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Handedness is an essential attribute of chiral nanocrystals, having a major influence on their properties. During chemical growth, the handedness of nanocrystals is usually tuned by selecting the corresponding enantiomer of chiral molecules involved in asymmetric growth, often known as chiral inducers. We report that, even using the same chiral inducer enantiomer, the handedness of chiral gold nanocrystals can be reversed by using Au nanorod seeds with either single crystalline or pentatwinned structure. This effect holds for chiral growth induced both by amino acids and by chiral micelles. Although it was challenging to discern the morphological handedness for L-cystine-directed particles, even using electron tomography, both cases showed circular dichroism bands of opposite sign, with nearly mirrored chiroptical signatures for chiral micelle-directed growth, along with quasi-helical wrinkles of inverted handedness. These results expand the chiral growth toolbox with an effect that might be exploited to yield a host of interesting morphologies with tunable optical properties., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Liquid crystal elastomers (LCEs) with promising applications in the field of actuators and soft robotics are reported. However, most of them are activated by external heating or light illumination. The examples of electroactive LCEs are still limited; moreover, they are monofunctional with one type of deformation (bending or contraction). Here, the study reports on trilayer electroactive LCE (eLCE) by intimate combination of LCE and ionic electroactive polymer device (i-EAD). This eLCE is bi-functional and can perform either bending or contractile deformations by the control of the low-voltage stimulation. By applying a voltage of ±2 V at 0.1 Hz, the redox behavior and associated ionic motion provide a bending strain difference of 0.80%. Besides, by applying a voltage of ±6 V at 10 Hz, the ionic current-induced Joule heating triggers the muscle-like linear contraction with 20% strain for eLCE without load. With load, eLCE can lift a weight of 270 times of eLCE-actuator weight, while keeping 20% strain and affording 5.38 kJ·m -3 work capacity. This approach of combining two smart polymer technologies (LCE and i-EAD) in a single device is promising for the development of smart materials with multiple degrees of freedom in soft robotics, electronic devices, and sensors., (© 2023 The Authors. Small published by Wiley‐VCH GmbH.)

The catalytic mechanisms of nitrogen reduction reaction (NRR) on the pristine and Co/α-MoC(001) surfaces were explored by density functional theory calculations. The results show that the preferred pathway is that a direct N≡N cleavage occurs first, followed by continuous hydrogenations. The production of second NH 3 molecule is identified as the rate-limiting step on both systems with kinetic barriers of 1.5 and 2.0 eV, respectively, indicating that N 2 -to-NH 3 transformation on bimetallic surface is more likely to occur. The two components of the bimetallic center play different roles during NRR process, in which Co atom does not directly participate in the binding of intermediates, but primarily serves as a reservoir of H atoms. This special synergy makes Co/α-MoC(001) have superior activity for ammonia synthesis. The introduction of Co not only facilitates N 2 dissociation, but also accelerates the migration of H atom due to the antibonding characteristic of Co-H bond. This study offers a facile strategy for the rational design and development of efficient catalysts for ammonia synthesis and other reactions involving the hydrogenation processes., (© 2023 Wiley-VCH GmbH.)

