Nanoscale Metal‐Organic Frameworks: Synthesis,Biocompatibility, Imaging Applications,and Thermal and Dynamic Therapy of Tumors

Nanoscale metal‐organic frameworks (NMOFs) have attracted increasing attention for biomedical applications due to their large specific surface area, good biocompatibility, adjustable structures, and diverse functions. By choosing appropriate metal ions and ligands, NMOFs can be synthesized and regulated to assist the diagnosis and treatment of cancer, acting as imaging agents, drug carriers, and cancer therapeutic agents. This review summarizes the recent advances of NMOFs in synthesis, biocompatibility, imaging, and applications in cancer therapies. Among these, the term “biocompatibility” is used to outline their various biological characteristics, and it is mainly discussed from the aspects of size and surface properties of NMOFs. The imaging section mainly emphasizes the application advantages of NMOFs as imaging agents in magnetic resonance, computed tomography, and fluorescence imaging. The applications of NMOFs in four cancer therapies, including phototherapy, radiotherapy, microwave therapy, and ultrasonic therapy, are addressed, especially for thermal and dynamic therapy. Finally, the prospects and challenges of NMOFs in imaging and cancer therapies are also discussed.     

Engineering the Pore Structure and Functionality of Ionic Porous Polymers for Separating Acetylene over Carbon Dioxide

Precise engineering of organic porous polymers to realize the selective separation of structurally similar gases presents a great challenge. In this study, a new class of ionic porous polymers P(Ph3Im-Br-nDVB) with a high ionic density and microporous surface area are constructed through a facile copolymerization strategy, providing an efficient path to rational control over pore structure and functionality. The first example of ionic porous organic polymers is reported to address the challenge of discriminating the subtle difference of C₂H₂ and CO₂, which have almost identical molecular sizes and similar physicochemical properties, which achieve the highest C₂H₂/CO₂ selectivity (17.9) among porous organic polymers. These ionic porous polymers exhibit high stability and excellent dynamic breakthrough performance for binary C₂H₂/CO₂ mixtures, indicating their practical feasibility. Modeling studies reveal that anions are the specific binding sites for preferential C₂H₂ capture because of Br⁻···HCCH interactions. This study not only demonstrates an efficient strategy to build novel ionic porous polymers integrating abundant micropores and ionic sites but also sheds some light on the development of functionalized materials for the separation of structurally similar gas molecules.     

新型层状结构SnO的合成、光学性质及其表面缺陷

采用无模板水热法在温和的反应条件下成功合成了形貌结构均一的层状结构氧化亚锡(SnO).利用X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)和能量散射X射线探测器(EDX)对所合成样品的晶体结构、形貌结构和化学成分分别进行了表征.利用荧光光谱仪和显微拉曼光谱仪研究了所合成样品的光致发光(PL)光谱和拉曼散射谱.光致发光第一次观察到了所合成的氧化亚锡在较宽波长范围(350～550 nm)内蓝紫光的发光带,分析认为这是由其表面的大量缺陷引起的,并结合拉曼光谱研究分析了其表面缺陷.此结构氧化亚锡的蓝光发光带可能在LED方面具有潜在应用.     

Novel Biological Functions of ZIF‐NP as a Delivery Vehicle: High Pulmonary Accumulation,Favorable Biocompatibility,and Improved Therapeutic Outcome

Though zeolitic imidazole framework (ZIF) emerges as an advanced functional material for small‐molecule delivery due to its unique features such as high loading and pH‐sensitive degradation, there are extreme short of knowledge regarding its biological functions. To qualify this category of delivery vehicle, ZIF‐8 nanoparticles (ZIF‐NPs) with or without cargo are engineered and comprehensively investigated in vitro and in vivo. Interestingly, ZIF‐NPs demonstrate strong bioadhesion but with limited internalization themselves, which enhance the membrane‐mediated ROS and are different from that of inorganic ZnO inducing mitochondria‐mediated reactive oxygen species (ROS) without biomembrane damage. Unexpected high concentration is found in lung, probably due to the particle size and distribution of the nanocarriers; however, the drug levels drop dramatically with time, revealing the fast degradation and elimination. At the given doses, ZIF‐NPs exhibit reasonably biosafety in animal tests as evidenced by their acceptable system and blood biocompatibilities, and minimal impacts on the liver and renal functions, immune cells, inflammatory factors, etc. ZIF‐NPs with fluorouracil loading (5F@ZIF‐NPs) significantly improve the therapeutic outcome of lung metastasis tumor in a nude mice model. Generally, ZIF‐NPs demonstrate unique biological functions in terms of bio–nano interaction, pulmonary accumulation, biocompatibility, and antitumor therapy, which endow them potential as the delivery vehicles.     

