Bridging the Bays, Both Ways: A Janus Butterfly-Shaped Intense NIR-Emitting Terrylene Diimide.

Molecules with intense near-IR (NIR) emission are beneficial for modern applications such as night vision, bio-imaging etc. However, elaborate synthetic manipulations make them demanding to accomplish. Herein, we present a simple yet exciting strategy to obtain novel Janus butterfly-shaped terrylene diimide derivatives with carbazole wings having absorption and intense emission in the NIR. Especially, unsymmetrically substituted terrylene diimides (TDIs) have been observed to have impressive emission quantum yields (up to 93 %), highest for this class of compounds. Minimal structural distortion as evidenced from structural characterization has been shown to correlate with these observations. Also, a novel two-tiered TDI-carbazole having an intense emission at 897 nm is also reported. Our strategy demonstrates that efficient near-IR luminophores can be achieved via precise functionalization.

The Making of a Clinical Ethicist: A Personal Tribute to Al Jonsen.

In this account, the author shares her long-standing personal and professional relationship with her mentor, Albert R. Jonsen, PhD, a prominent figure in the history of bioethics.

Corrole-BODIPY Dyad as Small-Molecule Donor for Bulk Heterojunction Solar Cells.

Dyes based on charge-transfer (CT) characteristics are attractive candidates for organic photovoltaics due to their intense and broad absorption window. In these molecular frameworks, electron-rich donors and electron-deficient acceptors are covalently linked to achieve an effective CT process. Corrole, a tetrapyrrolic congener of porphyrin, is an excellent example of an electron-rich molecule with a large molar extinction coefficient. BODIPY, on the other hand, is a well-known electron-deficient bypyrrolic boron difluoride complex with intense absorption complementary to the corrole. A combination of these two structural motifs should result in a dyad having a wide absorption window, which will be suitable for organic photovoltaics. Herein, a corrole derivative has been envisaged as an efficient donor for solution-processed bulk heterojunction solar cells with PC71BM as an acceptor for the first time. The current molecule exhibits broad absorption in the visible range in solution as well as in thin films, with a high molar extinction coefficient and a low band gap of 1.79 eV. Frontier molecular orbital energy levels were found to be complementary to those of the well-known acceptor PC71BM. The optimized devices based on Cor-BODIPY:PC71BM showed a high power conversion efficiency (PCE) of 6.6% with Jsc = 11.46 mA/cm2, Voc = 0.90 V, and FF = 0.61. A remarkable value of incident photon-to-current conversion efficiency (IPCE) of 61% has also been observed.

Metal-free Annulation at the Ortho- and Bay-Positions of Perylene Bisimide Leading to Lateral π-Extension with Strong NIR Absorption.

A novel ortho/ bay annulation reaction of perylene bisimide (PBI) has been explored in a single step synthetic procedure using perylene bisimide 1 and 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) in the absence of any metal catalyst. The single crystal solid-state X-ray diffraction structure showed a distorted framework of DBU-fused PBI 2. Compound 2 exhibited intense near-infrared absorption up to 950 nm. Reversible protonation and deprotonation accompany drastic changes in the photophysical characteristics. Further, the reaction of perylene biscarboxyanhydride with DBU offered a caprolactam ring-substituted perylene bisimide 3.

Selective Imaging of Lipids in Adipocytes by Using an Imidazolyl Derivative of Perylene Bisimide.

A small molecule, perylene bisimide imidazolyl derivative (PBI-ID), has been identified and developed as a specific marker for labelling multifunctional fat bodies in various organisms, including Drosophila and mammalian adipocytes. Interestingly, PBI-ID neither labels the plasma membranes nor cell nuclei by trapping into it. A remarkable feature of unbound PBI-ID is diminished fluorescence, which reduces the background emission noise, while contrasting the bound state effectively.

Implementing California's Law on Assisted Dying.

On October 5, 2015, Governor Jerry Brown approved bill ABX2 15, the End of Life Option Act, making California the fifth state in the country to allow physician-assisted dying. The law was modeled after Oregon's 1997 Death with Dignity Act. When the legislative special session ended on March 10, 2016, California health care providers had only ninety days to respond to the state mandate before the law would take effect, on June 9, 2016. Experience with the law so far suggests several challenges with implementation.

Highly fluorescent 1,2-dihydropyrimido[1,6-α]indole: an efficient metal free synthesis and photophysical study.

A metal free route to highly fluorescent 1,2-dihydropyrimido[1,6-α]indole derivatives has been developed via base catalyzed aldol followed by the Mannich reaction of indole-2-carboxaldehyde with ethyl N-arylideneglycinate at room temperature. This transformation consists of the sequential formation of two new bonds to afford highly functionalized pyrimidoindole derivatives under mild reaction conditions. Photophysical properties of the products have also been reported.