Amorphous iron-calcium phosphate (Fe-ACP) plays a vital role in the mechanical properties of teeth of some rodents, which are very hard, but its formation process and synthetic route remain unknown. Here, the synthesis and characterization of an iron-bearing amorphous calcium phosphate in the presence of ammonium iron citrate (AIC) are reported. The iron is distributed homogeneously on the nanometer scale in the resulting particles. The prepared Fe-ACP particles can be highly stable in aqueous media, including water, simulated body fluid, and acetate buffer solution (pH 4). In vitro study demonstrates that these particles have good biocompatibility and osteogenic properties. Subsequently, Spark Plasma Sintering (SPS) is utilized to consolidate the initial Fe-ACP powders. The results show that the hardness of the ceramics increases with the increase of iron content, but an excess of iron leads to a rapid decline in hardness. Calcium iron phosphate ceramics with a hardness of 4 GPa can be achieved, which is higher than that of human enamel. Furthermore, the ceramics composed of iron-calcium phosphates show enhanced acid resistance. This study provides a novel route to prepare Fe-ACP, and presents the potential role of Fe-ACP in biomineralization and as starting material to fabricate acid-resistant high-performance bioceramics., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Biocompatible and bio-active coatings can enhance and accelerate osseointegration via chemical binding onto substrates. Amorphous calcium phosphate (ACP) has been shown as a precursor to achieve mineralization in vertebrates and invertebrates under the control of biological macromolecules. This work presents a simple bioinspired Gelatin-CaPO 4 (Gel-CaP) composite coating on titanium surfaces to improve osseointegration. The covalently bound Gel-CaP composite is characterized as an ACP-Gel compound via SEM, FT-IR, XRD, and HR-TEM. The amorphous compound coating exhibits a nanometer range thickness and improved elastic modulus, good wettability, and nanometric roughness. The amount of grafted carboxyl groups and theoretical thickness of the coatings are also investigated. More importantly, MC3T3 cells, an osteoblast cell line, show excellent cell proliferation and adhesion on the Gel-CaP coating. The level of osteogenic genes is considerably upregulated on Ti with Gel-CaP coatings compared to uncoated Ti, demonstrating that Gel-CaP coatings possess a unique osteogenic ability. To conclude, this work offers a new perspective on functional, bioactive titanium coatings, and Gel-CaP composites can be a low-cost and promising candidate in bone regeneration., (© 2023 The Authors. Advanced Healthcare Materials published by Wiley-VCH GmbH.)

Precisely controlling the morphologies of plasmonic metal nanoparticles (NPs) is of great importance for many applications. Here, a facile seed-mediated growth method is demonstrated that tailors the morphologies of Au@Ag NPs from cubes/cuboids to chiral truncated cuboids/octahedra, well-defined octahedra, and tetrahedra, via simply increasing the concentrations of AgNO 3  and cysteine in the halide surfactant systems. Accordingly, the particle symmetries are also tuned. The method is quite robust where seeds with distinct shapes including irregular ones can all lead to uniform Au@Ag NPs. The evolution of these shapes can be illustrated by a recently proposed symmetry-based kinematic theory (SBKT). Furthermore, SBKT shows a strategy to optimize the preparation of chiral/dissymmetric NPs, and the experimental results confirm such a dissymmetric synthesis strategy. Cuboids and octahedra with corners differently truncated are identified as two different chiral forms. The chirality of the NPs is additionally probed by electrochemistry, where the chiral NPs show enantioselectivity in the oxidation of d- and l-glucose. Altogether, the results gain fundamental insights into tailoring the plasmonic NP morphologies, and also suggest strategies to obtain chiral NPs., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The design for non-Cu-based catalysts with the function of producing C 2+ products requires systematic knowledge of the intrinsic connection between the surface state as well as the catalytic activity and selectivity. In this work, photochemical in situ spectral surface characterization techniques combined with the first principle calculations (DFT) were applied to investigate the relationships between the composition of surface states, coordinated motifs, and catalytic selectivity of a titanium oxynitride catalyst. When the catalyst mediates CO 2 photoreduction, C 2 product selectivity is positively correlated with the surface Ti 2+ /Ti 3+ ratio and the surface oxidation state is regulated and controlled by coordinated motifs of N-Ti-O/V[O], which can reduce the potential dimerization energy barriers of *CO-CO* and promote spontaneous formation of the subsequent *CO-CH 2 * intermediate. This phenomenon provides a new perspective for the design of heterogeneous catalysts for photoreduction of CO 2 into useful products., (© 2022 Wiley-VCH GmbH.)

