSION: These results indicated that D-FP was of promising quality being utilized in food or medical industries and the optimal DES-assisted extraction method might be applied as a sustainable process for the effective extraction of bioactive pectin from fig peels with the excellence of low equipment requirements and simple operation. © 2024 Society of Chemical Industry.

Temperature-affected nano-deformation behavior of nanometals in ultrahigh-strain-rate formation processes.

As metal forming processes move toward high speed, high throughput, high precision and small scale with temperature dependence, clarifying the fundamental nano-deformation behavior of metals is critical for the optimization of manufacturing processes, and the control of nano-optical, electrical, mechanical or surface properties. Unfortunately, limited by the time scale and sample size, the effect of temperature on the deformation behavior of nano-metals during the ultrahigh-strain-rate forming process remains largely unexplored. This study demonstrates the nonlinear effect of temperature on the formability of nano-metals for the first time. Temperatures below 673 K facilitated the formability of nano-metals benefiting from the temperature-promoted dislocation proliferation process, whereas temperatures above 673 K weakened the plasticity of the nano-metal due to the activation of phase transformation. Frequent phase transition activation and accelerated dislocation annihilation at high temperatures reduced interstitial transport channels and delayed atomic transfer. Based on the temperature response of nano-metals in deformation mechanisms, defect evolution behavior and formability, the constitutive model and nano-deformation mechanism map of nano-metals in ultrahigh-strain-rate forming processes are proposed. The objective of this work is to provide basic support for the reasonable matching of nano-forming technology and processing temperature, and the determination of the optimal process window through fundamental nano-deformation behavior exploration.

Infancy, childhood, and puberty on the Silk Road revealed with isotopic analysis of incremental dentine.

Childhood is a unique phase in human life history, in which newborns are breastfed and weaned, and are progressively familiarized to adult diets. By investigating dietary changes from infancy to adolescence, valuable information regarding past cultural behaviors and aspects of human lives can be explored and elucidated. Here, in conjunction with published isotopic results of serial dentine (n = 21) from Yingpan Man, new δ13C and δ15N results are obtained from 172 samples of incremental dentine from 8 teeth of 8 individuals of the Yingpan cemetery, located in Xinjiang, China. The δ13C values range from - 18.2 to - 14.6‰ with a mean ± SD value of - 16.3 ± 0.9‰, and the δ15N results range between 13.4 and 19.9‰ with a mean ± SD value of 16.0 ± 1.4‰. This indicates that the childhood diets were mixtures of C3 and C4 dietary resources and were clearly influenced by breastfeeding and weaning practices. In particular, the findings indicate that there were significant inter-individual differences in terms of the timing and duration of breastfeeding and weaning practices as well as childhood dietary practices at Yingpan. For instance, three individuals were exclusively breastfed after birth, while, two individuals and Yingpan Man were not. In addition, the post-weaning diets of most Yingpan individuals were relatively stable, but one individual and Yingpan Man displayed clear evidence of increased consumption of C4 foods, likely millet, during late and post-weaning periods. Further, 7 individuals had unique dietary changes between 9 to 14 years old. Potential factors related to this are presented from the perspective of changes in social roles that might be caused by their early participation in the social division of labor or puberty and marriage.

Laser Shock-Induced Nano-Twist of Transition Metal Dichalcogenides.

Mechanical strain, such as stretching, compression, bending, and rotation, significantly alters the photonic and electronic properties of 2D materials. The laser shock process, which allows 2D materials to deform at an ultrahigh strain rate, is a promising technology for alleviating the low strain transfer efficiency caused by the low interfacial bonding strength of the layered 2D materials. However, the mechanical strain introduced by shock waves is currently limited to uniaxial compression or bending deformation, and the monotonic strain patterns constrain the strain diversity and performance expansion space of 2D materials. This work proposed a novel strategy for nano-twist manufacturing using laser shock processing, based on partial interfacial decoupling behavior. Apart from the conventional uniaxial strain, we demonstrated experimentally and theoretically that the manufacturing of nano-twist allows the introduction of interlayer tensile and rotational strains in TMDCs. The microstructure and properties of the strained 2D materials were investigated. Furthermore, the dynamic deformation response of WSe2 during the shock process was studied using molecular dynamics simulations. The correlation between the laser shock-induced dynamic loading process, interfacial behavior, and deformation behavior of 2D materials was comprehensively explored. The primary contribution of this study lies in the introduction of diversified strain modes through nano-twist manufacturing by the laser shock process, which is expected to provide a convenient nano-twist fabrication process for the strain engineering and twistronics fields.

