A dual-catalysis approach enables the small-molecule catalyzed kinetic resolution of allylic amines by acylation. By employing 2 mol % of each 4-(pyrrolidino)pyridine (PPY) and a readily available chiral hydrogen-bonding cocatalyst, the first nonenzymatic kinetic resolution of allylic amines was accomplished with s factors of up to 20.

The emergence of visible light photoredox catalysis has enabled the productive use of lower energy radiation, leading to highly selective reaction platforms. Polypyridyl complexes of iridium and ruthenium have served as popular photocatalysts in recent years due to their long excited state lifetimes and useful redox windows, leading to the development of diverse photoredox-catalyzed transformations. The low abundances of Ir and Ru in the earth's crust and, hence, cost make these catalysts nonsustainable and have limited their application in industrial-scale manufacturing. Herein, we report a series of novel acridinium salts as alternatives to iridium photoredox catalysts and show their comparability to the ubiquitous [Ir(dF-CF3-ppy)2(dtbpy)](PF6).

Electrochemical codeposition of vanadium oxide (V2O5) and polypyrrole (PPy) is conducted from vanadyl sulfate (VOSO4) and pyrrole in their aqueous solution to get V2O5-PPy composite, during which one-dimensional growth of polypyrrole (PPy) is directed. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) are used to characterize the composite, while scanning electron microscopy (SEM) is used to investigate their morphologies. Cyclic voltammetry (CV), chronopotentiometry (CP) for galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) are used to study electrochemical activities and pseudocapacitive properties of the composite. The influences of VOSO4 to pyrrole ratio in the electro-codeposition solution on morphologies and pseudocapacitive properties of the composite are discussed. Due to the organic-inorganic synergistic effect, V2O5-PPy composite exhibits good charge-storage properties in a large potential window from -1.4 to 0.6 V vs SCE, with a specific capacitance of 412 F/g at 4.5 mA/cm(2). A model supercapacitor assembled by using the V2O5-PPy composite as the electrode materials displays a high operating voltage of 2 V and so a high energy density of 82 Wh/kg (at the power density of 800 W/kg).

The synthesis and photophysical characterization of a series of (N,C(2')-(2-para-tolylpyridyl))2 Ir(LL') [(tpy)2 Ir(LL')] (LL' = 2,4-pentanedionato (acac), bis(pyrazolyl)borate ligands and their analogues, diphosphine chelates and tert-butylisocyanide (CN-t-Bu)) are reported. A smaller series of [(dfppy)2 Ir(LL')] (dfppy = N,C(2')-2-(4',6'-difluorophenyl)pyridyl) complexes were also examined along with two previously reported compounds, (ppy)2 Ir(CN)2- and (ppy)2 Ir(NCS)2- (ppy = N,C(2')-2-phenylpyridyl). The (tpy)2 Ir(PPh2CH2)2 BPh2 and [(tpy)2 Ir(CN-t-Bu)2](CF3SO3) complexes have been structurally characterized by X-ray crystallography. The Ir-C(aryl) bond lengths in (tpy)2 Ir(CN-t-Bu)2+ (2.047(5) and 2.072(5) A) and (tpy)2 Ir(PPh2CH2)2 BPh2 (2.047(9) and 2.057(9) A) are longer than their counterparts in (tpy)2 Ir(acac) (1.982(6) and 1.985(7) A). Density functional theory calculations carried out on (ppy)2 Ir(CN-Me)2+ show that the highest occupied molecular orbital (HOMO) consists of a mixture of phenyl-pi and Ir-d orbitals, while the lowest unoccupied molecular orbital is localized primarily on the pyridyl-pi orbitals. Electrochemical analysis of the (tpy)2 Ir(LL') complexes shows that the reduction potentials are largely unaffected by variation in the ancillary ligand, whereas the oxidation potentials vary over a much wider range (as much as 400 mV between two different LL' ligands). Spectroscopic analysis of the cyclometalated Ir complexes reveals that the lowest energy excited state (T1) is a triplet ligand-centered state (3LC) on the cyclometalating ligand admixed with 1MLCT (MLCT = metal-to-ligand charge-transfer) character. The different ancillary ligands alter the 1MLCT state energy mainly by changing the HOMO energy. Destabilization of the 1MLCT state results in less 1MLCT character mixed into the T1 state, which in turn leads to an increase in the emission energy. The increase in emission energy leads to a linear decrease in ln(k(nr)) (k(nr) = nonradiative decay rate). Decreased 1MLCT character in the T1 state also increases the Huang-Rhys factors in the emission spectra, decreases the extinction coefficient of the T1 transition, and consequently decreases the radiative decay rates (k(r)). Overall, the luminescence quantum yields decline with increasing emission energies. A linear dependence of the radiative decay rate (k(r)) or extinction coefficient (epsilon) on (1/deltaE)2 has been demonstrated, where deltaE is the energy difference between the 1MLCT and 3LC transitions. A value of 200 cm(-1) for the spin-orbital coupling matrix element 3LC absolute value(H(SO)) 1MLCT of the (tpy)2 Ir(LL') complexes can be deduced from this linear relationship. The (fppy)2 Ir(LL') complexes with corresponding ancillary ligands display similar trends in excited-state properties.

