Controllable Fabrication of Highly Uniform Sub-10 nm Nanoparticles from Spontaneous Confined Nanoemulsification.

Sub-10 nm nanoparticles are known to exhibit extraordinary size-dependent properties for wide applications. Many approaches have been developed for synthesizing sub-10 nm inorganic nanoparticles, but the fabrication of sub-10 nm polymeric nanoparticles is still challenging. Here, a scalable, spontaneous confined nanoemulsification strategy that produces uniform sub-10 nm nanodroplets for template synthesis of sub-10 nm polymeric nanoparticles is proposed. This strategy introduces a high-concentration interfacial reaction to create overpopulated surfactants that are insoluble at the droplet surface. These overpopulated surfactants act as barriers, resulting in highly accumulated surfactants inside the droplet via a confined reaction. These surfactants exhibit significantly changed packing geometry, solubility, and interfacial activity to enhance the molecular-level impact on interfacial instability for creating sub-10 nm nanoemulsions via self-burst nanoemulsification. Using the nanodroplets as templates, the fabrication of uniform sub-10 nm polymeric nanoparticles, as small as 3.5 nm, made from biocompatible polymers and capable of efficient drug encapsulation is demonstrated. This work opens up brand-new opportunities to easily create sub-10 nm nanoemulsions and advanced ultrasmall functional nanoparticles.

Sulfur-Mediated Formal Allylic C-H Cyclopropanation of α-Methylstyrenes.

Allylic C-H cyclopropanation of α-methylstyrene and its derivatives was realized through a one-pot two-step sequence, formally converting two aliphatic C-H bonds to C-C bonds with a good yield and high diastereoselectivity, thus providing a quick entry to the synthetically useful vinyl cyclopropane structures.

Chiral Phosphoric Acid Catalyzed Enantioselective Synthesis of α-Tertiary Amino Ketones from Sulfonium Ylides.

Herein we disclose a new catalytic asymmetric approach for the synthesis of chiral α-amino ketones, which is particularly useful for the less accessible acyclic α-tertiary cases. By a protonation-amination sequence, our approach represents a rare asymmetric H-heteroatom bond insertion by α-carbonyl sulfonium ylides, an attractive surrogate of diazocarbonyls. The mild intermolecular C-N bond formation was catalyzed by chiral phosphoric acids with excellent efficiency and enantioselectivity. The products are precursors to other important chiral amine derivatives, including drug molecules and chiral ligands. The enantioselectivity was controlled by dynamic kinetic resolution in the amination step, rather than the initial protonation. This process opens up a new platform for the development of other related insertion reactions.

Sulfur-Mediated Allylic C-H Arylation, Epoxidation, and Aziridination.

Transition-metal-free, sulfur-mediated allylic C-H arylation, epoxidation, and aziridination were realized through one-pot procedures. The reaction design involved initial addition between olefins and triflic anhydride activated sulfoxides, followed by subsequent reactions of the allylic sulfur ylides generated under basic conditions with arylboronic acids, aldehydes, or aldimines, to give allylic arylation, epoxidation, or aziridination products, respectively.

Sulfur-Mediated Electrophilic Cyclization of Aryl-Substituted Internal Alkynes.

A sulfur-mediated electrophilic cyclization reaction of aryl-tethered internal alkynes has been developed. Triflic anhydride-activated sulfoxides induced the electrophilic cyclization and then demethylation with triethylamine in one pot, affording 3-sulfenyl-1,2-dihydronaphthalenes and related types of products in yields of ≤96%.

Nucleophilic Organic Base DABCO-Mediated Chemospecific Meinwald Rearrangement of Terminal Epoxides into Methyl Ketones.

Nucleophilic organic base DABCO (1,4-diazabicyclo[2.2.2]octane)-mediated Meinwald rearrangement of various epoxides was investigated. 2-Aryl-, alkenyl-, and alkynylepoxides generate the corresponding methyl ketones chemospecifically in good to excellent yields. The current DABCO-mediated Meinwald rearrangement of epoxides features readily accessible starting materials, a wide substrate scope, a transition-metal- and acid-free environment, and chemospecificity in the isomerization of epoxides.

Synthesis of N-Alkylpyridin-4-ones and Thiazolo[3,2-a]pyridin-5-ones through Pummerer-Type Reactions.