Large-Scale Ultrafast Strain Engineering of CVD-Grown Two-Dimensional Materials on Strain Self-Limited Deformable Nanostructures toward Enhanced Field-Effect Transistors.

Strain engineering of 2D materials is capable of tuning the electrical and optical properties of the materials without introducing additional atoms. Here, a method for large-scale ultrafast strain engineering of CVD-grown 2D materials is proposed. Locally nonuniform strains are introduced through the cooperative deformation of materials and metal@metal oxide nanoparticles through cold laser shock. The tensile strain of MoS2 changes and the band gap decreases after laser shock. The mechanism of the ultrafast straining is investigated by MD simulations. MoS2 FETs were fabricated, and the field-effect mobility of devices could be increased from 1.9 to 44.5 cm2 V-1 s-1 by adjusting the strain level of MoS2. This is currently the maximum value of MoS2 FETs grown by CVD with SiO2 as the dielectric. As a large-scale and ultrafast manufacturing method, laser shock provides a universal strategy for large-scale adjustment of 2D material strain, which will help to promote the manufacturing of 2D nanoelectronic devices.

Revealing lost secrets about Yingpan Man and the Silk Road.

Yingpan Man, is one of the most exquisitely preserved mummies found in the Xinjiang Uyghur Autonomous Region of China. Here links between Yingpan Man and the Silk Road are explored through a detailed isotopic and bioarchaeological investigation of his life history. Analytical techniques of carbon, nitrogen, and sulfur stable isotope ratio analysis on hair, teeth, muscle and bones as well as associated animal and plant remains, radiocarbon dating and starch grain analysis of dental calculus are presented to visualize never before seen aspects of Yingpan Man's life, including: environment, breastfeeding and weaning practices, adolescent and adult diet, disease and nutritional status as well as season of death. Furthermore, in combination with a detailed review of his associated grave goods, this research examines the social status and identity of Yingpan Man, and demonstrates the profound impact and cultural fusion that the Silk Road had upon the peoples of Xinjiang and Eurasia.

First direct evidence of conservative foraging ecology of early Gigantopithecus blacki (~2 Ma) in Guangxi, southern China.

OBJECTIVES: Gigantopithecus blacki, the largest hominoid known, is one of the representative Pleistocene mammals in southern China and northern Southeast Asia. Here we investigate the feeding ecology of G. blacki in its core habitat (Guangxi, Southern China) during the early Early Pleistocene, which was the early period in its evolution. MATERIALS AND METHODS: The stable isotopic (C, O) analysis of tooth enamel of the fauna associated with G. blacki (n = 58), including the largest number of G. blacki teeth (n = 12) to date from the Liucheng Gigantopithecus Cave (~2 Ma), Guangxi, China, is undertaken. RESULTS: The δ13 C values of Liucheng fauna range from -12.9 to -19.0‰ with an average of -16.1 ± 1.3‰ (n = 58) and the δ18 O values range from -4.3 to -9.6‰ with an average of -6.9 ± 1.2‰ (n = 58). The δ13 C values of G. blacki range from -15.9‰ to -17.0‰ with an average of -16.5 ± 0.4‰ (n = 12), and the δ18 O values vary from -5.9‰ to -7.5‰ with an average of -6.6 ± 0.5‰ (n = 12). CONCLUSIONS: The isotopic data show Guangxi was characterized by closed C3 forest and humid climate in the early Early Pleistocene. Niche partitioning is found among G. blacki, Sinomastodon, Ailuropoda and Stegodon, the typical megafauna in South China in the early Early Pleistocene. This could be one of the important factors for them to co-exist until the Middle Pleistocene. Smallest isotopic variations of G. blacki are found compared with those of contemporary animals, indicating a conservative foraging ecology i.e., limited foraging area and/or narrow dietary flexibility. Furthermore, the more confined foraging ecology of G. blacki is also seen in comparison with fossil and extant large-bodied primates. However, the unique dietary pattern of G. blacki does not seem to have hindered its survival. The environment in Guangxi during the early Early Pleistocene offered the suitable conditions for G. blacki to become one of the typical species in the faunal assemblages.

Dietary shifts and diversities of individual life histories reveal cultural dynamics and interplay of millets and rice in the Chengdu Plain, China during the Late Neolithic (2500-2000 cal. BC).