The mRNA for the epithelial Na(+) channel gamma subunit (gammaENaC) is regulated developmentally in the lung, colon and distal nephron and in response to Na(+) deprivation and systemic corticosteroids in the distal colon. Because such regulation is likely to be at the level of gene transcription, we examined the function of the promoter and other 5' flanking elements of the human gammaENaC gene. The proximal 5' flanking region contains two GC boxes but does not contain a TATA box. A 450 bp human gammaENaC fragment (-459 to +40) directed the expression of luciferase in H441 cells and primer extension analysis in transfected cells confirmed the correct initiation of human gammaENaC-luciferase chimaeric transcripts. By deletional analysis, GC boxes at -21 and -52 were found to be critical for this promoter activity. To begin to identify transcription factors that bind to the core promoter, a double-stranded oligonucleotide that corresponded to this region was synthesized and tested in a gel mobility-shift assay. Incubation of this radiolabelled oligonucleotide with nuclear extracts from H441 and FRTL5 cells resulted in the formation of four specific and distinct DNA-protein complexes. On the basis of antibody 'supershift' assays, one of these factors corresponds to Sp1, whereas the other three correspond to Sp3. Further upstream, an approx. 300 nt (-1143 to -839) polypurine-polypyrimidine tract (PPy tract) containing internal mirror repeats was identified. When contained in a supercoiled plasmid, the approx. 1200 nt 5' flanking region was sensitive to S1 endonuclease, which was consistent with the formation of an intramolecular triplex DNA ('H-DNA') structure with an unpaired single strand. High-resolution mapping with S1 endonuclease and sequencing of S1-generated clones confirmed that all S1-sensitive sites were within the PPy tract. Finally, a negative regulatory element was identified between -1525 and -1296 that functioned in lung, colon and collecting duct cell lines.

The emitting triplet state of fac-Ir(ppy)(3) (fac-tris(2-phenylpyridine)iridium) is studied for the first time on the basis of highly resolved optical spectra in the range of the electronic 0-0 transitions. For the compound dissolved in CH(2)Cl(2) and cooled to cryogenic temperatures, three 0-0 transitions corresponding to the triplet substates I, II, and III are identified. They lie at 19,693 cm(-1) (507.79 nm, I → 0), 19,712 cm(-1) (507.31 nm, II → 0), and 19,863 cm(-1) (503.45 nm, III → 0). From the large total zero-field splitting (ZFS) of 170 cm(-1), the assignment of the emitting triplet term as a (3)MLCT state (metal-to-ligand charge transfer state) is substantiated, and it is seen that spin-orbit couplings to higher lying (1,3)MLCT states are very effective. Moreover, the studies provide emission decay times for the three individual substates of τ(I) = 116 μs, τ(II) = 6.4 μs, and τ(III) = 200 ns. Further, group-theoretical considerations and investigations under application of high magnetic fields up to B = 12 T allow us to conclude that all three substates are nondegenerate and that the symmetry of the complex in the CH(2)Cl(2) matrix cage is lower than C(3). It follows that the triplet parent term is of (3)A character. Studies of the emission decay time and photoluminescence quantum yield, Φ(PL), of Ir(ppy)(3) in poly(methylmethacrylate) (PMMA) in the temperature range of 1.5 ≤ T ≤ 370 K reveal average and individual radiative and nonradiative decay rates and quantum yields of the substates. In the range 80 ≤ T ≤ 370 K, Φ(PL) is as high as almost 100%. The quantum yield Φ(PL) drops to ∼88% when cooled to T = 1.5 K. The investigations show further that the emission properties of Ir(ppy)(3) depend distinctly on the complex's environment or the matrix cage according to distinct changes of spin-orbit coupling effectiveness. These issues also have consequences for optimizations of the material's properties if applied as an organic light-emitting diode (OLED) emitter.