N-Alkylated 4-pyridones were obtained through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride-activated sulfoxides and 4-fluoropyridine derivatives, followed by hydrolysis. On the other hand, triflic anhydride-activated benzyl 6-fluoro-2-pyridyl sulfoxide could react with alkenes or alkynes to afford thiazolo[3,2-a]pyridin-5-ones, via the pyridinium salt intermediates.

Synthesis of N-alkylated 2-pyridones through Pummerer type reactions of activated sulfoxides and 2-fluoropyridine derivatives.

N-Alkylated 2-pyridone products were obtained in good to excellent yields through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride activated sulfoxides and 2-fluoropyridine derivatives, followed by hydrolysis. This is a rare case that uses 2-fluoropyridine as a nucleophile in Pummerer type reactions.

Modeling Vehicle Collision Angle in Traffic Crashes Based on Three-Dimensional Laser Scanning Data.

In road traffic accidents, the analysis of a vehicle's collision angle plays a key role in identifying a traffic accident's form and cause. However, because accurate estimation of vehicle collision angle involves many factors, it is difficult to accurately determine it in cases in which less physical evidence is available and there is a lack of monitoring. This paper establishes the mathematical relation model between collision angle, deformation, and normal vector in the collision region according to the equations of particle deformation and force in Hooke's law of classical mechanics. At the same time, the surface reconstruction method suitable for a normal vector solution is studied. Finally, the estimation model of vehicle collision angle is presented. In order to verify the correctness of the model, verification of multi-angle collision experiments and sensitivity analysis of laser scanning precision for the angle have been carried out using three-dimensional (3D) data obtained by a 3D laser scanner in the collision deformation zone. Under the conditions with which the model has been defined, validation results show that the collision angle is a result of the weighted synthesis of the normal vector of the collision point and the weight value is the deformation of the collision point corresponding to normal vectors. These conclusions prove the applicability of the model. The collision angle model proposed in this paper can be used as the theoretical basis for traffic accident identification and cause analysis. It can also be used as a theoretical reference for the study of the impact deformation of elastic materials.

Traffic safety comprehensive evaluation of urban tunnel visual guiding system based on extension matter-element model: a case study in tunnel curves.

OBJECTIVE: The visual guiding system, as a tunnel traffic safety improvement method by using visual guiding facilities to actively guide driving safely, has been widely used in countries with many tunnels, in recent years. This paper aims to quantitatively study the comprehensive evaluation of traffic safety of the visual guiding system in tunnels, which has certain engineering application value and can provide support for the quantitative evaluation and optimal design of tunnel traffic safety. METHODS: Based on the analysis of the relevant factors of urban tunnel traffic safety, a multi-factor comprehensive evaluation system with 5 upper-level indicators and 12 basic-level indicators was proposed. Considering the independent and incompatible indicators, a comprehensive evaluation method of traffic safety of the visual guiding system in urban tunnels was constructed by using the extension matter-element model. Taking the scene of 4 types of tunnel curves, such as no facilities, horizontal stripe, chevron alignment sign, and LED arch, as examples, the comprehensive evaluation of various schemes were carried out by using simulation tests. RESULTS: The traffic safety comprehensive evaluation system of visual guiding system in urban tunnels can be analyzed from five aspects: perception reaction, guidance ability, driver factor, driving task, and facility appearance. The results demonstrated significant the comprehensive evaluation result of the target level of scene 1 was L4, scene 2 was L3, scene 3 was L2, and scene 4 was L1. That is, the final results of the comprehensive evaluation of the four scenes were poor, medium, good, and very good, respectively. CONCLUSIONS: In the scheme of visual guiding system for urban tunnel curves, the effectiveness of the three types of designs, from high to low, was the LED arch, chevron alignment sign, and horizontal stripe, and the safety of the scene without facilities was the lowest. Hence, setting the LED arch in the urban tunnel curve has a good effect in the aspects of guidance ability, sight distance, and sight zone, and is conducive to the driver's perception reaction and driving task.

Designable Micro-/Nano-Structured Smart Polymeric Materials.

Smart polymeric materials with dynamically tunable physico-chemical characteristics in response to changes of environmental stimuli, have received considerable attention in myriad fields. The diverse combination of their micro-/nano-structural and molecular designs creates promising and exciting opportunities for exploiting advanced smart polymeric materials. Engineering micro-/nano-structures into smart polymeric materials with elaborate molecular design enables intricate coordination between their structures and molecular-level response to cooperatively realize smart functions for practical applications. In this review, recent progresses of smart polymeric materials that combine micro-/nano-structures and molecular design to achieve designed advanced functions are highlighted. Smart hydrogels, gating membranes, gratings, milli-particles, micro-particles and microvalves are employed as typical examples to introduce their design and fabrication strategies. Meanwhile, the key roles of interplay between their micro-/nano-structures and responsive properties to realize the desired functions for their applications are emphasized. Finally, perspectives on the current challenges and opportunities of micro-/nano-structured smart polymeric materials for their future development are presented.

