17 research outputs found
Cascade Synthesis of Fenpiprane and Related Pharmaceuticals via Rhodium-Catalyzed Hydroaminomethylation
A novel rhodium catalytic system with Naphos as ligand was developed for an efficient hydroaminomethylation of 1,1-diphenylethene under relatively mild conditions. This will allow for an atom-economic and environmentally benign synthesis of fenpiprane and related pharmaceuticals
Rhodium-Catalyzed Highly Regioselective Hydroaminomethylation of Styrenes with Tetraphosphorus Ligands
The highly linear-selective hydroaminomethylation of styrenes is very challenging. Herein, an efficient, highly chemoselective, and linear-selective hydroaminomethylation (l/b up to >99:1) of styrenes using Rh(nbd)<sub>2</sub>SbF<sub>6</sub> with a pyrrole-based 3,3′,5,5′-substituted tetraphosphorus ligand is documented. This is in sharp contrast to other available processes leading to branched amines and provides a novel atom economic approach to 3-arylpropylamines
Cascade Synthesis of Fenpiprane and Related Pharmaceuticals via Rhodium-Catalyzed Hydroaminomethylation
A novel rhodium catalytic system with Naphos as ligand was developed for an efficient hydroaminomethylation of 1,1-diphenylethene under relatively mild conditions. This will allow for an atom-economic and environmentally benign synthesis of fenpiprane and related pharmaceuticals
Exploration of Novel Botanical Insecticide Leads: Synthesis and Insecticidal Activity of β‑Dihydroagarofuran Derivatives
The
discovery of novel leads and new mechanisms of action is of
vital significance to the development of pesticides. To explore lead
compounds for botanical insecticides, 77 β-dihydroagarofuran
derivatives were designed and synthesized. Their structures were mainly
confirmed by <sup>1</sup>H NMR, <sup>13</sup>C NMR, DEPT-135°,
IR, MS, and HRMS. Their insecticidal activity was evaluated against
the third-instar larvae of Mythimna separata Walker, and the results indicated that, of these derivatives, eight
exhibited more promising insecticidal activity than the positive control,
celangulin-V. Particularly, compounds <b>5.7</b>, <b>6.6</b>, and <b>6.7</b> showed LD<sub>50</sub> values of 37.9, 85.1,
and 21.1 μg/g, respectively, which were much lower than that
of celangulin-V (327.6 μg/g). These results illustrated that
β-dihydroagarofuran ketal derivatives can be promising lead
compounds for developing novel mechanism-based and highly effective
botanical insecticides. Moreover, some newly discovered structure–activity
relationships are discussed, which may provide some important guidance
for insecticide development
Assessing the Influence of Side-Chain and Main-Chain Aromatic Benzyltrimethyl Ammonium on Anion Exchange Membranes
3,3′-diÂ(4″-methyl-phenyl)-4,4′-difluorodiphenyl
sulfone (DMPDFPS), a new monomer with two pendent benzyl groups, was
easily prepared by Suzuki coupling reaction in high yield. A series
of side-chain type ionomers (PAES-Qs) containing pendant side-chain
benzyltrimethylammonium groups, which linked to the backbone by alkaline
resisting conjugated C–C bonds, were synthesized via polycondensation,
bromination, followed by quaternization and alkalization. To assess
the influence of side-chain and main-chain aromatic benzyltrimethylammonium
on anion exchange membranes (AEMs), the main-chain type ionomers (MPAES-Qs)
with the same backbone were synthesized following the similar procedure.
GPC and <sup>1</sup>H NMR results indicate that the bromination shows
no reaction selectivity of polymer configurations and ionizations
of the side-chain type polymers display higher conversions than that
of the main-chain type ones do. These two kinds of AEMs were evaluated
in terms of ion exchange capacity (IEC), water uptake, swelling ratio,
λ, volumetric ion exchange capacity (IEC<sub>Vwet</sub>), hydroxide
conductivity, mechanical and thermal properties, and chemical stability,
respectively. The side-chain type structure endows AEMs with lower
water uptake, swelling ratio and λ, higher IEC<sub>Vwet</sub>, much higher hydroxide conductivity, more robust dimensional stability,
mechanical and thermal properties, and higher stability in hot alkaline
solution. The side-chain type cationic groups containing molecular
configurations have the distinction of being practical AEMs and membrane
electrode assemblies of AEMFCs
Porphyrin Cosensitization for a Photovoltaic Efficiency of 11.5%: A Record for Non-Ruthenium Solar Cells Based on Iodine Electrolyte
Dye-sensitized
solar cells (DSSCs) are promising for utilizing
solar energy. To achieve high efficiencies, it is vital to synergistically
improve the photocurrent (<i>J</i><sub>sc</sub>) and the
photovoltage (<i>V</i><sub>oc</sub>). In this respect, conjugation
framework extension and cosensitization are effective for improving
the absorption and the <i>J</i><sub>sc</sub>, which, however,
is usually accompanied by undesirably decreased <i>V</i><sub>oc</sub>. Herein, based on a rationally optimized porphyrin
dye, we develop a targeted coadsorption/cosensitization approach for
systematically improving the <i>V</i><sub>oc</sub> from
645 to 727, 746, and 760 mV, with synergistical <i>J</i><sub>sc</sub> enhancement from 18.83 to 20.33 mA cm<sup>–2</sup>. Thus, the efficiency has been dramatically enhanced to 11.5%, which
keeps the record for nonruthenium DSSCs using the I<sub>2</sub>/I<sub>3</sub><sup>–</sup> electrolyte. These results compose an
alternative approach for developing highly efficient DSSCs with relatively
high <i>V</i><sub>oc</sub> using traditional iodine electrolyte
Comparative Study on Pyrido[3,4‑<i>b</i>]pyrazine-Based Sensitizers by Tuning Bulky Donors for Dye-Sensitized Solar Cells
Dye-sensitized
solar cells (DSSCs) with cobalt electrolytes have
gained increasing attention. In this Research Article, two new pyridoÂ[3,4-<i>b</i>]Âpyrazine-based sensitizers with different cores of bulky
donors (indoline for <b>DT-1</b> and triphenylamine for <b>DT-2</b>) were designed and synthesized for a comparative study
of their photophysical and electrochemical properties and device performance
and were also analyzed through density functional theory calculations.