OBJECTIVES: We undertook a more comprehensive analyses than our previous study (Yi et al., International Journal of Osteoarchaeology, 2018, 28, 636-644) at the Gaoshan site (~2500-2000 cal. BC) to expand our understanding of the different roles of rice and millets to human subsistence strategies, diachronic shift of human diets, diversity of human life histories and cultural influence (dental ablation) to human population. MATERIALS AND METHODS: Carbon and nitrogen isotopic analyses of human (ribs and long bones, n = 68) and animal (n = 15) bones as well as carbonized seeds from rice and millets (n = 8) were undertaken. Human bones were directly AMS-14 C dated. In addition, sequential sampling of 16 individuals with varied age and sex and cultural contexts for isotopic analysis was also conducted. RESULTS: The calibrated dating results (n = 27) indicate that there existed two periods of occupation at the site, ~2500-2200 BC and ~2200-1900 BC. Moderate high δ15 N values were found in the crops. Isotopic data from bone collagen suggest that the humans mainly relied on C3 -based animal protein and were supplemented by C4 -based foods. This isotopic pattern is also seen in pigs. Significant difference of human δ13 C values (Mann-Whitney U test, p < 0.05) between the two periods was observed. Compared to the bones, the isotopic data of human dentine serial sections show a much wider variability and higher δ13 C values. DISCUSSION: The crops (millets and rice) were probably manured. Human individuals subsisted on rice/millet agriculture and pigs in general. In combination with the radiocarbon dates, the increase of C3 (rice) consumption by the humans was found from the early (2500-2200 cal. BC) to late (2200-2000 cal. BC) periods, indicating the intensification of rice agriculture through time. However, four categories of human life histories during childhood are identified given different isotopic profiles of dentine sections, demonstrating that C3 (rice) and C4 (millets)-based foods played different roles in human lives. Even though, there were similar weaning practices among the human populations. It is surprising that human individuals with dental ablation, cultural characteristic in the Middle and Lower Yangtze River Valley, consumed more millets during childhood in the early period than those without dental ablation in the late period. Our study here provides novel insights into cultural dynamics and the interplay between rice and millets in rice-millet agricultural system during the Late Neolithic in Southwest China.

Osteobiography of a seventh-century potter at the Oupan kiln, China by osteological and multi-isotope approach.

In recent years, the reconstruction of individual life history by the multi-isotope analysis of different skeletal elements has become an active topic in bioarchaeological field. However, most studies focus on the persons with high social status and none cares for craftsmen with low social status. In this study, we undertook a comprehensive analysis on a human skeleton buried in the Oupan kiln, Anhui, China to recover his osteobiography. The archaeological context and dating result (534-644 cal. AD) indicate that he might be a potter at the kiln during the Sui and early Tang Dynasty, characteristic of low social hierarchy. The osteological investigation suggests that he had abnormal vertebrae related to long-term physical labor. In general, the isotopic data demonstrate that he mainly consumed C3(wheat, beans)/C4(millets)-based terrestrial foods. The isotopic (C, N) profiles of dentin sections and isotopic data (C, O) of bone apatite and teeth enamel indicate that he had experienced dramatic dietary changes and/or several migrations throughout the childhood and adulthood. His turbulent life trajectory was highly relevant to his identity and low social status. Our study provides a pilot insight into the life history of craftsmen who was generally overlooked in archaeological, historic and anthropological research.

Laser-Shock-Induced Nanoscale Kink-Bands in WSe2 2D Crystals.

The response of materials to high stress and strain rates in nature has been a long-term scientific interest. The formation of kinks is a common deformation feature under high pressure and strain rates among foliated structures, such as rock-forming minerals. Although deformation of foliated rock layers in geology has been investigated for a century, the deformation behavior of their nanoscale counterparts, such as two-dimensional (2D) layered materials, under high stress and strain rates has not been investigated. 2D transition metal dichalcogenides have very strong in-plane rigidity, whereas the interlayer shear modulus is 3 orders of magnitude lower than their in-plane Young's modulus. Here, we study the structure and property changes in multilayer WSe2 2D layers during a 3D nanoshaping process where laser-shock pressure at the GPa level is applied to imprint the 2D multilayers into a designed nanomold, forming a large local bending strain of 5-6%. The microstructure of the 2D multilayers after laser shock is observed to be a nanoscale kink-band, similar to that of strained geological layered crystals, due to the high-pressure-induced bending and shearing. The deformed kink-band structure is investigated experimentally by high-resolution transmission electron microscopy and atomic force microscopy and validated by molecular dynamics simulations. The changes in the resulting electronic band structure are investigated by first-principles calculations. The laser-shock straining technology to induce kink-band structures can enrich the understanding and facilitate the applications of many 2D materials.