Synthesis,Electronic Structure,and Charge Transport Characteristics of Naphthalenediimide‐Based Co‐Polymers with Different Oligothiophene Donor Units

Naphthalenediimide (NDI)‐based polymers co‐polymerized with thienyl units are an interesting class of polymer semiconductors because of their good electron mobilities and unique film microstructure. Despite these properties, understanding how the extension of the thienyl co‐monomer affects charge transport properties remains unclear. With this goal in mind, we have synthesized a series of NDI derivatives of the parent poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) (P(NDI2OD‐T2)), which exhibited excellent electron mobility. The strategy comprises both the extension of the donor o‐conjugation length and the heteroatomic fusion of the thiophene rings. These newly synthesized compounds are characterized experimentally and theoretically vis‐à‐vis with P(NDI2OD‐T2) as the reference. UV‐vis data and cyclic‐voltammetry are adopted to assess the effect of the donor modification on the frontier energy levels and on the bandgap. Intra‐molecular polaronic effects are accounted for by computing the internal reorganization energy with density functional theory (DFT) calculations. Finally electrons and holes transport is experimentally investigated in field‐effect transistors (FETs), by measuring current‐voltage characteristics at variable temperatures. Overall we have identified a regime where inter‐molecular effects, such as the wavefunction overlap and the degree of energetic disorder, induced by the different donor group prevail over polaronic effects and are the leading factors in determining electrons mobility.     

Biological Assemblies Provide Novel Templates for the Synthesis of Biocomposites and Facilitate Cell Adhesion

Mechanical mismatch and the lack of interactions between implants and the natural tissue environment are major drawbacks in bone tissue engineering. Biomaterials mimicking the self‐assembly process and the composition of the bone matrix should provide new routes for fabricating biomaterials possessing novel osteoconductive and osteoinductive properties for bone repair. In the present study, bioinspired strategies are employed to design de novo self‐assembled chimeric protein hydrogels comprising leucine zipper motifs flanking a dentin matrix protein 1 domain, which is characterized as a mineralization nucleator. Results show that this chimeric protein could function as a hydroxyapatite nucleator in pseudo‐physiological buffer with the formation of highly oriented apatites similar to biogenic bone mineral. It could also function as an inductive substrate for osteoblast adhesion, promote cell surface integrin presentation and clustering, and modulate the formation of focal contacts. Such biomimetic “bottom‐up” construction with dual osteoconductive and osteoinductive properties should open new avenues for bone tissue engineering.     

Mechanical Properties of Conjugated Polymers and Polymer‐Fullerene Composites as a Function of Molecular Structure

Despite the importance of mechanical compliance in most applications of semiconducting polymers, the effects of structural parameters of these materials on their mechanical properties are typically not emphasized. This paper examines the effect of length of the pendant group on the tensile modulus and brittleness for a series of regioregular poly(3‐alkylthiophenes) (P3ATs) and their blends with a soluble fullerene derivative, PCBM. The tensile modulus decreases with increasing length of the alkyl side‐chain, from 1.87 GPa for butyl side chains to 0.16 GPa for dodecyl chains. The moduli of P3AT:PCBM blends films are greater than those of the pure polymers by factors of 2–4. A theoretical model produces a trend in the effect of alkyl side chain on tensile modulus that follows closely to the experimental measurements. Tensile modulus correlates with brittleness, as the strain at which cracks appear is 6% for P3BT and >60% for P3OT. Adhesion of the P3AT film to a polydimethylsiloxane (PDMS) substrate is believed to play a role in an apparent increase in brittleness from P3OT to P3DDT. The additive 1,8‐Diiodooctane (DIO) reduces the modulus of P3HT:PCBM blend by a factor of 3. These results could enable mechanically robust, flexible, and stretchable electronics.     