Enzyme and microwave co-assisted extraction, structural characterization and antioxidant activity of polysaccharides from Purple-heart Radish.

A novel method of simultaneous extraction and separation of diverse polysaccharides from Purple-heart Radish was developed by integrating EAE with MAATPE. The effects of different enzymes, the ATPS composition, extraction temperature, time etc. were investigated by single-factor experiments and RSM. Under the optimum conditions, the extraction yields of PTP, PBP and total polysaccharides were 9.107 ± 0.391%, 32.506 ± 0.046% and 41.613 ± 0.437%, respectively. By means of HPGPC and PMP-HPLC, Mw of PTP and Mw of PBP were 15935 Da and 27962 Da, respectively. PTP and PBP were mainly composed of mannose, glucuronic acid, aminogalactose, glucose, galactose and arabinose. Moreover, both polysaccharides exhibited stronger antioxidant activities for scavenging multiple radicals and anti-lipid peroxidation. Compared to the conventional extraction methods, EAE-MAATPE achieved higher extraction efficiency due to the synergistic effect between EAE and MAATPE leading to rupture and enzymolysis of cell. Thus, EAE-MAATPE provided an efficient alternative to simultaneous extraction of different polysaccharides from natural products.

Microwave-assisted organic acid-base-co-catalyzed tandem Meinwald rearrangement and annulation of styrylepoxides.

A novel organic acid-base-co-catalyzed conversion of styrylepoxides into [1,1'-biaryl]-3-carbaldehydes was realized under microwave irradiation. Styrylepoxides first underwent an acid-catalyzed Meinwald rearrangement followed by a tandem base-catalyzed Michael addition, aldol addition, and aromatization sequence to generate [1,1'-biaryl]-3-carbaldehydes.

Sequential extraction and enrichment of flavonoids from Euonymus alatus by ultrasonic-assisted polyethylene glycol-based extraction coupled to temperature-induced cloud point extraction.

A green method for simultaneous extraction and enrichment of flavonoids from Euonymus alatus was developed by ultrasonic-assisted extraction (UAE) and temperature-induced cloud point extraction (TICPE) using PEG-base aqueous solution as the extractant. Based on screening different molecular weights of PEGs, PEG-400/water was used as the extractant, and the effects of key factors on extraction yields of flavonoids were investigated by single-factor experiments and response surface methodology (RSM). The optimum conditions of UAE were as follows: PEG-400 concentration of 16% (w/w), particle size of 80 mesh, solvent-to-material ratio of 60:1, extraction temperature of 90 °C and extraction time of 15 min. The results obtained by validation experiments were consistent with the values predicted by RSM. Temperature-induced formation of the aqueous two-phase system (ATPS) and TICPE process were further investigated by controlling temperature and adding (NH4)2SO4. In the presence of (NH4)2SO4, the ATPS formed at 75 â„ƒ and pH 3.5 could effectively improve separation and recovery of flavonoids with enrichment factor of above five times. Gallic acid, catechin, dihydromyricetin and ellagic acid in the extract were identified and confirmed by UPLC-Q-TOF-MS and the corresponding standards. The UAE-TICPE coupled to HPLC was successfully applied for extraction and determination of flavonoids in two batches of Euonymus alatus. The extraction yields of catechin, dihydromyricetin and total flavonoids were 0.377-0.684 mg/g, 1.091-1.353 mg/g and 2.612-3.146 mg/g, respectively. Compared to conventional extraction methods, PEG-based UAE integrated with TICPE in one-step procedure exhibited higher extraction efficiency and better extraction selectivity.

Lewis acid catalyzed inverse-electron-demand Diels-Alder reaction of tropones.

Lewis acid catalyzed inverse-electron-demand Diels-Alder reaction of tropone derivatives was developed. Up to 97% ee was obtained for the chiral dinucleus BINOL-aluminum complex catalyzed reaction between tropones and ketene diethyl acetal to give bicyclo[3.2.2] ring structures, which opens up a unique way of making chiral seven-membered rings.

Synthesis of α-heterosubstituted ketones through sulfur mediated difunctionalization of internal alkynes.