A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology may hold the key to the practical utilization of these materials. An optimized chiral growth method to prepare fourfold twisted gold nanorods is described herein, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges are found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl 4 , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent. From detailed electron microscopy analysis of the crystallographic structures, it is proposed that the dissymmetry results from the development of chiral facets in the form of protrusions (tilted ridges) on the initial nanorods, eventually leading to a twisted shape. The role of cysteine is attributed to assisting enantioselective facet evolution, which is supported by density functional theory simulations of the surface energies, modified upon adsorption of the chiral molecule. The development of R-type and S-type chiral structures (small facets, terraces, or kinks) would thus be non-equal, removing the mirror symmetry of the Au NR and in turn resulting in a markedly chiral morphology with high plasmonic optical activity., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Triple-negative breast cancer (TNBC) exhibits resistance to conventional treatments due to the presence of cancer stem cells (CSCs), causing postsurgical relapse and a dismal prognosis. Umbilical cord blood natural killer (UCB-NK) cell-based immunotherapy represents a promising strategy for cancer treatment. However, its therapeutic efficacy is greatly restrained by downregulation of the NK cell activation ligand MHC class I-related chain A/B (MICA/B) and autophagy-mediated degradation of NK cell-derived granzyme B (GZMB) in CSCs. Herein, it is demonstrated that suberoylanilide hydroxamic acid (SAHA) epigenetically downregulates let-7e-5p and miR-615-3p to increase MICA/B expression and that 3-methyl adenine (3MA) inhibits autophagy-mediated GZMB degradation, thereby sensitizing breast CSCs to UCB-NK cells. Then, an injectable hydrogel is designed to codeliver SAHA and 3MA to enhance UCB-NK cell infusion efficacy in TNBC. The hydrogel precursors can be smoothly injected into the tumor resection bed and form a stable gel in situ, allowing for a pH-sensitive sustained release of SAHA and 3MA. Moreover, UCB-NK cell infusion in combination with the hydrogel efficiently controls postsurgical relapse of TNBC. In addition, the hydrogel exhibits good hemostasis and wound-healing functions. Therefore, the work provides proof of concept that an injectable epigenetic autophagic modulatory hydrogel augments UCB-NK cell therapy to combat postsurgical relapse of TNBC., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The growth of crystalline nanoparticles (NPs) generally involves three processes: nucleation, growth, and shape evolution. Among them, the shape evolution is less understood, despite the importance of morphology for NP properties. Here, we propose a symmetry-based kinematic theory (SBKT) based on classical growth theories to illustrate the process. Based on the crystal lattice, nucleus (or seed) symmetry, and the preferential growth directions under the experimental conditions, the SBKT can illustrate the growth trajectories. The theory accommodates the conventional criteria of the major existing theories for crystal growth and provides tools to better understand the symmetry-breaking process during the growth of anisotropic structures. Furthermore, complex dendritic growth is theoretically and experimentally demonstrated. Thus, it provides a framework to explain the shape evolution, and extends the morphogenesis prediction to cases, which cannot be treated by other theories., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

CD8 + T cell responses play a critical regulatory role in protection against mycoplasma infection-related respiratory diseases. Nanovesicles derived from cell membranes have been shown to induce CD8 + T cell responses. Moreover, the short residence time of mycoplasma membrane-related vaccines in local lymph nodes limits the efficacy of current mycoplasma vaccines. Here, a long-residence pneumonia vaccine is developed using nanovesicles prepared by cell membrane fusion of Mycoplasma hyopneumoniae and interferon-γ (IFN-γ   )-primed macrophages, which are grafted with polyethylene glycol to increase residence time in the lymph nodes. Upregulation of intercellular adhesion molecule-1 (ICAM-1) on the membrane of IFN-γ-primed macrophages increases the targeting of the hybrid nanovesicle vaccine to the local lymph nodes, with increased CD8 + T cell activation. A mechanistic study reveals that CD8 + T cell activation is achieved via a pathway involving upregulation of C-C motif chemokine ligand 2/3 expression by E26 transformation-specific sequences, followed by increased immune-stimulatory activity of dendritic cells. In vivo, prophylactic testing reveals that the hybrid nanovesicle vaccine triggers a long-term immune response, as evidenced by a memory CD8 + T cell response against mycoplasma infection. The current study provides a new design strategy for mycoplasma vaccines that involves a hybrid method using biological sources and artificial modification., (© 2021 Wiley-VCH GmbH.)

