Anisotropic gold nanoplates (NPLs) have raised the interesting possibility that their reduced geometrical symmetry allows fine tuning of their optical properties associated with the excitation of localized surface plasmon resonances (LSPRs). Recent developments have greatly improved LSPR tunability by utilizing the spatial distribution of LSPR modes. However, the nanoscale interplay between defect-induced mechanical strain and the spatial variation of LSPR modes remains poorly understood. In this work, the combination of high spatial- and spectral-resolution mapping of LSPR modes and nanoscale strain mapping using aberration-corrected transmission electron microscopy are applied to investigate the nanoscale distribution of LSPR modes in an ultrathin single hexagonal gold NPL and the effect of defect-induced strains on its LSPR properties. The electron energy-loss spectral maps reveal four distinct LSPR components and intensity distributions of all LSPR modes in a hexagonal gold NPL. Furthermore, the strain maps provide experimental evidence that the tensile strain field induced by a Z-shaped faulted dipole is responsible for the asymmetric distribution of LSPR intensity in a hexagonal gold NPL.

Despite the tremendous attempts to improve the solar-to-hydrogen conversion efficiency of TiO2 based photoelectrochemical photoanode, further progress is still needed to utilize the TiO2 as the promising photoanode materials. Herein, a highly enhanced photoanode composed of the nanostructured In2S3/TiO2 is synthesized. The photocurrent density approximately 3.5 times (2.74 mA cm−2) as high as the pristine TiO2 was obtained due to the improved carrier concentration and fast charge separation. The incident photon-to-current efficiency shows a 65.8 % while pristine TiO2 nanorods shows only 24.7 % of efficiency. Further studies on the carrier lifetime and band position were performed and clarify the generation of type-Ⅱ heterojunction between the In2S3 nanoparticles and TiO2 nanorod arrays. This study proposes the methodologies and the theoretical evidence for achieving significant improvements in the TiO2 based photoanode. Moreover, this study's all-solution-based process provides the facile and scalable method for the highly enhanced photoelectrode and allows environmentally friendly production.

A large fraction of metalloenzymes harbors multiple metal-centers that are electronically and/or functionally arranged within their proteinaceous environments. To explore the orchestration of inorganic and biochemical components and to develop bioinorganic catalysts and materials, we have described selected examples of artificial metalloproteins having multiple metallocofactors that were grouped depending on their initial protein scaffolds, the nature of introduced inorganic moieties, and the method used to propagate the number of metal ions within a protein. They demonstrated that diverse inorganic moieties can be selectively grafted and modulated in protein environments, providing a retrosynthetic bottom-up approach in the design of versatile and proficient biocatalysts and biomimetic model systems to explore fundamental questions in bioinorganic chemistry.

Three-dimensional (3D) visualization of tumor vasculature is a key factor in accurate evaluation of RNA interference (RNAi)-based antiangiogenic nanomedicine, a promising approach for cancer therapeutics. However, this remains challenging because there is not a physiologically relevant in vitro model or precise analytic methodology. To address this limitation, a strategy based on 3D microfluidic angiogenesis-on-a-chip and 3D tumor vascular mapping was developed for evaluating RNAi-based antiangiogenic nanomedicine. We developed a microfluidic model to recapitulate functional 3D angiogenic sprouting when co-cultured with various cancer cell types. This model enabled efficient and rapid assessment of antiangiogenic nanomedicine in treatment of hyper-angiogenic cancer. In addition, tissue-clearing-based whole vascular mapping of tumor xenograft allowed extraction of complex 3D morphological information in diverse quantitative parameters. Using this 3D imaging-based analysis, we observed tumor sub-regional differences in the antiangiogenic effect. Our systematic strategy can help in narrowing down the promising targets of antiangiogenic nanomedicine and then enables deep analysis of complex morphological changes in tumor vasculature, providing a powerful platform for the development of safe and effective nanomedicine for cancer therapeutics.

There have been many engineered Cas9 variants that were developed to minimize unintended cleavage of off-target DNAs, but detailed mechanism for the way they regulate the target specificity through DNA:RNA heteroduplexation remains poorly understood. We used single-molecule FRET assay to follow the dynamics of DNA:RNA heteroduplexation for various engineered Cas9 variants with respect to on-target and off-target DNAs. Just like wild-type Cas9, these engineered Cas9 variants exhibit a strong correlation between their conformational structure and nuclease activity. Compared with wild-type Cas9, the fraction of the cleavage-competent state dropped more rapidly with increasing base-pair mismatch, which gives rise to their enhanced target specificity. We proposed a reaction model to quantitatively analyze the degree of off-target discrimination during the successive process of R-loop expansion. We found that the critical specificity enhancement step is activated during DNA:RNA heteroduplexation for evoCas9 and HypaCas9, while it occurs in the post-heteroduplexation stage for Cas9-HF1, eCas9, and Sniper-Cas9. This study sheds new light on the conformational dynamics behind the target specificity of Cas9, which will help strengthen its rational designing principles in the future.