Synthesis and Evaluation of Novel Functional Polymers Derived from Renewable Jasmine Lactone for Stimuli-Responsive Drug Delivery

Instances of synthetic polymers obtained from renewable feedstock with the possibility of post-synthesis functionalization are scarce. Herein, the first ever synthesis and drug delivery application of amphiphilic block copolymer (mPEG-b-PJL) derived from renewable jasmine lactone with free allyl groups on the backbone is presented. The polymer is synthesized via facile ring-opening polymerization and subsequently, UV mediated thiol-ene click chemistry is utilized for post-functionalization. The introduction of hydroxyl, carboxyl, and amine functionality to mPEG-b-PJL polymer is successfully established. As a proof-of-concept demonstration, doxorubicin (DOX) is conjugated on hydroxyl-terminated polymer (mPEG-b-PJL-OH) via redox responsive disulfide linkage to obtain PJL-DOX. PJL-DOX is readily self-assembled into micelles with an average hydrodynamic size of ≈ 150 nm and demonstrates reduction-responsive DOX release. Micelles are evaluated in vitro for cytocompatibility and selective drug release in cancer cells (MDA-MB-231) using 10 mm glutathione as a reducing agent. Cytotoxicity and microscopy results confirm a redox-triggered release of DOX, which is further confirmed by flow cytometry. The introduction of these novel functional polymers can pave the way forward in designing polymer-drug conjugate-based smart nano-carriers.     

Covalent Layer‐by‐Layer Assembly of Conjugated Polymers and CdSe Nanoparticles: Multilayer Structure and Photovoltaic Properties

Hybrid thin films of conjugated polymers and CdSe nanoparticles have been fabricated by using a layer‐by‐layer (LbL) approach driven by covalent coupling reactions. This method permits facile covalent crosslinking of the polymer/nanoparticle interlayers in common organic solvents, which provides a general route for preparing robust and uniform functional thin films. The deposition process is linearly related to the number of bilayers as monitored by UV‐vis absorption spectroscopy and ellipsometry. Characterization of the multilayer structures has been carried out by fluorescence spectroscopy, X‐ray photoelectron spectroscopy (XPS), and grazing‐angle Fourier‐transform infrared spectroscopy (FTIR). Techniques such as atomic force microscopy (AFM) and scanning electron microscopy (SEM) have also been used. A preliminary application of the hybrid films in the development of organic photovoltaics is presented. Upon illumination with white light at 10 mW cm^–2, the self‐assembled multilayer films exhibit steady photocurrent responses with an overall optical‐to‐electrical power conversion efficiency of 0.71 %.     

Effect of Immobilized Nerve Growth Factor on Conductive Polymers: Electrical Properties and Cellular Response

The use of biologically active dopants in conductive polymers allows the polymer to be tailored for specific applications. The incorporation of nerve growth factor (NGF) as a co‐dopant in the electrochemical deposition of conductive polymers is evaluated for its ability to elicit specific biological interactions with neurons. The electrochemical properties of the NGF‐modified conducting polymers are studied by impedance spectroscopy and cyclic voltammetry. Impedance measurements at the neurobiologically important frequency of 1 kHz reveal that the minimum impedance of the NGF‐modified polypyrrole (PPy) film, 15 kΩ, is lower than the minimum impedance of peptide‐modified PPy film (360 kΩ). Similar results are found with NGF‐modified poly(3,4‐ethylene dioxythiophene) (PEDOT). The microstructure of the conductive polymer films is characterized by optical microscopy and electron microscopy and indicates that the NGF‐functionalized polymer surface topology is similar to that of the unmodified polymer film. Optical and fluorescence microscopy reveal that PC‐12 (rat pheochromacytoma) cells adhered to the NGF‐modified substrate and extended neurites on both PPy and PEDOT, indicating that the NGF in the polymer film is biologically active. Taken together these data indicate that the incorporation of NGF can modify the biological interactions of the electrode without compromising the conductive properties or the morphology of the polymeric film.     

Perovskite Single Crystals: Synthesis,Properties, and Applications

Perovskite single crystals have gained enormous attention in recent years due to their facile synthesis and excellent optoelectronic properties including the long carrier diffusion length, high carrier mobility, low trap density, and tunable absorption edge ranging from ultra-violet (UV) to near-infrared (NIR), which offer potential for applications in solar cells, photodetectors (PDs), lasers, etc. In this review, we summarized the synthesis, properties, and applications of organic-inorganic mixed and all-inorganic perovskite single crystals, particularly those through the solution synthesis approach. Challenges towards the crystal growth and stability with future perspectives were also briefly described at the end of this paper.     

