Correlation between Interfacial Structures and Device Performance: The Double-Edged Sword Effect of Lead Iodide in Perovskite Solar Cells

The interfacial electronic structure of perovskite layers and transport layers is critical for the performance and stability of perovskite solar cells (PSCs). The device performance of PSCs can generally be improved by adding a slight excess of lead iodide (PbI₂) to the precursor solution. However, its underlying working mechanism is controversial. Here, we performed a comprehensive study of the electronic structures at the interface between CH₃NH₃PbI₃ and C₆₀ with and without the modification of PbI₂ using in situ photoemission spectroscopy measurements. The correlation between the interfacial structures and the device performance was explored based on performance and stability tests. We found that there is an interfacial dipole reversal, and the downward band bending is larger at the CH₃NH₃PbI₃/C₆₀ interface with the modification of PbI₂ as compared to that without PbI₂. Therefore, PSCs with PbI₂ modification exhibit faster charge carrier transport and slower carrier recombination. Nevertheless, the modification of PbI₂ undermines the device stability due to aggravated iodide migration. Our findings provide a fundamental understanding of the CH₃NH₃PbI₃/C₆₀ interfacial structure from the perspective of the atomic layer and insight into the double-edged sword effect of PbI₂ as an additive.     

Fluorous Tagged Peptides for Intracellular Delivery and Biomedical Imaging

Fluorous tagged peptides have shown promising features for biomedical applications such as drug delivery and multimodal imaging. The bioconjugation of fluoroalkyl ligands onto cargo peptides greatly enhances their proteolytic stability and membrane penetration via a proposed “fluorine effect”. The tagged peptides also efficiently deliver other biomolecules such as DNA and siRNA into cells via a co-assembly strategy. The fluoroalkyl chains on peptides with antifouling properties enable efficient gene delivery in the presence of serum proteins. Besides intracellular biomolecule delivery, the amphiphilic peptides can be used to stabilized perfluorocarbon-filled microbubbles for ultrasound imaging. The fluorine nucleus on fluoroalkyls provides intrinsic probes for background-free magnetic resonance imaging. Labeling of fluorous tags with radionuclide ¹⁸F also allows tracing the biodistribution of peptides via positron emission tomography imaging. This mini-review will discuss properties and mechanism of the fluorous tagged peptides in these applications.     

Thermal and environmental stability of poly(4-ethynyl-p-xylylene-co-p-xylylene) thin films

The aim of this paper was to test the thermal and environmental stability of poly(4-ethynyl-p-xylyleneco-p-xylylene) thin films prepared by chemical vapor deposition(CVD) and to optimize the reaction conditions of the polymer.Fourier transformed infrared spectroscopy(FTIR),thermogravimetric analysis(TGA) and fluorescence microscopy were employed to investigate the stability of the reactive polymer coatings in various environmental conditions.Chemical reactivity of the thin films were then tested by Huisgen 1,3-dipolar cycloaddition reaction(‘‘click' reaction).The alkyne functional groups on poly(4-ethynyl-p-xylylene-co-p-xylylene) thin films were found to be stable under ambient storage conditions and thermally stable up to 100 8C when annealed at 0.08 Torr in argon.We also optimized the click reaction conditions of azide-functionalized molecules with poly(4-ethynyl-p-xylylene-co-p-xylylene).The best reaction result was achieved,when copper concentration was 0.5 mmol/L,sodium ascorbate concentration to copper concentration was 5:1.In contrast,the azide concentration and temperature had no obvious effect on the surface reaction.     

Graphene Quantum Dots Assembled with Metalloporphyrins for “Turn on” Sensing of Hydrogen Peroxide and Glucose

Noncovalent and multifunctional hybrids have been generated via π–π stacking and electrostatic interactions by combining the nanometer‐scale graphene structure of graphene quantum dots (GQDs) with Fe^III 5,10,15,20‐tetrakis(1‐methyl‐4‐pyridyl)porphine (FeTMPyP). The inner filter effect (IFE) of FeTMPyP on the GQDs results in substantial PL quenching of the GQDs. The quenched PL of GQDs by the FeTMPyP can be switched back “on” in response to the reaction between FeTMPyP and H₂O₂, which causes rupture of the cyclic tetrapyrrolic nucleus with consequential loss of iron from FeTMPyP, and then proceeds further to produce colorless dipyrroles and monopyrroles. This “turn on” system can be applied for simple and convenient H₂O₂ sensing and can be further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) through the oxidation of glucose and formation of H₂O₂. Because of the inherent synthetic control available for the design of metalloporphyrins, the GQDs‐based optical sensing approach described here has the potential to be highly versatile for other target analytes.     