In the present study, we examined the therapeutic potential of human amnion-derived insulin-secreting cells for type 1 diabetes. Human amniotic mesenchymal stem cells (hAMs) were isolated from amnion and cultivated to differentiate into insulin-secreting cells in vitro. After culture in vitro, the differentiated cells (hAM-ISCs) were intensively stained with dithizone and secreted insulin and c-peptide in a high-glucose-dependent manner. They expressed mRNAs of pancreatic cell-related genes, including INS, PDX1, Nkx6-1, NEUROG3, ISL1, NEUROD1, GLUT1, GLUT2, PC1/3, PC2, GCK, PPY, SST, and GC, and were positive for human insulin and c-peptide. Transplantation of hAM-ISCs into the kidneys of mice with streptozotocin-induced diabetes restored body weight and normalized the blood glucose levels, which lasted for 210 days. Only human insulin and c-peptide were detected in the blood of normalized mice after 2 months of transplantation, but little mouse insulin and c-peptide. Removal of graft-bearing kidneys from these mice resulted in causing hyperglycemia again. Human cell-specific gene, hAlu, and human pancreatic cell-specific genes, insulin, PDX1, GLUT1, GLP1R, Nkx6-1, NEUROD1, and NEUROG3, were detected in the graft-bearing kidneys. Colocalization of human insulin and human nuclei antigen was also observed. These results demonstrate that hAMs could differentiate into functional insulin-secreting cells in vitro, and human insulin secreted from hAM-ISCs following transplantation into type 1 diabetic mice could normalize hyperglycemia, overcoming immune rejection for a long period.

Femtosecond photoluminescence (PL) and transient absorption (TA) studies have been carried out on the red phosphorescent metal complex tris(1-phenylisoquinoline)iridium(III) [Ir(piq)(3)] following excitation of the metal-ligand charge transfer singlet state. Rapid decay of the PL observed at 270 meV above the phosphorescence peak and TA dynamics are indicative of intersystem crossing, which occurs with a time constant of 70 fs. PL decays at 140 meV above the phosphorescence peak are biexponential with time constants of 95 fs and 3 ps, attributed to intramolecular vibrational redistribution (IVR) and vibrational cooling. The larger Ir(piq)(3) ligands facilitate faster dissipation of excess energy by IVR than the smaller Ir(ppy)(3) core.

BACKGROUND

Emerging HIV epidemics have been documented among people who inject drugs (PWID) in the Middle East and North Africa (MENA). This study estimates the HIV incidence among PWID due to sharing needles/syringes in MENA. It also delineates injecting drug use role as a driver of the epidemic in the population, and estimates impact of interventions.

METHODS

A mathematical model of HIV transmission among PWID was applied in seven MENA countries with sufficient and recent epidemiological data and HIV prevalence ≥1% among PWID. Estimations of incident and/or prevalent infections among PWID, ex-PWID and sexual partners of infected current and ex-PWID were conducted.

RESULTS

The estimated HIV incidence rate for 2017 among PWID ranged between 0.7% per person-year (ppy) in Tunisia and 7.8% ppy in Pakistan, with Libya being an outlier (24.8% ppy). The estimated number of annual new infections was lowest in Tunisia (n = 79) and Morocco (n = 99), and highest in Iran and Pakistan (approximately n = 6700 each). In addition, 20 to 2208 and 5 to 837 new annual infections were estimated across the different countries among sexual partners of PWID and ex-PWID respectively. Since epidemic emergence, the number of total ever acquired incident infections across countries was 706 to 90,015 among PWID, 99 to 18,244 among sexual partners of PWID, and 16 to 4360 among sexual partners of ex-PWID. The estimated number of prevalent infections across countries was 341 to 23,279 among PWID, 119 to 16,540 among ex-PWID, 67 to 10,752 among sexual partners of PWID, and 12 to 2863 among sexual partners of ex-PWID. Increasing antiretroviral therapy (ART) coverage to the global target of 81% - factoring in ART adherence and current coverage - would avert about half of new infections among PWID and their sexual partners. Combining ART with harm reduction could avert over 90% and 70% of new infections among PWID and their sexual partners respectively.

CONCLUSIONS

There is considerable HIV incidence among PWID in MENA. Of all new infections ultimately due to injecting drug use, about 75% are among PWID and the rest among sexual partners. Of all prevalent infections ultimately attributed to injecting drug use as epidemic driver, about half are among PWID, 30% among ex-PWID and 20% among sexual partners of PWID and ex-PWID. These findings call for scale-up of services for PWID, including harm reduction as well as testing and treatment services.