The results of density function theory calculations reveal the limited
electronic communication between the biphenyl branch at the cis-position
of <i>N</i>-phenylindoline and the indoline core, which
could act as an insulating blocking group and inhibit the dye aggregation
and charge recombination at the interface of TiO<sub>2</sub>/dye/electrolyte.
As expected, DSSCs based on <b>DT-1</b> with cobalt redox electrolyte
gained a higher photoelectric conversion efficiency of 8.57% under
standard AM 1.5 G simulated sunlight, with <i>J</i><sub>sc</sub> = 16.08 mA cm<sup>–2</sup>, <i>V</i><sub>oc</sub> = 802 mV, and FF = 0.66. Both electrochemical impedance
spectroscopy (EIS) and intensity-modulated photovoltage spectroscopy
(IMVS) suggest that charge recombination in DSSCs based on <b>DT-1</b> is much less than that in their counterparts of <b>DT-2</b>, owing to the bigger donor size and the insulating blocking branch
in the donor of <b>DT-1</b>
Cosensitized Porphyrin System for High-Performance Solar Cells with TOF-SIMS Analysis
To
date, development of organic sensitizers has been predominately focused
on light harvesting, highest occupied molecular orbital and lowest
unoccupied molecular orbital energy levels, and the electron transferring
process. In contrast, their adsorption mode as well as the dynamic
loading behavior onto nanoporous TiO<sub>2</sub> is rarely considered.
Herein, we have employed the time-of-flight secondary ion mass spectrometry
(TOF-SIMS) to gain insight into the competitive dye adsorption mode
and kinetics in the cosensitized porphyrin system. Using novel porphyrin
dye <b>FW-1</b> and D–A−π–A featured
dye <b>WS-5</b>, the different bond-breaking mode in TOF-SIMS
and dynamic dye-loading amount during the coadsorption process are
well-compared with two different anchoring groups, such as benzoic
acid and cyanoacrylic acid. With the bombardment mode in TOF-SIMS
spectra, we have speculated that the cyano group grafts onto nanoporous
TiO<sub>2</sub> as tridentate binding for the common anchoring unit
of cyanoacrylic acid and confirmed it through extensive first-principles
density functional theory calculation by anchoring either the carboxyl
or cyano group, which shows that the cyano group can efficiently participate
in the adsorption of the <b>WS-5</b> molecule onto the TiO<sub>2</sub> nanocrystal. The grafting reinforcement interaction between
the cyano group and TiO<sub>2</sub> in <b>WS-5</b> can well-explain
the rapid adsorption characteristics. A strong coordinate bond between
the lone pair of electrons on the nitrogen or oxygen atom and the
Lewis acid sites of TiO<sub>2</sub> can increase electron injection
efficiencies with respect to those from the bond between the benzoic acid group and the Brønsted
acid sites of the TiO<sub>2</sub> surface. Upon optimization of the
coadsorption process with dye <b>WS-5</b>, the photoelectric
conversion efficiency based on porphyrin dye <b>FW-1</b> is
increased from 6.14 to 9.72%. The study on the adsorption dynamics
of organic sensitizers with TOF-SIMS analysis might provide a new
venue for improvement of cosensitized solar cells
Development of a Series of (1-Benzyl-3-(6-methoxypyrimidin-3-yl)-5-(trifluoromethoxy)‑1<i>H</i>‑indol-2-yl)methanols as Selective Protease Activated Receptor 4 (PAR4) Antagonists with in Vivo Utility and Activity Against γ‑Thrombin
Here,
we describe the development of a series of highly selective
PAR4 antagonists with nanomolar potency and selectivity versus PAR1,
derived from the indole-based <b>3</b>. Of these, <b>9j</b> (PAR4 IC<sub>50</sub> = 445 nM, PAR1 response IC<sub>50</sub> >
30 μM) and <b>10h</b> (PAR4 IC<sub>50</sub> = 179 nM,
PAR1 response IC<sub>50</sub> > 30 μM) maintained an overall
favorable in vitro DMPK profile, encouraging rat/mouse in vivo pharmacokinetics
(PK) and activity against γ-thrombin
Development of a Series of (1-Benzyl-3-(6-methoxypyrimidin-3-yl)-5-(trifluoromethoxy)‑1<i>H</i>‑indol-2-yl)methanols as Selective Protease Activated Receptor 4 (PAR4) Antagonists with in Vivo Utility and Activity Against γ‑Thrombin
Here,
we describe the development of a series of highly selective
PAR4 antagonists with nanomolar potency and selectivity versus PAR1,
derived from the indole-based <b>3</b>. Of these, <b>9j</b> (PAR4 IC<sub>50</sub> = 445 nM, PAR1 response IC<sub>50</sub> >
30 μM) and <b>10h</b> (PAR4 IC<sub>50</sub> = 179 nM,
PAR1 response IC<sub>50</sub> > 30 μM) maintained an overall
favorable in vitro DMPK profile, encouraging rat/mouse in vivo pharmacokinetics
(PK) and activity against γ-thrombin