Tianshanbeilu and the Isotopic Millet Road: reviewing the late Neolithic/Bronze Age radiation of human millet consumption from north China to Europe.

The westward expansion of human millet consumption from north China has important implications for understanding early interactions between the East and West. However, few studies have focused on the Xinjiang Uyghur Autonomous Region, the vast geographical area directly linking the ancient cultures of the Eurasian Steppe and the Gansu Corridor of China. In this study, we present the largest isotopic investigation of Bronze Age China (n = 110) on material from the key site of Tianshanbeilu, in eastern Xinjiang. The large range of δ13C values (-17.6‰ to -7.2‰; -15.5 ± 1.2‰) provides direct evidence of unique dietary diversity and consumption of significant C4 resources (millets). The high δ15N results (10.3‰ to 16.7‰; 14.7 ± 0.8‰) likely reflect sheep/goat and wild game consumption and the arid climate of the Taklamakan Desert. Radiocarbon dates from four individuals indicate Tianshanbeilu was in use between 1940 and 1215 cal bc. The Tianshanbeilu results are then analysed with respect to 52 Bronze Age sites from across Eurasia, to investigate the spread and chronology of significant human millet consumption and human migration. This isotopic survey finds novel evidence that the second millennium bc was a dynamic period, with significant dietary interconnectivity occurring between north China, Central Asia and Siberia. Further, we argue that this 'Isotopic Millet Road' extended all the way to the Mediterranean and Central Europe, and conclude that these C4 dietary signatures of millet consumption reflect early links (migration and/or resource transfer) between the Bronze Age inhabitants of modern-day China and Europe.

Laser Shock Tuning Dynamic Interlayer Coupling in Graphene-Boron Nitride Moiré Superlattices.

In the emergence of graphene and many two-dimensional (2D) materials, the most exciting applications come from stacking them into 3D devices, promising many excellent possibilities for neoteric electronics and optoelectronics. Layers of semiconductors, insulators, and conductors can be stacked to form van der Waals heterostructures, after the weak bonds formed between the layers. However, the interlayer coupling in these heterostructures is usually hard to modulate, resulting in difficulty to realize their emerging optical or electronic properties. Especially, the relationship between interlayer distance and interlayer coupling remains to be investigated, due to the lack of effective technology. In this work, we have used laser shocking to controllably tune the interlayer distance between graphene (Gr) and boron nitride (BN) in the Gr/BN/Gr heterostructures and the strains in the 2D heterolayers, providing a simple and effective way to modify their optic and electronic properties. After lase shocking, the reduction of interlayer distance is calculated by molecular dynamics (MD) simulation. Some atoms in Gr or BN are out-of-plane as well. In Raman measurements, the G peak in the heterostructure shows a red-shifted trend after laser shocking, indicating the strong phonon coupling in the interlayer. Moreover, the larger transparency after laser shocking also verifies the stronger photon coupling in the heterostructure. To investigate the effects of the interlayer coupling of heterostructure on its out-of-plane electronic behavior, we have investigated the electronic tunneling behavior. The heterostructure after laser shock reveals a lager tunneling current and lower tunneling threshold, proving an unexpected better electrical property. From DFT calculations, laser shocking can modulate the band gap structure of graphene in Gr/BN/Gr heterostructures; therefore, the heterostructures can be implemented as a unique photonic platform to modulate the emission characters of the anchored CdSe/ZnS core-shell quantum dots. Remarkably, the effective laser shocking method is also applicable to various otherwise noninteracting 2D materials, resulting in many new phenomena, which will lead science and technology to unexplored territories.

A grazing Gomphotherium in Middle Miocene Central Asia, 10 million years prior to the origin of the Elephantidae.

Feeding preference of fossil herbivorous mammals, concerning the coevolution of mammalian and floral ecosystems, has become of key research interest. In this paper, phytoliths in dental calculus from two gomphotheriid proboscideans of the middle Miocene Junggar Basin, Central Asia, have been identified, suggesting that Gomphotherium connexum was a mixed feeder, while the phytoliths from G. steinheimense indicates grazing preference. This is the earliest-known proboscidean with a predominantly grazing habit. These results are further confirmed by microwear and isotope analyses. Pollen record reveals an open steppic environment with few trees, indicating an early aridity phase in the Asian interior during the Mid-Miocene Climate Optimum, which might urge a diet remodeling of G. steinheimense. Morphological and cladistic analyses show that G. steinheimense comprises the sister taxon of tetralophodont gomphotheres, which were believed to be the general ancestral stock of derived "true elephantids"; whereas G. connexum represents a more conservative lineage in both feeding behavior and tooth morphology, which subsequently became completely extinct. Therefore, grazing by G. steinheimense may have acted as a behavior preadaptive for aridity, and allowing its lineage evolving new morphological features for surviving later in time. This study displays an interesting example of behavioral adaptation prior to morphological modification.