OBJECTIVE

The objective was to describe epidemiologic features and usage patterns of pediatric emergency medical services (EMS) transports in Kansas City, Missouri.

METHODS

The study consisted of a retrospective analysis of transports from January 1, 2002, to December 31, 2004, for Kansas City, Missouri, residents younger than 15 years of age (excluding interfacility transports. Data included demographics, insurance, day and time of transport, patient zip code, chief complaint, and number of individual transports. Rates were calculated using intercensal estimates for the denominator. All rates were expressed as number of transports per 1,000 persons per year (PPY).

RESULTS

A total of 5,717 pediatric transports occurred in the 3-year study period. Transport rates were 18 PPY for all users, 42 PPY for those <1 year old, 23 PPY for ages 1-4 years, 12 PPY for ages 5-9 years, and 14 PPY for ages 10-14 years. Infants <1 year were more likely than children aged 5-9 years to use EMS (relative risk [RR] = 3.7, 95% confidence interval [CI] = 3.4 to 4.0). Males were more likely than females to use EMS (RR = 1.2, 95% CI = 1.1 to 1.3). Most (64%) were insured by Medicaid. Transports peaked between 4 pm and 8 pm, and lowest usage was 4 am to 8 am (p < 0.001). Overall usage did not vary by weekday or season. Respiratory transports were more common in the fall and winter, while trauma transports were more common in the summer (p < 0.001). The most common diagnoses were trauma (27%), neurologic (19%), and respiratory (18%). Eleven percent of users accessed EMS more than once (26% of all transports). There was a significant inverse linear relationship between transport rate and median family income by zip code (r = -0.36, p < 0.001).

CONCLUSIONS

Children in zip codes with lower incomes, infants, and males were more likely to use EMS. Factors related to these increased transport rates are unknown.

We present a new type of electrochemical supercapacitors based on graphene nanowires. Graphene oxide (GO)/polypyrrole (PPy) nanowires are prepared via electrodepostion of GO/PPy composite into a micoroporous Al2O3 template, followed by the removal of template. PPy is electrochemically doped by oxygen-containing functional groups of the GO to enhance the charging/discharging rates of the supercapacitor. A high capacitance 960 F g(-1) of the GO/PPy nanowires is obtained due to the large surface area of the vertically aligned nanowires and the intimate contact between the nanowires and the substrate electrode. The capacitive performance remains stable after charging and discharging for 300 cycles. To improve the thermal stability and long-term charge storage, GO is further electrochemically reduced into graphene and PPy is subsequently thermally carbonized, leading to a high capacitance of 200 F g(-1) for the resultant pure reduced graphene oxide/carbon based nanowire supercapacitor. This value of capacitance (200 F g(-1)) is higher than that of conventional porous carbon materials while the reduced graphene oxide/carbon nanowires show a lower Faraday resistance and higher thermal stability than the GO/PPy nanowires.

A molecularly imprinted polymer (MIP) polypyrrole (PPy)-based film was fabricated for the determination of ascorbic acid. The film was prepared by incorporation of a template molecule (ascorbic acid) during the electropolymerization of pyrrole onto a pencil graphite electrode (PGE) in aqueous solution using a cyclic voltammetry method. The performance of the imprinted and non-imprinted (NIP) films was evaluated by differential pulse voltammetry (DPV). The effect of pH, monomer and template concentrations, electropolymerization cycles and interferents on the performance of the MIP electrode was investigated and optimized. The molecularly imprinted film exhibited a high selectivity and sensitivity toward ascorbic acid. The DPV peak current showed a linear dependence on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 0.25 to 7.0 mM of ascorbic acid with a correlation coefficient of 0.9946. The detection limit (3σ) was determined as 7.4x10-5 M (S/N=3). The molecularly-imprinted polypyrrole-modified pencil graphite electrode showed a stable and reproducible response, without any influence of interferents commonly existing in pharmaceutical samples. The proposed method is simple and quick. The PPy electrodes have a low response time, good mechanical stability and are disposable simple to construct.