The research on soft actuators including liquid crystal elastomers (LCEs) becomes more and more appealing at a time when the expansion of artificial systems is blooming. Among the various LCE actuators, the bending deformation is often in the origin of many actuation modes. Here, a new strategy with plasma technology is developed to prepare single-layer main-chain LCEs with thermally actuated bending and contraction deformations. Two distinct reactions, plasma polymerization and plasma-induced photopolymerization, are used to polymerize in one step the nematic monomer mixture aligned by magnetic field. The plasma polymerization forms cross-linked but disoriented structures at the surface of the LCE film, while the plasma-induced photopolymerization produces aligned LCE structure in the bulk. The actuation behaviors (bending and/or contraction) of LCE films can be adjusted by plasma power, reaction time, and sample thickness. Soft robots like crawling walker and flower mimic are built by LCE films with bending actuation., (© 2020 Wiley-VCH GmbH.)

A facile one-step solvothermal approach to engineer a van der Waals integrated heteromaterial self-assembled superstructure composed of two structurally distinct species that is polyoxomolybdate and zirconia (POM-ZrO 2 ) is reported. Nonclassical aggregation-based self-assembly process grows the superstructure. The introduced POM not only behaves as a catalytically active component of the hybrid structure but also imparts flexibility to the developed POM-ZrO 2 superstructures. The material shows high performance toward oxygenation of thioethers as a result of its morphology, composition, and structure. This growing strategy may introduce a viable pathway to the rational design of Van der Waals integrated complex hybrid, catalytically active assemblies with potential applications in different fields., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A hierarchically assembled necklace composed of amphiphilic diblock copolymer micelles is exquisitely produced by capitalizing on two concurrent self-assembly processes at different scales (i.e., "breath figure" strategy of diblock copolymer micelles solution evaporating in humid air to yield rings at the microscopic scale in conjunction with self-assembly of diblock copolymer micelles within individual ring at the nanometer scale). Intriguingly, hierarchical rings of diblock copolymer micelles comprising gold precursors or fluorescent dyes can also be crafted using this strategy. Upon exposure to hydrophilic block-selective solvent, core-corona inversion of micelles within the microscopic rings occurs. In contrast, such inversion is inhibited when the micelles are impregnated by gold precursors. This simple yet effective strategy for engineering diblock copolymer micelles may be extended to produce hierarchically assembled structures consisting of other functional block copolymers (e.g., stimuli-responsive block copolymer) and nanocrystals (e.g., semiconducting, magnetic, ferroelectric, etc.) with unique catalytic, magnetic, ferroelectric, optical, electronic, and optoelectronic properties., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Size is one of the central issues in nanoscience. The practical meaning of the term "sub-nanometric material (SNM)" requires two aspects: (1) its size should be at the atomic level; (2) it shows unique (size-related) properties compared to its nano-counterparts with larger sizes. Here, SNMs in the form of wires (SNWs) and the unique properties arising from their special size are reviewed. First, their polymer-like behavior, including rheological behavior and self-assembly, is dicussed. Their origins may stem from the special size and the ligands around the wire. Even a slight increase in diameter would risk the polymer-like behavior. Meanwhile, the ligands on SNWs are proportional to the inorganic entity at this scale. Consequently, surface ligands should have a profound impact on the properties, like catalysis, self-assembly, optics, etc. To reveal more potential applications, their applications in energy conversion are comprehensively reviewed. To some extent, characterization can greatly influence the way things are observed. Thus, some appropriate characterization techniques are briefly introduced. Finally, another emerging part of SNWs (atomic chain material) is briefly introduced. It is hoped that this review can provide new insights to this special scale., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