Millet manuring as a driving force for the Late Neolithic agricultural expansion of north China.

Research in to the nature of Neolithic agriculture in China is often focused on topics such as the domestication and spread of cereal crops and the reconstruction of human and animal diets in the past. Field management practices, such as organic manuring, have not been systematically investigated in Chinese archaeology. Here we present an isotopic dataset for archaeological foxtail millet (Setaria italica) and common millet (Panicum miliaceum) grains as well as associated faunal remains (both domesticated and wild) from seven sites in the Baishui Valley of north China, in order to find direct evidence of organic manuring during the Late Neolithic period. The elevated nitrogen isotope values of the millet grains (5500-3500 cal BP) in comparison with the estimated local vegetation indicates that millets were organically manured by animal dung, mostly likely originating from domestic pigs. Considering the low nitrogen contents of loess soils and their unsuitability for intensive cultivation, this organic manuring by animal dung would have played a key role in maintaining soil productivity and crop yield, which was necessary to support the demands of agriculture and cultural expansion during the Late Neolithic on the Loess Plateau of China.

Straining effects in MoS2 monolayer on nanostructured substrates: temperature-dependent photoluminescence and exciton dynamics.

Strain-engineering of two-dimensional (2D) transition metal dichalcogenides (TMDs) has great potential to alter their electronic and optical properties. Thus far, experimental studies of the straining effects in 2D TMDs primarily focused on the static property measurements at room temperature. However, low-temperature and temperature-dependence studies are essential in understanding the underlying mechanisms of the unique properties of monolayer TMDs. Herein, the temperature-dependent dynamic properties of laser shock strain-engineered monolayer MoS2 were studied using temperature-dependent photoluminescence (PL) and pump-probe spectroscopy. Both the photoluminescence spectra and exciton dynamics exhibit the differences between the MoS2 monolayers transferred on the flat and nanostructured surfaces by laser shock strain engineering and display a strong temperature dependence. The laser-induced straining effect and temperature-dependent dynamic behavior of MoS2 were studied through molecular dynamics simulation. The observed behaviors can be explained by the thermally induced strain in the monolayer MoS2 due to the mismatching thermal expansion coefficients of the monolayer and the substrate, which are coupled by the van der Waals forces. The ultrafast pump-probe experiments were performed to investigate the effect of strain on the exciton dynamics upon optical excitation. The results from the pump-probe measurements indicate that the effects of strain extend beyond that of the static properties and profoundly influence the valley carrier dynamics. This report extends the understanding of the substrate-induced straining effect to temperature-dependent luminescence behaviors and dynamic behaviors of the TMD materials.

Alpha Lead Oxide (α-PbO): A New 2D Material with Visible Light Sensitivity.

Even though transition metal dichalcogenides (TMDCs) are deemed to be novel photonic and optoelectronic 2D materials, the visible band gap being often limited to monolayer, hampers their potential in niche applications due to fabrication challenges. Uncontrollable defects and degraded functionalities at elevated temperature and under extreme environments further restrict their prospects. To address such limitations, the discovery of a new 2D material, α-PbO is reported. Micromechanical as well as sonochemical exfoliation of 2D atomic sheets of α-PbO are demonstrated and its optical behavior is investigated. Spectroscopic investigations indicate layer dependent band gaps. In particular, even multilayered PbO sheets exhibit visible band gap > 2 eV (direct) which is rare among semiconducting 2D materials. The emission lifetime of multilayer PbO atomic sheets is 7 ns (dim light) as compared to the monolayer which gives 2.5 ns lifetime and an intense light. Density functional theory calculations of layer dependent band structure of α-PbO matches well with experimental results. Experimental findings suggest that PbO atomic sheets exhibit hydrophobic nature, thermal robustness, microwave stability, anti-corrosive behaviour and acid resistance. This new low-cost, abundant and robust 2D material is expected to find many applications in the fields of electronics, optoelectronics, sensors, photocatalysis and energy storage.

