Zhejiang Sci-Tech University

Peptide drug development has made great progress in the last decade thanks to new production, modification, and analytic technologies. Peptides have been produced and modified using both chemical and biological methods, together with novel design and delivery strategies, which have helped to overcome the inherent drawbacks of peptides and have allowed the continued advancement of this field. A wide variety of natural and modified peptides have been obtained and studied, covering multiple therapeutic areas. This review summarizes the efforts and achievements in peptide drug discovery, production, and modification, and their current applications. We also discuss the value and challenges associated with future developments in therapeutic peptides.

Because of the importance of novel macrocycles in supramolecular science, interest in the preparation of these substances has grown considerably. However, the discovery of a new class of macrocycles presents challenges because of the need for routes to further functionalization of these molecules and good host-guest complexation. Furthermore, useful macrocylic hosts must be easily synthesized in large quantities. With these issues in mind, the recently discovered pillararenes attracted our attention. These macrocycles contain hydroquinone units linked by methylene bridges at para positions. Although the composition of pillararenes is similar to that of calixarenes, they have different structural characteristics. One conformationally stable member of this family is pillar[5]arene, which consists of five hydroquinone units. The symmetrical pillar architecture and electron-donating cavities of these macrocycles are particularly intriguing and afford them with some special and interesting physical, chemical, and host-guest properties. Due to these features and their easy accessibility, pillararenes, especially pillar[5]arenes, have been actively studied and rapidly developed within the last 4 years. In this Account, we provide a comprehensive overview of pillararene chemistry, summarizing our results along with related studies from other researchers. We describe strategies for the synthesis, isomerization, and functionalization of pillararenes. We also discuss their macrocyclic cavity sizes, their host-guest properties, and their self-assembly into supramolecular polymers. The hydroxyl groups of the pillararenes can be modified at all positions or selectively on one or two positions. Through a variety of functionalizations, researchers have developed many pillararene derivatives that exhibit very interesting host-guest properties both in organic solvents and in aqueous media. Guest molecules include electron acceptors such as viologen derivatives and (bis)imidazolium cations and alkyl chain derivatives such as n-hexane, alkanediamines, n-octyltrimethyl ammonium, and neutral bis(imidazole) derivatives. These host-guest studies have led to the fabrication of (pseudo)rotaxanes or poly(pseudo)rotaxanes, supramolecular dimers or polymers, artificial transmembrane proton channels, fluorescent sensors, and other functional materials.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTSynthesis of Heterocycles via Palladium-Catalyzed CarbonylationsXiao-Feng Wu*†‡, Helfried Neumann‡, and Matthias Beller*‡View Author Information† Department of Chemistry, Zhejiang Sci-Tech University, Xiasha Campus, Hangzhou, Zhejiang Province, P. R. China 310018‡ Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany*E-mail: [email protected]; [email protected]Cite this: Chem. Rev. 2013, 113, 1, 1–35Publication Date (Web):October 5, 2012Publication History Received8 March 2012Published online5 October 2012Published inissue 9 January 2013https://pubs.acs.org/doi/10.1021/cr300100shttps://doi.org/10.1021/cr300100sreview-articleACS PublicationsCopyright © 2012 American Chemical SocietyRequest reuse permissionsArticle Views24230Altmetric-Citations1086LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Alcohols,Carbonylation,Catalysts,Inorganic carbon compounds,Lactones Get e-Alerts

The management of bacterial infections is becoming a major clinical challenge due to the rapid evolution of antibiotic resistant bacteria. As an excellent candidate to overcome antibiotic resistance, antimicrobial peptides (AMPs) that are produced from the synthetic and natural sources demonstrate a broad-spectrum antimicrobial activity with the high specificity and low toxicity. These peptides possess distinctive structures and functions by employing sophisticated mechanisms of action. This comprehensive review provides a broad overview of AMPs from the origin, structural characteristics, mechanisms of action, biological activities to clinical applications. We finally discuss the strategies to optimize and develop AMP-based treatment as the potential antimicrobial and anticancer therapeutics.