Degradable Conjugated Polymers: Synthesis and Applications in Enrichment of Semiconducting Single‐Walled Carbon Nanotubes

Polymers which enrich semiconducting single‐walled carbon nanotubes (SWNTs) and are also removable after enrichment are highly desirable for achieving high‐performance field‐effect transistors (FETs). We have designed and synthesized a new class of alternating copolymers containing main‐chain fluorene and hydrofluoric acid (HF) degradable disilane for sorting and preferentially suspending semiconducting nanotube species. The results of optical absorbance, photoluminescence emission, and resonant Raman scattering show that poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐co‐1,1,2,2‐tetramethyl‐disilane] preferentially suspends semiconducting nanotubes with larger chiral angle (25°–28°) and larger diameter (1.03 nm–1.17 nm) (specifically (8,7), (9,7) and (9,8) species) present in HiPCO nanotube samples. Computer simulation shows that P1 preferentially interacts with (8,7) (semiconducting) over (7,7) (metallic) species, confirming that P1 selects larger diameter, larger chiral angle semiconducting tubes. P1 wrapped on the surface of SWNTs is easily washed off through degradation of the disilane bond of the alternating polymer main chain in HF, yielding “clean” purified SWNTs. We have applied the semiconducting species enriched SWNTs to prepare solution‐processed FET devices with random nanotube network active channels. The devices exhibit stable p‐type semiconductor behavior in air with very promising characteristics. The on/off current ratio reaches up to 15 000, with on‐current level of around 10 μA and estimated hole mobility of 5.2 cm² V^?1 s^?1.     

Semiconducting Polymers Based on Isoindigo and Its Derivatives: Synthetic Tactics,Structural Modifications,and Applications

The past few decades have witnessed the tremendous development of semiconducting polymers in electronic applications, which is inextricably related to the diversity of polymer structure. The change of polymer structure significantly influences the polymer packing, thin film morphology, and other optoelectronic properties, thus meeting the need for different device applications. With the development of synthetic chemistry and theoretical computation, many high-performance building blocks and polymers have emerged. Among them, isoindigo- and isoindigo derivatives-based polymers are widely studied in various fields of organic electronics, and many of them showed excellent properties. This review summarizes the synthetic tactics of isoindigo-derived monomers and polymers. Moreover, the structural modification strategies of polymers are discussed in detail, including the modification of isoindigo derivatives and the regulation of polymer type. Using isoindigo-derived polymers, various applications, such as organic field-effect transistors, chemical sensors, organic electrochemical transistors, organic phototransistors, organic photovoltaics, organic thermoelectrics, organic spin valves, and biophotonic applications, are introduced to illustrate the important effects of structural modification.     

Silver Doped with Acidic/Basic Polymers: Novel,Reactive Metallic Composites

We report the preparation and properties of metallopolymeric composites with acidic and basic properties. The composites are prepared via the recently developed method of entrapping organic molecules within metals. Specifically, we describe the entrapment of the polyacid Nafion or the polybase poly(vinylbenzyltrimethylammonium hydroxide) within silver. The resulting acidic or basic metallic composites decrease or increase, respectively, the pH of water through an ion‐exchange process. Furthermore, silver doped with Nafion can be employed as an acid catalyst, as shown for the pinacol–pinacolone rearrangement and for the dehydration of an alcohol. Characterization of these novel materials via microscopy and adsorption studies reveals a three‐level hierarchical structure: clusters of ≈ 10 μm in size built from ≈ 1 μm aggregates of ≈ 100 Å silver crystals. Thermogravimetric analysis of the entrapped polymers reveals a catalytic effect of the metal on this process. The two polymers are entrapped differently, and the differences are discussed. Applications ranging from ion‐exchange electrodes to bifunctional catalysts are envisaged.     

Covalent Organic Frameworks: Structures,Synthesis, and Applications

Covalent organic frameworks (COFs) are crystalline porous polymers formed by a bottom‐up approach from molecular building units having a predesigned geometry that are connected through covalent bonds. They offer positional control over their building blocks in two and three dimensions. This control enables the synthesis of rigid porous structures with a high regularity and the ability to fine‐tune the chemical and physical properties of the network. This Feature Article provides a comprehensive overview over the structures realized to date in the fast growing field of covalent organic framework development. Different synthesis strategies to meet diverse demands, such as high crystallinity, straightforward processability, or the formation of thin films are discussed. Furthermore, insights into the growing fields of COF applications, including gas storage and separations, sensing, electrochemical energy storage, and optoelectronics are provided.     