The Case.

Mr. Hope is a 40-year-old man who has resided at a long-term care facility for the past 10 years. The resident was originally admitted to the nursing home for his inability to care for himself secondary to advanced AIDS and complications from progressive multifocal leukoencephalopathy (PML). When he initially arrived at the nursing home, Mr. Hope was able to smile and appeared to respond to some of the staff's requests. Now, he responds by wincing when told that procedures are being performed and especially when he is told that he has to go back to the hospital. He is extremely contracted, with his arms wedded to his chest in a crossed fashion, as though he is protecting himself from blows. Mr. Hope's family consists of a partner, his parents, and one sibling. Numerous conversations have been had with the family, and according to the facility staff, "they persist in continuing aggressive measures with the hope that the patient will wake up and walk out of the facility." What had been frequent visits to the local hospital ER have increased substantially in the last few months, for what appear to be new infections and pneumonia. During most visits he ultimately spends a few days in the hospital to resolve his acute issues. On his most recent return to the long-term care facility, the medical staff approached the family about Mr. Hope's code status. The family continues to insist on a full code status and that he be provided every opportunity to "live." The staff is very concerned about Mr. Hope and his welfare. Many of the nursing staff have grown attached to him over the years, and watching him deteriorate has been distressing. They see part of their role as being his advocate and supporting him in ways that his own family has not. They express very strong reservations about performing CPR on Mr. Hope because they think it will be ineffective and they will have to break his upper extremities in order to gain access to his chest for resuscitation. The staff has contacted the ethics consultation service with the request that Mr. Hope needs protection and that his own family is not making the best decisions for him.

The Case.

KS is a 76-year-old Burmese woman who presented to the hospital with right-sided weakness that had begun two days prior. Although KS had been diagnosed earlier with dementia and had a medical history of stroke, she was living at a nursing home and was able to walk on her own and use her right arm to feed herself. Since her last stroke three years ago, she had also developed aphasia, and her speech has been minimal. During her current hospitalization, KS was found to have a cerebral hemorrhage, but after consultation with neurosurgery, the team determined that no medical interventions were available, and a higher level of care was not required. She also presented with other medical conditions, including severe hypertension, chronic kidney disease, and depression. The patient's blood pressure has remained high. She has now failed a swallow evaluation and is refusing the insertion of a nasogastric feeding tube. The patient has a younger sister who believes, from a cultural perspective, that only the patient should make her medical decisions. As a result, she feels helpless in assisting the team. The medical team has asked for an ethics consultation to direct the patient's care and to guide decisionmaking.

Novel azepino-perylenebisimides: synthesis, structure, and properties.

The first example of an azepine ring formation by counterintuitive nucleophilic participation of DBU was observed at the sterically crowded bay area of electron-deficient perylenebisimide (PBI). This is also a rare example of the formation of a seven-membered ring via two consecutive C-N bond formations in a single step. Azepino-PBIs reveal panchromatic absorption covering the whole visible region. Further novelty of these PBIs lies within the fact that their photophysical characteristics can easily be modulated by suitable substituents.

Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides: synthesis, structure, and photophysical properties.

Perylene bisimide (PBI) derivatives with various alkynyl-phenyl substituents at a single bay position have been synthesised by Sonogashira coupling. NMR spectroscopic studies reveal the unsymmetric nature of the dyads. All of the dyads undergo two reversible reductions, which demonstrates their structural and electrochemical rigidity. The synthesised dyads show a remarkable redshift in their absorption maxima and sharp vibronic progression. Electron-rich substituents facilitate efficient charge transfer from the substituent HOMO to the electron-deficient PBI core. The most interesting spectral signatures were exhibited by a PBI with a strongly electron-donating ethynyl(dimethylaminophenyl) substituent. The steady-state features of this PBI showed a broad absorption that covered almost the whole visible region with no emission. A twisted intramolecular charge-transfer (TICT) process, related to the rotational motion of ethynyl(dimethylaminophenyl) PBI, was also demonstrated. Computational investigations shed light on the coplanarity of the various substituents with respect to the PBI core; the PBI core itself remains flat without any noticeable deformation even after mono-functionalisation. This illustrates that mono-functionalisation exerts meagre steric hindrance on the bay positions relative to disubstituted analogues. Despite several previous reports on the structural characterisation of 1,7-disubstituted PBI derivatives, we present the first structural characterisation of a mono-bay ethynyl-phenyl substituted PBI. The solid-state structure of the phenyl derivative has a flat PBI core without any noticeable steric constraints from the substituents, as predicted. In contrast, single-crystal X-ray analysis for the mono-bromo bay-substituted PBI shows that the bromine substituent is not in the plane of the PBI core.