Interplay between Energy-Level Position and Charging Effect of Manganese Phthalocyanines on an Atomically Thin Insulator

Understanding the energy-level alignment and charge transfer of organic molecules at large bandgap semiconductors is of crucial importance to optimize device performance in organic electronics. We have studied submonolayer coverage of manganese phthalocyanine (MnPc) on hexagonal boron nitride (h-BN) on Rh(111) as a model system by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). The adsorbed molecules show three distinctly different bias-dependent topographic signatures, which depend on their adsorption positions on the h-BN. Among these three types of MnPc, one shows pronounced charging because of the proximity of the highest occupied molecular orbital (HOMO) to the Fermi level on the decoupling h-BN substrate. The charging of the MnPc from its neutral to the MnPc⁺ state leads to a down shift of the Mn 3<i>d</i>-related orbital by 840 meV as determined from the difference in energy position between high- and low-bias charging. We find that the charging field is linearly related to the HOMO position with respect to the Fermi level, with a clear correlation to the adsorption orientations of the MnPc. Our results show how critically energy level alignment and field-induced charge transfer process can depend on adsorption configurations, even on an apparently low-interacting substrate like metal supported monolayer h-BN

Correction to Synthesis of β‑Halo-pyrrolidinones through a Tandem Sequence of 5‑Endo Halolactamization and C–H Oxidative Functionalization

Correction to Synthesis of β‑Halo-pyrrolidinones through a Tandem Sequence of 5‑Endo Halolactamization and C–H Oxidative Functionalizatio

Controlled Preparation of High Quality Bubble-Free and Uniform Conducting Interfaces of Vertical van der Waals Heterostructures of Arrays

Sharp and clean interfaces of van der Waals (vdW) heterostructures are highly demanded in two-dimensional (2D) materials-based devices. However, current assembly methods usually cause interfacial bubbles and wrinkles, hindering carrier interlayer transport. The preparation of a large-scale vdW heterostructure with a bubble-free interface is still a challenge. Although many efforts have been made to eliminate bubbles, the evolution processes of the interfacial bubbles are rarely studied. Here, the interface bubble formation and evolution of the transferred 2D materials and their vdW heterostructure are systemically studied by the atomic force microscopy (AFM) technique and high-resolution surface current mapping. A thermal annealing procedure is developed to reduce the number of bubbles and to improve the quality of interfaces. In addition, influences of the interface residues and nanosteps on bubble evolution are also discussed. Further, we develop the polystyrene (PS)-mediated polydimethyl­siloxane (PDMS) transfer technique to realize the high-quality transfer of heterostructure arrays. Finally, high-resolution surface current mapping results confirm that we can now produce highly uniform electrical conduction interfaces of heterojunctions. This study provides guidance for assembling high quality interfaces and paves the way for production of bubble-free heterostructure-based electronic devices with high performance and good uniformity

Evidence for the Role of Mast Cells in Cystitis-Associated Lower Urinary Tract Dysfunction: A Multidisciplinary Approach to the Study of Chronic Pelvic Pain Research Network Animal Model Study

<div><p>Bladder inflammation frequently causes cystitis pain and lower urinary tract dysfunction (LUTD) such as urinary frequency and urgency. Although mast cells have been identified to play a critical role in bladder inflammation and pain, the role of mast cells in cystitis-associated LUTD has not been demonstrated. Interstitial cystitis/bladder pain syndrome (IC/BPS) is a chronic and debilitating inflammatory condition of the urinary bladder characterized by the hallmark symptoms of pelvic pain and LUTD. In this study we investigated the role of mast cells in LUTD using a transgenic autoimmune cystitis model (URO-OVA) that reproduces many clinical correlates of IC/BPS. URO-OVA mice express the membrane form of the model antigen ovalbumin (OVA) as a self-antigen on the urothelium and develop bladder inflammation upon introduction of OVA-specific T cells. To investigate the role of mast cells, we crossed URO-OVA mice with mast cell-deficient <i>Kit</i>^<i>W-sh</i> mice to generate URO-OVA/<i>Kit</i>^<i>W-sh</i> mice that retained urothelial OVA expression but lacked endogenous mast cells. We compared URO-OVA mice with URO-OVA/<i>Kit</i>^<i>W-sh</i> mice with and without mast cell reconstitution in response to cystitis induction. URO-OVA mice developed profound bladder inflammation with increased mast cell counts and LUTD, including increased total number of voids, decreased mean volume voided per micturition, and decreased maximum volume voided per micturition, after cystitis induction. In contrast, similarly cystitis-induced URO-OVA/<i>Kit</i>^<i>W-sh</i> mice developed reduced bladder inflammation with no mast cells and LUTD detected. However, after mast cell reconstitution URO-OVA/<i>Kit</i>^<i>W-sh</i> mice restored the ability to develop bladder inflammation and LUTD following cystitis induction. We further treated URO-OVA mice with cromolyn, a mast cell membrane stabilizer, and found that cromolyn treatment reversed bladder inflammation and LUTD in the animal model. Our results provide direct evidence for the role of mast cells in cystitis-associated LUTD, supporting the use of mast cell inhibitors for treatment of certain forms of IC/BPS.</p></div

Mast cell-deficient URO-OVA/<i>Kit</i>^<i>W-sh</i> mice exhibited no significant changes in voiding habits after cystitis induction.

<p>At day 6 after cystitis induction URO-OVA mice (B), URO-OVA/<i>Kit</i>^<i>W-sh</i> mice (D), and mast cell-reconstituted URO-OVA/<i>Kit</i>^<i>W-sh</i> mice (F) were placed in micturition cages for 24-hour micturition recording (see <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0168772#pone.0168772.t002" target="_blank">Table 2</a>). The baseline voiding habits of URO-OVA (A), URO-OVA/<i>Kit</i>^<i>W-sh</i> (C), and mast cell-reconstituted URO-OVA/<i>Kit</i>^<i>W-sh</i> mice (E) were included for comparison. Data are shown as the amount (gram) of urine collected in 2-minite intervals during the 24-hour period. The results are representative of 5 mice for each of the three groups. The dark period is indicated by red lines.</p

Cromolyn treatment reverses bladder inflammation in URO-OVA mice after cystitis induction.

<p>Mice were treated with saline or cromolyn daily beginning one day before cystitis induction up to day 13. The bladders were collected at day 14 and processed for histological H&E staining (A), flow cytometric analysis of bladder infiltrating CD8⁺ T cells and CD8⁺Vα2⁺ T cells (B), and RT-PCR analysis of mRNAs for inflammatory factors IFN-γ, IL-6, TNF-α, NGF and substance P precursor (pre-SP) (C). GAPDH was used as an internal control. M, a 100 bp DNA marker. *<i>p</i><0.05. The images are representative of 8 bladders per group.</p

Changes in voiding habits after cystitis induction.

<p>Changes in voiding habits after cystitis induction.</p