MOFs are a type of ideal crystalline material with rigid reticular structures whereas microcapsules are usually prepared from soft mater, such as polymers or supramolecules. The synthesis of MOF-based microcapsules with novel nanostructures at the molecular scale remains a great challenge. Herein, we develop a competitive coordination strategy to synthesize MOF-based microcapsules with novel bowl-like structures. During the competitive coordination process, the infinite structures of MOFs are partially broken by the competitive reagents, thus flexibility is introduced into the rigid skeletons and results in the formation of bowl-like microcapsules. Owing to the unique structure and composition of these nano-structures, the microcapsules exhibit excellent performance and stability in adsorbing and removing iodine for both vapor and solution. This work describes new opportunities in designing MOF-based microcapsules with novel structures., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Although much attention has been paid to the exploration of highly active electrocatalysts, especially catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), the development of multifunctional catalysts remains a challenge. Here, we utilize AuNi heterodimers as the starting materials to achieve high activities toward HER, OER and ORR. The HER and ORR activities in an alkali environment are similar to those of Pt catalysts, and the OER activity is very high and better than that of commercial IrO 2 . Both the experimental and calculated results suggest that the surface oxidation under oxidative conditions is the main reason for the different activities. The NiO/Ni interface which exists in the as-synthesized heterodimers contributes to high HER activity, the Ni(OH) 2 -Ni-Au interface and the surface Ni(OH) 2 obtained in electrochemical conditons gives rise to promising ORR and OER activities, respectively. As a comparison, a Au@Ni core-shell structure is also synthesized and examined. The core-shell structure shows lower activities for HER and OER than the heterodimers, and reduces O 2 selectively to H 2 O 2 . The work here allows for the development of a method to design multifunctional catalysts via the partial oxidation of a metal surface to create different active centers., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Synthesizing ultrathin 2D metal-organic framework nanosheets in high yields has received increasing research interest but remains a great challenge. In this work, ultrathin zirconium-porphyrinic metal-organic framework (MOF) nanosheets with thickness down to ≈1.5 nm are synthesized through a pseudoassembly-disassembly strategy. Owing to the their unique properties originating from their ultrathin thickness and highly exposed active sites, the as-prepared ultrathin nanosheets exhibit far superior photocatalysis performance compared to the corresponding bulk MOF. This work highlights new opportunities in designing ultrathin MOF nanosheets and paves the way to expand the potential applications of MOFs., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Single atoms immobilized on metal-organic frameworks (MOFs) with unique nanostructures have drawn tremendous attention in the application of catalysis but remain a great challenge. Various single noble-metal atoms have now been successfully anchored on the well-defined anchoring sites of the zirconium porphyrin MOF hollow nanotubes, which are probed by aberration-corrected scanning transmission electron microscopy and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy. Owing to the hollow structure and excellent photoelectrochemical performance, the HNTM-Ir/Pt exhibits outstanding catalytic activity in the visible-light photocatalytic H 2 evolution via water splitting. The single atom immobilized on MOFs with hollow structures are expected to pave the way to expand the potential applications of MOFs., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reducing costs while maintaining high activities and stabilities of oxygen reduction reaction (ORR) catalysts has long been pursued for applications to membrane fuel cells. Here, an absorption-reaction method is used to prepare a zeolitic imidazolate framework coated commercial carbon, and the pyrolysis of such material brings about impressive ORR activities and stabilities with large diffusion-limited current density, half-wave potential, and no obvious decay after 10 000 cyclic voltammetry cycles, which is even better than that of the commercial Pt/C catalysts. The absorption-reaction method is realized by simply