This paper investigates humidity sensing characteristics of a silicon metal oxide semiconductor field effect transistor (Si MOSFET)-based humidity sensor having horizontal floating-gate (FG) interdigitated with control-gate (CG). The sensing material of the humidity sensor is graphene quantum dots (GQDs), deposited locally on the interdigitated CG-FG area by an ink-jet printing method using a small amount of the GQDs solution. The humidity sensing characteristics of the sensor are measured as a parameter of relative humidity (RH). The response of the humidity sensor is 78 % to the humid air of 81.3 % RH. We also adopt a pulsed pre-bias method to improve the response and recovery characteristics of the humidity sensor. The response and recovery characteristics of the sensor can be improved 30 % and 40 % respectively by applying a pre-bias of 2 V and -1 V to the CG. In all relative humidity ranges, the FET-type humidity sensor has highly stable and reproducible characteristics in long-term measurements for 5 months.

Glutathione (GSH) is the most abundant biological thiol and involved in antioxidant defense systems in human cells. Lack of GSH increases the risk of oxidative stress, resulting in the progression of cancer. Therefore, a selective detection method for GSH is highly required. Herein, we report phosphorescent and electrochemiluminescent dual sensors (1-3) based on iridium complexes for the selective detection of GSH. These sensors have a 1,10-phenanthroline-5,6-dione (pdo) ancillary ligand as a common reaction site for GSH. Reduction of the pdo moiety to 1,10-phenanthroline-5,6-diol (phen(OH)2) upon reaction of sensors with GSH triggered fluorescence turn-on response and electrochemiluminescence turn-off response with high selectivity for GSH. Sensing mechanisms were elucidated by DFT calculations and cyclic voltammetry. Sensor 1 was successfully applied to determination of GSH concentrations in human serum samples by ECL methods.

Novel polymeric MacMillan catalysts were prepared from modified chiral imidazolidin-4-one monomers via sulfur(VI) fluoride exchange chemistry. The resulting polysulfates containing chiral imidazolidin-4-one units could be employed as polymeric organocatalysts for the asymmetric Diels–Alder reaction. With the use of these polysulfate catalysts, sufficient catalytic activity and enantioselectivity were obtained, which were similar to those obtained by monomeric catalysts in a homogeneous catalytic reaction. In addition, the polysulfate catalysts could be recovered and reused five times without a considerable loss of activity and selectivity.

Cyanine (Cy) dyes are among the most useful organic fluorophores that have found a wide range of applications in single-molecule and super-resolution imaging as well as in other biophysical studies. However, recent observations that blueshifted derivatives of Cy dyes are formed via photoconversion have raised concerns as to the potential artifacts in multicolor imaging. Here, we report the mechanism for the photoconversion of Cy5 to Cy3 that occurs upon photoexcitation during fluorescent imaging. Our studies show that the formal C2H2 excision from Cy5 occurs mainly through an intermolecular pathway involving a combination of bond cleavage and reconstitution while unambiguously confirming the identity of the fluorescent photoproduct of Cy5 to be Cy3 using various spectroscopic tools. The carbonyl products generated from singlet oxygen-mediated photooxidation of Cy5 undergo a sequence of carbon–carbon bond-breaking and -forming events to bring about the novel dye-to-dye transformation. We also show that the deletion of a two-methine unit from the polymethine chain, which results in the formation of blueshifted products, commonly occurs in other cyanine dyes, such as Alexa Fluor 647 (AF647) and Cyanine5.5. The formation of a blueshifted congener dye can obscure the multicolor fluorescence imaging, leading to misinterpretation of the data. We demonstrate that the potentially deleterious photoconversion, however, can be exploited to develop a new photoactivation method for high-density single-particle tracking in a living cell without using UV illumination and cell-toxic additives.

Heat stress adversely affects an array of molecular and cellular events in plant cells, such as denaturation of protein and lipid molecules and malformation of cellular membranes and cytoskeleton networks. Genome organization and DNA integrity are also disturbed under heat stress, and accordingly, plants have evolved sophisticated adaptive mechanisms that either protect their genomes from deleterious heat-induced damages or stimulate genome restoration responses. In particular, it is emerging that DNA damage responses are a critical defense process that underlies the acquirement of thermotolerance in plants, during which molecular players constituting the DNA repair machinery are rapidly activated. In recent years, thermotolerance genes that mediate the maintenance of genome integrity or trigger DNA repair responses have been functionally characterized in various plant species. Furthermore, accumulating evidence supports that genome integrity is safeguarded through multiple layers of thermoinduced protection routes in plant cells, including transcriptome adjustment, orchestration of RNA metabolism, protein homeostasis, and chromatin reorganization. In this review, we summarize topical progresses and research trends in understanding how plants cope with heat stress to secure genome intactness. We focus on molecular regulatory mechanisms by which plant genomes are secured against the DNA-damaging effects of heat stress and DNA damages are effectively repaired. We will also explore the practical interface between heat stress response and securing genome integrity in view of developing biotechnological ways of improving thermotolerance in crop species under global climate changes, a worldwide ecological concern in agriculture.