As a result of their outstanding attributes, organic light-emitting diodes (OLEDs) and white organic light-emitting diodes (WOLEDs) have been recognized in recent years as the most promising candidates for future flat-panel display technologies and next generation solid-state energy-saving lighting sources. New advancements in the area of high performance triplet emitters become vital for realizing more practical applications. In this regard, several critical issues must be carefully identified and addressed, and these include the ways to enhance device efficiency and suppress efficiency roll-off, to achieve versatile color tuning and simple device manufacture, as well as to obtain high-quality white light from WOLEDs. It has been shown that some functionalized phosphorescent Ir(III) and Pt(II) ppy-type cyclometalated complexes (ppy = 2-phenylpyridine) possess unique features that are suitable for solving these difficult and challenging tasks. In this Focus Review, we will highlight the recent design tactics adopted for these functional metallophosphors and the critical roles they may play in developing more realistic devices.

In this paper a method of electrospinning conducting and nonconducting biphasic Janus nanofibers using microfluidic polydimethylsiloxane (PDMS)-based manifolds is described. Key benefits of using microfluidic devices for nanofiber synthesis include rapid prototyping, ease of fabrication, and the ability to spin multiple Janus fibers in parallel through arrays of individual microchannels. Biphasic Janus nanofibers of polyvinylpyrrolidone (PVP)+polypyrrole (PPy)PVP nanofibers with an average diameter of 250 nm were successfully fabricated using elastomeric microfluidic devices. Fiber characterization and confirmation of the Janus morphology was subsequently carried out using a combination of scanning electron microscopy, energy dispersion spectroscopy, and transmission electron microscopy.

The bioluminescence resonance energy transfer (BRET) between firefly luciferase from Photinus pyralis (Ppy) with core/shell semiconductive quantum rods (QRs) has been studied as a function of QR aspect ratio and internal microstructure. The QRs were found to be ideal energy acceptors, and Ppy-to-core distances were optimized using rod-in-rod microstructures that were achieved by the synthetic control of rod morphology, surface chemistry, and Ppy:QR loading. The BRET ratios of >44 measured are the highest efficiencies to date.

Poly(N-isopropylacrylamide) (pNIPAM) composite microgels incorporating polypyrrole (PPy) nanoparticles were produced using droplet microfluidics. The composite microgels exhibited site-specific de-swelling-swelling properties that were activated by near-infrared light. Their applications for programmable drug release by pulsed-light control were also demonstrated.

Electricity has a long history of being used as an alternative clinical treatment and as an effective approach to modifying cellular behaviours in vitro. It has been difficult, however, to take advantage of this modality in tissue generation because of the lack of suitable conductive, biocompatible scaffolding materials. In this study, in order to electrically regulate cell activities, a largely biodegradable conductor made of 5% conductive polypyrrole and 95% biodegradable poly(L-lactide) (PPy/PLLA) was prepared. Human cutaneous fibroblasts were cultured on the conductors in the presence or absence of a direct current (DC) electrical field (EF) of 50 mV/mm. The growth of the cells was characterized using fluorescent staining, SEM, and a MTT assay. The RNA expressions of interleukin-6 (IL-6) and interleukin-8 (IL-8) were assayed by RT-PCR. The amounts of IL-6 and IL-8 secreted by the fibroblasts were quantified by ELISA. The results showed that the PPy/PLLA conductors supported cell adhesion, spreading, and proliferation in both the presence and absence of the EF. Electrical stimulation (ES) applied through PPy/PLLA conductors dramatically enhanced cytokine secretion approximately 10-fold when compared to the non-ES controls. This effect lasted several days after the end of the ES. These findings highlight for the first time the possibility of a potent, effective approach to regulating tissue regeneration in conductive scaffolds through ES-modulated cytokine secretion, and to increasing cytokine productivity for biotechnological applications.

The prevalence of obesity has reached epidemic proportions worldwide and the incidence of overweight and obesity continues to rise. Diet plays a significant role in the modulation of body weight and there is some evidence to suggest that calcium or dairy intake may modulate body weight and body fat mass. Several mechanisms through which calcium or dairy products may affect body weight or fat have been suggested, including a possible effect on appetite and food intake. A recent study investigated to what extent people could compensate for increased energy intake from dairy products and found that a 7-day increase in dairy intake had no effect on appetite and no evidence of complete compensation for the raised energy intake. In another study, the effects of altered calcium content of a dairy-based test meal was evaluated in obese subjects; the findings indicated that although a higher calcium content of the meal reduced the extent of post-prandial chylomicron-associated triglyceridemia, there was no effect on appetite-related hormones (CCK, ghrelin, GLP-1, or PPY) or on energy intake from a subsequent ad libitum test meal. Thus, this new evidence does not support the hypothesis that high calcium or dairy intake reduces appetite or food intake.