soaking the commercial carbon black sequentially in Co(NO 3 ) 2 and 2-methylimidazole solutions at ambient conditions. The detailed analysis on such carbon materials reveals that both Co and N are essential to activities, even the amount of N and Co species is very low. The reduction of raw materials and simplified handling procedures result in well-controlled costs in applications., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A synthesis strategy for the preparation of trimetallic PtCoFe alloy nanoparticle superlattices is reported. Trimetallic PtCoFe alloy monolayer array of nanoparticle superlattices with a large density of high index facets and platinum-rich surface are successfully prepared by coreduction of metal precursors in formamide solvent. The concentration of cetyl trimethyl ammonium bromide plays a vital role for the formation of a monolayer array of nanoparticle superlattices, while the size of nanoparticles is determined by NaI. The prepared monolayer array of nanoparticle superlattices is the superior catalyst for oxygen reduction reaction as well as for ethanol oxidation owing to their specific structural and compositional characteristics., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Porous PtCuBiMn nanosheets are developed with a thickness of ≈3-4 nm. The specific and mass activities of these nanosheets are ten and seven times greater than that of commercial Pt/C catalyst, respectively. PtCuBiMn nanosheets demonstrate superior catalytic performance for the oxygen reduction reaction, as well as resistance to methanol cross-over effects, suggesting that it is a promising catalyst for direct methanol fuel cells., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fullerene-like nickel oxysulfide hollow nanospheres with ≈50 nm are constructed by in situ growth on the surface of nickel foam by taking advantage of solvothermal reaction. The as-prepared composite exhibits exhilaratingly high HER and OER performance in 1 m KOH, which opens up a very promising aspect for non-noble metal chalcogenides as bifunctional electrocatalysts., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reversible tuning of ultra-small multimetallic Pt-Pd-Rh-Ag nanoframes is achieved. These nanoframes showed tunable and reversible modes for the oxidation of small organic molecules by simply inducing segregation with adsorbates, such as SO 4 2- and OH - . This is the first example of reversible segregation under electrocatalytic conditions in atomic-sized electrocatalysts. These nanoframes also showed a controllable activity and good stability for the oxidation of small organic molecules., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Spontaneous formation of concentric lamellae was observed in self-assembling giant surfactants consisting of a fluorinated polyhedral oligomeric silsesquioxane (FPOSS) head and flexible polymer tail(s). Owing to the asymmetrical sizes of the head and tail blocks and the rectangular molecular interface, the giant surfactants assumed a truncated-wedge-like molecular shape, which induced morphological curvature during self-assembly, thus resulting in the formation of curved and concentric lamellae. These curved/concentric lamellae were observed in FPOSS-based giant surfactants with different architectures and compositions. The spontaneous curvature formation not only promotes our fundamental understanding of assembly principles, but also provides a promising and efficient approach to the fabrication of a wide range of high-performance devices., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Edges are special sites in nanomaterials. The atoms residing on the edges have different environments compared to those in other parts of a nanomaterial and, therefore, they may have different properties. Here, recent progress in nanomaterial fields is summarized from the viewpoint of the edges. Typically, edge sites in MoS 2 or metals, other than surface atoms, can perform as active centers for catalytic reactions, so the method to enhance performance lies in the optimization of the edge structures. The edges of multicomponent interfaces present even more possibilities to enhance the activities of nanomaterials. Nanoframes and ultrathin nanowires have similarities to conventional edges of nanoparticles, the application of which as catalysts can help to reduce the use of costly materials. Looking beyond this, the edge structures of graphene are also essential for their properties. In short, the edge structure can influence many properties of materials.