Graphene quantum dots (GQDs) that are flat 0D nanomaterials have attracted increasing interest because of their exceptional chemicophysical properties and novel applications in energy conversion and storage, electro/photo/chemical catalysis, flexible devices, sensing, display, imaging, and theranostics. The significant advances in the recent years are summarized with comparative and balanced discussion. The differences between GQDs and other nanomaterials, including their nanocarbon cousins, are emphasized, and the unique advantages of GQDs for specific applications are highlighted. The current challenges and outlook of this growing field are also discussed.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTDevelopment of Pseudorotaxanes and Rotaxanes: From Synthesis to Stimuli-Responsive Motions to ApplicationsMin Xue†, Yong Yang‡, Xiaodong Chi†, Xuzhou Yan†, and Feihe Huang*†View Author Information† State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China‡ Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 15, 7398–7501Publication Date (Web):March 3, 2015Publication History Received10 October 2014Published online3 March 2015Published inissue 12 August 2015https://pubs.acs.org/doi/10.1021/cr5005869https://doi.org/10.1021/cr5005869review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views24378Altmetric-Citations718LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Macrocycles,Polymers,Reaction products,Rotaxanes,Supramolecular chemistry Get e-Alerts

A new class of Co9 S8 @MoS2 core-shell structures formed on carbon nanofibers composed of cubic Co9 S8 as cores and layered MoS2 as shells is described. The core-shell design of these nanostructures allows the advantages of MoS2 and Co9 S8 to be combined, serving as a bifunctional electrocatalyst for H2 and O2 evolution.

Experience plays a crucial role in the development of face processing. In the study reported here, we investigated how faces observed within the visual environment affect the development of the face-processing system during the 1st year of life. We assessed 3-, 6-, and 9-month-old Caucasian infants' ability to discriminate faces within their own racial group and within three other-race groups (African, Middle Eastern, and Chinese). The 3-month-old infants demonstrated recognition in all conditions, the 6-month-old infants were able to recognize Caucasian and Chinese faces only, and the 9-month-old infants' recognition was restricted to own-race faces. The pattern of preferences indicates that the other-race effect is emerging by 6 months of age and is present at 9 months of age. The findings suggest that facial input from the infant's visual environment is crucial for shaping the face-processing system early in infancy, resulting in differential recognition accuracy for faces of different races in adulthood.

Abstract Halloysite nanotubes (HNTs) are types of naturally occurring 1:1 clays with nanotubular structures and similar chemical composition to kaolin. Due to various characteristics such as nanoscale lumens, high length‐to‐diameter ratio, relatively low hydroxyl group density on the surface, etc., numerous exciting applications have been discovered for this unique, cheap and abundantly deposited clay. After briefly summarizing applications in controlled release, nanotemplating and sorption, we emphasize the applications of HNTs in the fabrication of polymer nanocomposites. The unique structures and performance of HNT‐incorporated polymer nanocomposites processed by various routes are described. The results suggest that these nanocomposites exhibit remarkable performance such as reinforcing effects, enhanced flame retardancy and reduced thermal expansion. Accordingly, HNTs should be of interest in the area of polymer nanocomposites for structural and functional applications. Copyright © 2010 Society of Chemical Industry

The mechanism of Li(+) transport through the solid electrolyte interphase (SEI), a passivating film on electrode surfaces, has never been clearly elucidated despite its overwhelming importance to Li-ion battery operation and lifetime. The present paper develops a multiscale theoretical methodology to reveal the mechanism of Li(+) transport in a SEI film. The methodology incorporates the boundary conditions of the first direct diffusion measurements on a model SEI consisting of porous (outer) organic and dense (inner) inorganic layers (similar to typical SEI films). New experimental evidence confirms that the inner layer in the ∼20 nm thick model SEI is primarily crystalline Li(2)CO(3). Using density functional theory, we first determined that the dominant diffusion carrier in Li(2)CO(3) below the voltage range of SEI formation is excess interstitial Li(+). This diffuses via a knock-off mechanism to maintain higher O-coordination, rather than direct-hopping through empty spaces in the Li(2)CO(3) lattice. Mesoscale diffusion equations were then formulated upon a new two-layer/two-mechanism model: pore diffusion in the outer layer and knock-off diffusion in the inner layer. This diffusion model predicted the unusual isotope ratio (6)Li(+)/(7)Li(+) profile measured by TOF-SIMS, which increases from the SEI/electrolyte surface and peaks at a depth of 5 nm, and then gradually decreases within the dense layer. With no fitting parameters, our approach is applicable to model general transport properties, such as ionic conductivity, for SEI films on the surface of other electrodes, from the atomic scale to the mesoscale, as well as aging phenomenon.

Adults are sensitive to the physical differences that define ethnic groups. However, the age at which we become sensitive to ethnic differences is currently unclear. Our study aimed to clarify this by testing newborns and young infants for sensitivity to ethnicity using a visual preference (VP) paradigm. While newborn infants demonstrated no spontaneous preference for faces from either their own- or other-ethnic groups, 3-month-old infants demonstrated a significant preference for faces from their own-ethnic group. These results suggest that preferential selectivity based on ethnic differences is not present in the first days of life, but is learned within the first 3 months of life. The findings imply that adults' perceptions of ethnic differences are learned and derived from differences in exposure to own- versus other-race faces during early development.