High capacity and cycling stability of poly(diaminoanthraquinone) as an organic cathode for rechargeable lithium batteries

Poly(1,5‐diaminoanthraquinone) is synthesized by oxidative polymerization of diaminoanthraquinone monomers and investigated as an organic host for Li‐storage reaction. Benefiting from its high density of redox‐active, Li⁺‐associable benzoquinone groups attached to conducting polyaniline backbones, this polymer undergoes its cathodic reaction predominately through Li⁺‐insertion/extraction processes, delivering a very high reversible capacity of 285 mAh g^?1. In addition, the PDAQ polymer cathode exhibits an excellent rate capability (125 mAh g^?1 at 800 mA g^?1) and a considerable cyclability with a capacity retention of ～160 mAh g^?1 over 200 cycles, possibly serving as a sustainable, high capacity Li⁺ host cathode for Li‐ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 235–238     

Stereochemical determination of tetrahydropyran-substituted xanthones from fungus Chaetomium murorum

Chaetoxanthone D (1), a new tetrahydropyran-substituted xanthone originated from polyketide pathway, together with the four known natural products chaetoxanthone C (2), alternariol methyl ether (3), alternariol (4) and 2,5-dimethyl-7-hydroxychromone (5) was isolated from a strain of Chaetomium murorum. The structures of these compounds were elucidated based on extensive spectroscopic analyses. The absolute configurations of 1 and 2 were determined by using quantum chemical electronic circular dichroism (ECD) calculations.     

Photo‐responsive amphiphilic poly(α‐hydroxy acids) with pendent o‐nitrobenzyl ester constructed via copper‐catalyzed azide‐alkyne cycloaddition reaction

Photo‐responsive block copolymer mPEG‐b‐poly(Tyr)‐g‐NB was prepared by introduction of o‐nitrobenzyl ester group into the side chain of amphiphilic poly(ethylene glycol)‐b‐poly(α‐hydroxy acids) (mPEG‐b‐poly(Tyr)) containing pendent alkynyl group via copper‐catalyzed azide‐alkyne cycloaddition reaction. The amphiphilic mPEG‐b‐poly(Tyr) was synthesized via the ring‐opening polymerization of O‐carboxyanhydrides, with monomethoxy poly(ethylene glycol) (mPEG) as macroinitiator. The molecular structure, self‐assembly, and photo‐controlled release of the obtained mPEG‐b‐poly(Tyr)‐g‐NB were thoroughly investigated. mPEG‐b‐poly(Tyr)‐g‐NB could self‐assemble into spherical micelles in water and showed disassembly under UV light irradiation, which was demonstrated by means of UV‐vis spectroscopy, scan electron microscopes, and dynamic light scattering measurement. Fluorescence emission measurements demonstrated that Nile red, encapsulated by micelles, can be released upon UV irradiation. This study provides a convenient way to construct smart poly(α‐hydroxy acids)‐based nanocarriers for controlled release of hydrophobic drugs. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrolytic Macrocyclizations: Scalable Synthesis of a Diazonamide‐Based Drug Development Candidate

An electrochemical method to synthesize the core macrolactam of diazonamides is described. Large ring‐forming dehydrogenation is initiated by anodic oxidation at a graphite surface. The reaction requires no tailoring of the substrate and occurs at ambient temperature in aqueous DMF in an undivided cell open to air. This unique chemistry has enabled a concise, scalable preparation of DZ‐2384; a refined analog of diazonamide A slated for clinical development as a cancer therapeutic.     

双功能[Sn,Al]-Beta分子筛一步催化葡萄糖生成5-羟甲基糠醛

以部分脱铝的Beta分子筛为母体,采用同晶置换法将Sn植入骨架制备双功能[Sn,Al]-Beta分子筛,并应用于葡萄糖一步催化生成5-羟甲基糠醛(5-HMF)反应中.样品中Sn与Al的含量通过酸洗的浓度和酸洗的时间以及SnCl4处理的时间来控制.由于骨架中有与Al相关为B酸位,和Sn相关的L酸位,[Sn,Al]-Beta可作为一种双功能的固体酸催化剂.优化了[Sn,Al]-Beta催化葡萄糖一步催化生成5-HMF的反应参数,在最优Sn/Al比条件下,葡萄糖转化率为60.0%,5-HMF选择性为62.1%.     

Morphological and dimensional control via assembly of polyaniline crystals

A facile and general route to a new generation of polyaniline(PANI)-citric acid(CA) crystals such as 2D nanoplates, 2D nanosheets and 3D microrods self-assembled by the π-π stacking interaction is reported. Dramatic, 3D rectangular shaped microrods and 2D nanosheets are single crystals indicated by SAED patterns and HRTEM images. Moreover, the method does not depend on any specific equipment or heating, cooling and complex procedures. The novel polyaniline crystals will be useful for next generation organic electronics such as nano-transistors.