Atomically thick and flexible Pt-Cu alloy nanosheets are prepared and loaded with either Pd or Pt to produce sandwich structures or nanoring-like nanosheet structures, respectively. Core-shell alloy nanoparticles containing Rh, Ir, and Ru are also prepared. All of these structures exhibit superior specific and mass activities for the oxidation of formic acid for fuel cells for portable electronic devices as compared to commercial Pd/C catalyst., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The asymmetric synthesis of compounds that contain new C-C and C-O bonds remains one of the most important types of synthesis in organic chemistry. Over the years, many different types of catalysts have been designed and used effectively to carry out such transformations. Ionic-liquid-supported (ILS) catalysts represent a new and very effective class of catalysts that are used to facilitate the asymmetric synthesis of such compounds. There are many advantages to using ILS catalysts; they are nontoxic, environmentally benign, and, most important, recyclable. An overview of the design, synthesis, mode of action, and effectiveness of this class of catalysts is reported., (Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fifteen strains of mAb specific for HA of the A/Hong Kong/482/97 (H5N1) influenza virus were generated. The HA antigenic sites of the human A/Hong Kong/482/97 (H5N1) influenza virus were defined by using yeast cell surface-displaying system and anti-H5 HA mAb. Evolution analysis of H5 HA identified residues that exhibit diversifying selection in the antigenic sites and demonstrated surprising differences between residue variation of H5 HA and H3 HA. A conserved neutralizing epitope in the H5 HA protein recognized by mAb H5M9 was found using viruses isolated from 1997-2006. Seven single amino acid substitutions were introduced into the HA antigenic sites, respectively, and the alteration of antigenicity was assessed. The structure obtained by homology-modeling and molecular dynamic methods showed that a subtle substitution at residue 124 propagates throughout its nearby loop (152-159). We discuss how the structural changes caused by point mutation might explain the altered antigenicity of the HA protein. The results demonstrate the existence of immunodominant positions in the H5 HA protein, alteration of these residues might improve the immunogenicity of vaccine strains.

Altered peptide ligands with increased affinity of the peptide-MHC complex for the TCR provide an alternative strategy to natural T-cell epitopes for cancer immunotherapy, as they can recruit and stimulate stronger T-cell repertoires. However, it remains unclear how alterations of the TCR contact residues improve the interaction between the peptide-MHC complex and the TCR molecule. In this study, we introduced a molecular simulation strategy to optimize a tumor immunodominant epitope NY-ESO-1(157-165) by the substitution of the potential TCR contact residues. We correlated molecule simulation with T-cell activation capacity assay and detected the effect of modifications of TCR contact residues on T-cell recognition. An agonist peptide W5F with substitution at Trp5 with Phe was identified and it exhibits a stronger ability to induce a cross-reactive CTL response with the WT peptide. Additionally, the W5F-induced CTL could be maintained with the WT peptide and possess higher capacity in lysing native NY-ESO-1-expressing tumor cells. These results provide important insights into the enhanced immunogenicity of epitopes through substitution at the TCR contact sites and revealed a novel molecular simulation approach for rational therapeutic peptide vaccine design.

Vaccination with antigenic peptide-pulsed antigen-presenting cells (APC) represents an attractive approach for therapy for cancer and diseases caused by intracellular infections. It has been suggested that sufficient stable MHC/peptide complexes on the surface of APC might play an important role in the generation of antitumor and antiviral immunity in vivo. In this study, we observed that exogenous peptides that were artificially fused with an endoplasmic reticulum (ER) retrieval signal, a C-terminal Lys-Asp-Glu-Leu sequence, could be efficiently presented by intracellular MHC class I molecules in a TAP- and proteasome-independent, but brefeldin A-sensitive manner. The APC retained the capacity to display surface MHC/peptide complexes for a prolonged period. In addition, our results show that vaccination with DC bearing our fusion peptides induced greatly enhanced specific CTL response, and resulted in significant inhibition of tumor growth. Thus, the ER retrieval signal modification can be regarded as a novel method for targeting exogenous peptides into the intracellular MHC class I presentation pathway, and may improve the clinical utility of vaccines based on synthetic peptide pulsed DC.

The double ring-closing metathesis reaction of nitrogen-containing tetraenes was studied. The selectivity of the fused/dumbbell-type products can be controlled by the electronic/steric effects of the substituents attached to the C[double bond]C bonds and the s-cis/s-trans conformational ratios of the substrates. This methodology has also been successfully applied to the enantioselective synthesis of four stereoisomers of lupinine and their derivatives.