Synthesis of α-heterosubstituted ketones was achieved through sulfur mediated difunctionalization of internal alkynes in one pot. The reaction design involves: phenyl substituted internal alkyne attacking triflic anhydride activated diphenyl sulfoxide to give a sulfonium vinyl triflate intermediate, hydrolysis to give an α-sulfonium ketone, and then substitution with various nucleophiles. This method provides a unified route to access α-amino ketones, α-acyloxy ketones, α-thio ketones, α-halo ketones, α-hydroxy ketones, and related heterocyclic structures, in a rapid fashion.

Microwave-assisted aqueous two-phase extraction of diverse polysaccharides from Lentinus edodes: Process optimization, structure characterization and antioxidant activity.

Microwave-assisted aqueous two-phase extraction (MAATPE) was applied to simultaneous extraction of diverse polysaccharides from Lentinus edodes with aqueous two-phase extraction system (ATPS) of ethanol/ammonium sulfate as the biphasic extractant. Key factors in MAATPE process were optimized by response surface methodology, and the optimum conditions were concluded as follows: the ATPS composition of ethanol concentration 26.0% (w/w) and (NH4)2SO4 concentration 19.58% (w/w), extraction temperature 78.7 °C, extraction time 19.55 min and solid-to-solvent ratio 1:50. The extraction yields of the polysaccharides from the top phase (PTP) and the bottom phase (PBP) were 2.12 ±â€¯0.21% and 11.16 ±â€¯0.28%, respectively. By means of FT-IR, HPGPC and HPLC analysis, PTP and PBP were different from each other in chemical structure, their average molecular weight (MW) were respectively 119,533 Da and 3906 Da. Also, the mechanism of MAATPE process was explored by composition analysis and scanning electron microscopy. Both polysaccharides exhibited stronger antioxidant activities, EC50 values of scavenging DPPH, hydroxyl and superoxide radicals for PBP achieved 580 ±â€¯3, 83.1 ±â€¯3.6 and 91.1 ±â€¯0.5 µg/mL as against 560 ±â€¯4, 76.3 ±â€¯2.2 and 89.3 ±â€¯2.4 µg/mL of PTP, respectively. Compared with conventional methods using a mono-phase solvent, MAATPE can not only greatly improve extraction efficiency, but also selectively extract diverse polysaccharides.

Chiral Pentacarboxycyclopentadiene-Based Brønsted Acid-Catalyzed Enantioselective Desymmetrization of Meso-Epoxides by 2-Mercaptobenzothiazoles.

Enantioselective desymmetrization of meso-epoxides by 2-mercaptobenzothiazoles was realized by using the pentacarboxycyclopentadiene-based chiral Brønsted acid in combination of N-isopropylaniline as amine additive to give up to 90.5:9.5 er of the ring opening products.

Biochemistry and biomedicine of quantum dots: from biodetection to bioimaging, drug discovery, diagnostics, and therapy.

According to recent research, nanotechnology based on quantum dots (QDs) has been widely applied in the field of bioimaging, drug delivery, and drug analysis. Therefore, it has become one of the major forces driving basic and applied research. The application of nanotechnology in bioimaging has been of concern. Through in vitro labeling, it was found that luminescent QDs possess many properties such as narrow emission, broad UV excitation, bright fluorescence, and high photostability. The QDs also show great potential in whole-body imaging. The QDs can be combined with biomolecules, and hence, they can be used for targeted drug delivery and diagnosis. The characteristics of QDs make them useful for application in pharmacy and pharmacology. This review focuses on various applications of QDs, especially in imaging, drug delivery, pharmaceutical analysis, photothermal therapy, biochips, and targeted surgery. Finally, conclusions are made by providing some critical challenges and a perspective of how this field can be expected to develop in the future. STATEMENT OF SIGNIFICANCE: Quantum dots (QDs) is an emerging field of interdisciplinary subject that involves physics, chemistry, materialogy, biology, medicine, and so on. In addition, nanotechnology based on QDs has been applied in depth in biochemistry and biomedicine. Some forward-looking fields emphatically reflected in some extremely vital areas that possess inspiring potential applicable prospects, such as immunoassay, DNA analysis, biological monitoring, drug discovery, in vitro labelling, in vivo imaging, and tumor target are closely connected to human life and health and has been the top and forefront in science and technology to date. Furthermore, this review has not only involved the traditional biochemical detection but also particularly emphasized its potential applications in life science and biomedicine.