Liquid crystals of anisotropic colloids are of great significance in the preparation of their ordered macroscopic materials, for example, in the cases of carbon nanotubes and graphene. Here, we report a facile and scalable spinning process to prepare neat "core-shell" structured graphene aerogel fibers and three-dimensional cylinders with aligned pores from the flowing liquid crystalline graphene oxide (GO) gels. The uniform alignment of graphene sheets, inheriting the lamellar orders from GO liquid crystals, offers the porous fibers high specific tensile strength (188 kN m kg(-1)) and the porous cylinders high compression modulus (3.3 MPa). The porous graphene fibers have high specific surface area up to 884 m(2) g(-1) due to their interconnected pores and exhibit fine electrical conductivity (2.6 × 10(3) to 4.9 × 10(3) S m(-1)) in the wide temperature range of 5-300 K. The decreasing conductivity with decreasing temperature illustrates a typical semiconducting behavior, and the 3D interconnected network of 2D graphene sheets determines a dual 2D and 3D hopping conduction mechanism. The strong mechanical strength, high porosity, and fine electrical conductivity enable this novel material of ordered graphene aerogels to be greatly useful in versatile catalysts, supercapacitors, flexible batteries and cells, lightweight conductive fibers, and functional textiles.

Carbon-fiber reinforced composites are prepared using catalyst-free malleable polyimine networks as binders. An energy neutral closed-loop recycling process has been developed, enabling recovery of 100% of the imine components and carbon fibers in their original form. Polyimine films made using >21% recycled content exhibit no loss of mechanical performance, therefore indicating all of the thermoset composite material can be recycled and reused for the same purpose. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. The contents have been divided according to the electrophiles applied, followed by the different types of nucleophiles. Their reaction mechanisms and applications have been emphatically discussed.

Ultraviolet (UV) radiation has a variety of impacts including the health of humans, the production of crops, and the lifetime of buildings. Based on the photovoltaic effect, self-powered UV photodetectors can measure and monitor UV radiation without any power consumption. However, the current low photoelectric performance of these detectors has hindered their practical use. In our study, a super-high-performance self-powered UV photodetector based on a GaN/Sn:Ga2O3 pn junction was generated by depositing a Sn-doped n-type Ga2O3 thin film onto a p-type GaN thick film. The responsivity at 254 nm reached up to 3.05 A/W without a power supply and had a high UV/visible rejection ratio of R254 nm/R400 nm = 5.9 × 103 and an ideal detectivity at 1.69 × 1013 cm·Hz1/2·W–1, which is well beyond the level of previous self-powered UV photodetectors. Moreover, our device also has a low dark current (1.8 × 10–11A), a high Iphoto/Idark ratio (∼104), and a fast photoresponse time of 18 ms without bias. These outstanding performance results are attributed to the rapid separation of photogenerated electron–hole pairs driven by a high built-in electric field in the interface depletion region of the GaN/Sn:Ga2O3 pn junction. Our results provide an improved and easy route to constructing high-performance self-powered UV photodetectors that can potentially replace traditional high-energy-consuming UV detection systems.

A high efficiency and eco-friendly porous cellulose-based bioadsorbent was synthesized by grafting acrylic acid and acrylamide to remove anionic dye acid blue 93 (AB93) and cationic dye methylene blue (MB) from single and binary dye solutions. The effects of initial dye concentration, bioadsorbent dosage, contact time, solution pH value, temperature, ionic strength and surfactant content on the adsorption capacity of the bioadsorbent were investigated. The maximum adsorption capacities of the bioadsorbent for both AB93 and MB were 1372 mg g–1 at an initial concentration of 2500 mg L–1. The conditions-dependent adsorption characteristics of the bioadsorbent indicated a high efficiency of dyes removal. The appropriate isotherm model for the equilibrium process was the Freundlich, and the kinetic studies revealed that the adsorption of AB93 and MB followed the pseudo-second-order kinetic models. The adsorbent behaviors were dominated by the electrostatic interactions between the bioadsorbents and the dye molecules. Moreover, the recyclability experiments showed that the bioadsorbent could be reused for at least three cycles with stable adsorption capacity even in complex systems containing binary-dyes, salt, and surfactant. Thus, the cellulose-based bioadsorbent can be effectively used for the removal of dyes from industrial textile wastewater.

Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO's use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of carbonylation catalysis, many important research questions and challenges remain. Notably, apart from academic developments, industry applies carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via carbonylation of methanol (Monsanto or Cativa process). The carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions. In this Account, we discuss our work on various carbonylations of unsaturated compounds and related reactions. Rhodium-catalyzed isomerization and hydroformylation reactions of internal olefins provide straightforward access to higher value aldehydes. Catalytic hydroaminomethylations offer an ideal way to synthesize substituted amines and even heterocycles directly. More recently, our group has also developed so-called alternative metal catalysts based on iridium, ruthenium, and iron. What about the future of carbonylation reactions? CO is already one of the most versatile C1 building blocks for organic synthesis and is widely used in industry. However, because of CO's high toxicity and gaseous nature, organic chemists are often reluctant to apply carbonylations more frequently. In addition, new regulations have recently made the transportation of carbon monoxide more difficult. Hence, researchers will need to develop and more frequently use practical and benign CO-generating reagents. Apart from formates, alcohols, and metal carbonyls, carbon dioxide also offers interesting options. Industrial chemists seek easy to prepare catalysts and patent-free ligands/complexes. In addition, non-noble metal complexes will interest both academic and industrial researchers. The novel Lucite process for methyl methacrylate is an important example of an improved catalyst. This reaction makes use of a specific palladium/bisphosphine catalyst, which led to the successful implementation of the technology. More active and productive catalysts for related carbonylations of less reactive olefins would allow for other large scale applications of this methodology. From an academic point of view, researchers continue to look for selective reactions with more functionalized olefins. Finally, because of the volatility of simple metal carbonyl complexes, carbonylation reactions today remain a domain of homogeneous catalysis. The invention of more stable and recyclable heterogeneous catalysts or metal-free carbonylations (radical carbonylations) will be difficult, but could offer interesting challenges for young chemists.

Although magnesium (Mg) is one of the most important nutrients, involved in many enzyme activities and the structural stabilization of tissues, its importance as a macronutrient ion has been overlooked in recent decades by botanists and agriculturists, who did not regard Mg deficiency (MGD) in plants as a severe health problem. However, recent studies have shown, surprisingly, that Mg contents in historical cereal seeds have markedly declined over time, and two thirds of people surveyed in developed countries received less than their minimum daily Mg requirement. Thus, the mechanisms of response to MGD and ways to increase Mg contents in plants are two urgent practical problems. In this review, we discuss several aspects of MGD in plants, including phenotypic and physiological changes, cell Mg2 + homeostasis control by Mg2 + transporters, MGD signaling, interactions between Mg2 + and other ions, and roles of Mg2 + in plant secondary metabolism. Our aim is to improve understanding of the influence of MGD on plant growth and development and to advance crop breeding for Mg enrichment.

Abstract Electrospinning, considered as a low‐cost and straightforward approach, attracts tremendous attention because nanofibrous materials with functional properties prepared by it can be widely applied in numerous fields, including rechargeable batteries, filtration, and distillation. This paper aims to provide a comprehensive review of the latest advances in developing this unique technique, which starts with a brief introduction of the advantages of electrospinning and highlights ongoing research activities, followed by its principles and progress. Afterward, the corresponding properties of electrospun nanofibers are discussed. A future vision regarding challenges and perspectives in this area is proposed at the end. It is believed that this review would provide an extensive and comprehensive reference to utilize this advanced technique to generate novel nanofibers performing in high demanding areas.

This paper studies a multi-user multiple-input single-output (MISO) downlink system for simultaneous wireless information and power transfer (SWIPT), in which a set of single-antenna mobile stations (MSs) receive information and energy simultaneously via power splitting (PS) from the signal sent by a multi-antenna base station (BS). We aim to minimize the total transmission power at BS by jointly designing transmit beamforming vectors and receive PS ratios for all MSs under their given signal-to-interference-plus-noise ratio (SINR) constraints for information decoding and harvested power constraints for energy harvesting. First, we derive the sufficient and necessary condition for the feasibility of our formulated problem. Next, we solve this non-convex problem by applying the technique of semidefinite relaxation (SDR). We prove that SDR is indeed tight for our problem and thus achieves its global optimum. Finally, we propose two suboptimal solutions of lower complexity than the optimal solution based on the principle of separating the optimization of transmit beamforming and receive PS, where the zero-forcing (ZF) and the SINR-optimal based transmit beamforming schemes are applied, respectively.