Synthesis,Structure Transformation,and Electrochemical Properties of Li2MgSi as a Novel Anode for Li‐lon Batteries

In this work, a novel hexagonal Li₂MgSi anode is successfully prepared through a hydrogen‐driven chemical reaction technique. Electrochemical tests indicate significantly improved cycling stability for the as‐synthesized Li₂MgSi compared with that of Mg₂Si. Ball‐milling treatment induces a polymorphic transformation of Li₂MgSi from a hexagonal structure to a cubic structure, suggesting that the cubic Li₂MgSi is a metastable phase. The post‐24‐h‐milled Li₂MgSi delivers a maximum capacity of 807.8 mAh g^?1, which is much higher than that of pristine Li₂MgSi. In particular, the post‐24‐h‐milled Li₂MgSi retains 50% of its capacity after 100 cycles, which is superior to cycling stability of Mg₂Si. XRD analyses correlated with CV measurements do not demonstrate the dissociation of metallic Mg and/or Li–Mg alloy involved in the lithiation of Mg₂Si for the Li₂MgSi anode, which contributes to the improved lithium storage performance of the Li₂MgSi anode. The findings presented in this work are very useful for the design and synthesis of novel intermetallic compounds for lithium storage as anode materials of Li‐ion batteries.     

白钨矿结构BiVO4的水热合成及其可见光催化性能

以Bi(NO3)3·5H2O和NH4VO3为原材料,采用水热法合成了BiVO4可见光催化材料,并采用XRD、SEM和UV-Vis等对合成产物的物相结构、形貌、光吸收性能以及光催化性能进行了研究。研究表明,反应体系的pH值对合成产物的物相结构具有重要的影响,在酸性和弱碱性条件下可获得具有不规则纳米片状形貌的单斜白钨矿结构BiVO4晶体。合成产物对波长小于525nm的光具有强烈的吸收。水热条件的不同直接影响着产物对甲基橙溶液的可见光催化降解性能,在Bi∶V比例为1∶1,同时pH值为3.08并于160℃下水热处理1h所合成的BiVO4晶体对甲基橙溶液具有最佳的可见光催化活性。     

Synthesis,Structure, Properties,and Applications of Bimetallic Nanoparticles of Noble Metals

Bimetallic nanoparticles of noble metals are of high interest in imaging, biomedical devices, including nanomedicine, and heterogeneous catalysis. Synthesis, properties, characterization, biological properties, and practical applicability of nanoparticles on the basis of platinum group metals and the coin metals Ag and Au are discussed, also in comparison with the corresponding monometallic nanoparticles. In addition to the parameters that are required to characterize monometallic nanoparticles (mainly size, size distribution, shape, crystallographic nature, surface functionalization, charge), further information is required for a full characterization of bimetallic nanoparticles. This concerns the overall elemental composition of a bimetallic nanoparticle population (ratio of the two metals) and the internal distribution of the elements in individual nanoparticles (e.g., the presence of homogeneous alloys, core–shell systems, and possible intermediate stages). It is also important to ensure that all particles are identical in terms of elemental composition, that is, that the homogeneity of the particle population is given. Macroscopic properties like light absorption, antibacterial effects, and catalytic activity depend on these properties. The currently available methods for a full characterization of bimetallic nanoparticles are discussed, and future developments in this field are outlined.     

Bioinspired Surfaces with Superamphiphobic Properties: Concepts,Synthesis, and Applications

Among diverse wetting phenomena in surface science, superamphiphobicity is regarded as one of the most special super‐antiwetting states. In this paper, a systematic summary is presented to cover the characterization of surface wettability, the construction techniques, and selected functional applications. With respect to fabrication techniques, the following three types of technology routes, viz., “pre‐texturing + post‐modifying,” “pre‐modifying + post‐texturing,” and in situ one‐step construction will be discussed. The merits and demerits of each technology route are discussed. It is vital to rationally design or adopt appropriate construction strategies in diverse conditions. Appropriately constructed superamphiphobic multifunctional surfaces can be applied in many fields, however, most have not been scaled‐up and utilized for practical applications due to some specific difficulties required to be resolved in the future. These challenges and further outlook for super‐antiwetting surfaces are discussed in this review.