Breastfeeding, weaning, and dietary practices during the Western Zhou Dynasty (1122-771 BC) at Boyangcheng, Anhui Province, China.

OBJECTIVES: Here we investigate breastfeeding and weaning practices and adult dietary habits at the Western Zhou Dynasty (1122-771 BC) site of Boyangcheng () located in Anhui Province, China. In addition, we utilize the differences in bone collagen turnover rates between rib and long bones from the same individual to examine past life histories, such as changes in diet or residence. MATERIALS AND METHODS: Bone collagen from both the rib and long bones (either femora or humeri) of 42 individuals was measured for stable isotope ratios of carbon (δ13 C) and nitrogen (δ15 N). In addition, δ13 C and δ15 N values are reported for 35 animals (dogs, cows, horses, pigs, and deer). RESULTS: The human δ13 C values range from -20.7‰ to -12.0‰ with a mean value of -18.8 ± 1.6‰. The human δ15 N values range from 9.1‰ to 13.4‰ with a mean value of 10.9 ± 1.0‰. The animals display a wide range of δ13 C (-21.5‰ to -8.2‰; -15.8 ± 4.5‰) and δ15 N values (4.0‰ to 9.5‰; 6.5 ± 1.8‰). CONCLUSIONS: The adult δ13 C and δ15 N results indicate that mixed C3 (rice) and C4 (millet) terrestrial diets with varying levels of animal protein (mostly pigs and deer) were consumed. The elevated subadult δ15 N results return to adult levels by approximately 3-4 years of age, indicating that the weaning process was completed during this period. Individuals between 2 and 10 years old, with lower δ13 C and δ15 N results than the adult mean, possibly consumed more plant-based diets, and this is consistent with Chinese medical teachings ∼1500 years later during the Tang Dynasty (AD 618-907). The isotopic offsets between the ribs and long bones revealed that five adults experienced dramatic dietary shifts in their later lives, switching from predominately C3 /C4 to C3 diets. This research provides the first isotopic information about ancient Chinese breastfeeding and weaning practices and establishes a foundation for future studies to examine diachronic trends.

Graphene/PbS-Quantum Dots/Graphene Sandwich Structures Enabled by Laser Shock Imprinting for High Performance Photodetectors.

Quantum dots (QDs) integrated 2-dimensional (2D) materials have great potential for photodetector applications due to the excellent light absorption of QDs and ultrafast carrier transportation of 2D materials. However, there is a main issue that prevents efficient carrier transportation and ideal performance of photodetectors: the high interfacial resistance between 2D materials and QDs due to the bad contacts between 2D/0D interface, which makes sluggish carrier transfer from QDs to 2D materials. Here, a sandwich structure (graphene/PbS-QDs/graphene) with seamless 2D/0D contact was fabricated by laser shock imprinting, which opto-mechanically tunes the morphology of 2D materials to perfectly wrap on 0D materials and efficiently collect carriers from the PbS-QDs. It is found that this seamless integrated 2D/0D/2D structure significantly enhanced the carrier transmission, photoresponse gain (by 2×), response time (by 20×), and photoresponse speed (by 13×). The response time (∼30 ms) and Ip/ Id ratio (13.2) are both over 10× better than the reported hybrid graphene photodetectors. This is due to the tight contact and efficient gate-modulated carrier injection from PbS-QDs to graphene. The gate voltage dictates whether electrons or holes dominate the carrier injection from PbS-QDs to graphene.

Defects Mediated Corrosion in Graphene Coating Layer.

Mixed results were reported on the anticorrosion of graphene-coated metal surfaces-while graphene serves as an effective short-term barrier against corrosion and oxidation due to its low permeability to gases, the galvanic cell between graphene and the metal substrate facilitates extensive corrosion in the long run. Defects in the graphene layer provide pathways for the permeation of oxidizing species. We study the role of defects in graphene in the anticorrosion using first-principles theoretical modeling. Experiments in the highly reactive environment indicate that the oxidized products primarily distribute along the grain boundaries of graphene. We analyze the thermodynamics of the absorption of S and O on the grain boundaries of graphene on the basis of density functional theory. The insertion of S and O at the vacancy sites is energetically favorable. The interstitial impurities facilitate structural transformation of graphene and significantly decrease the mechanical strength of the graphene layer. Furthermore, the presence of the interstitial S and O reduces the chemical stability of graphene by enhancing the formation of vacancies and promoting dispersive growth of corrosive reactants along the grain boundaries.