A simple, rapid and highly sensitive method for simultaneous analysis of methamphetamine (MA) and 3,4-methylenedioxy methamphetamine (MDMA) in human serum was developed using the solid-phase microextraction (SPME) combined with ion mobility spectrometry (IMS). A dodecylsulfate-doped polypyrrole (PPy-DS) was applied as a new fiber for SPME. Electrochemically polymerized PPy is formed on the surface of a platinum wire and will contain charge-compensating anion (dodecylsulfate) incorporated during synthesis using cyclic voltammetry (CV) technique. The extraction properties of the fiber to MA and MDMA were examined, using a headspace-SPME (HS-SPME) device and thermal desorption in injection port of IMS. The results show that PPy-DS as a SPME fiber coating is suitable for the successful extraction of these compounds. This method is suitable for the identification and determination of MAs, is not time-consuming, requires small quantities of sample and does not require any derivatization. Parameters like pH, extraction time, ionic strength, and temperature of the sample were studied and optimized to obtain the best extraction results. The HS-SPME-IMS method provided good repeatability (RSDs<7.8 %) for spiked serum samples. The calibration graphs were linear in the range of 20-4000 ng ml(-1) (R(2)>0.99) and detection limits for MDMA and MA were 5 and 8 ng ml(-1), respectively. HS-SPME-IMS of non-spiked serum sample provided a spectrum without any peak from the matrix, supporting an effective sample clean-up. Finally, the proposed method was applied for analysis one of the ecstasy tablet.

A series of phosphorescent zwitterionic iridium(III) complexes, with 4-carboxy-2, 2'-bipyridine-4'-carboxylate (Hdcbpy) as ancillary ligand, Ir(C(wedge)N)(2)(Hdcbpy) (C(wedge)N = 1-phenylpyrazole (ppz), 1-phenyl-pyridine (ppy), 2-(4',6'-difluoro-phenyl)pyridine (dfppy), 1-phenyl-isoquinoline (piq), dibenzo[f,h]quinoxaline (dbq)), were prepared and characterized. Their photophysical properties were studied, and intense luminescence emissions were observed based on metal-to-ligand-charge-transfer ((3)MLCT), ligand-to-ligand charge-transfer ((3)LLCT), ligand-centered transitions ((3)LC, i.e., (3)pi ->> pi*), or intraligand-charge-transfer ((3)ILCT) excited states, which were confirmed by theoretical calculations. The quantum yield of Ir(dfppy)(2)(Hdcbpy) is as high as 0.106 in aqueous solution. With Hdcbpy as a hydrophilic part, their amphiphilic structures as further confirmed by X-ray single crystal data endow them with different solubilities in phosphate buffer solution (PBS, pH 7.0). The compounds were successfully applied as luminescent dyes for cell imaging in aqueous solution. Their different stain ability in cell imaging was fairly well supported by the experimental data based on the measurement of oil/water partition coefficients and encapsulation/release with liposomes.

The racemic ligands (±)-tris(isonicotinoyl)-cyclotriguaiacylene (L1), or (±)-tris(4-pyridyl-methyl)-cyclotriguaiacylene (L2) assemble with racemic (Λ,Δ)-[Ir(ppy)2 (MeCN)2 ]+ , in which ppy=2-phenylpyridinato, to form [{Ir(ppy)2 }3 (L)2 ]3+ metallo-cryptophane cages. The crystal structure of [{Ir(ppy)2 }3 (L1)2 ]⋅3BF4 has MM-ΛΛΛ and PP-ΔΔΔ isomers, and homochiral self-sorting occurs in solution, a process accelerated by a chiral guest. Self-recognition between L1 and L2 within cages does not occur, and cages show very slow ligand exchange. Both cages are phosphorescent, with [{Ir(ppy)2 }3 (L2)2 ]3+ having enhanced and blue-shifted emission when compared with [{Ir(ppy)2 }3 (L1)2 ]3+ .

We report on the development of bioinspired cardiac scaffolds made from electroconductive acid-modified silk fibroin-poly(pyrrole) (AMSF+PPy) substrates patterned with nanoscale ridges and grooves reminiscent of native myocardial extracellular matrix (ECM) topography to enhance the structural and functional properties of cultured human pluripotent stem cells (hPSC)-derived cardiomyocytes. Nanopattern fidelity was maintained throughout the fabrication and functionalization processes, and no loss in conductive behavior occurred due to the presence of the nanotopographical features. AMSF+PPy substrates were biocompatible and stable, maintaining high cell viability over a 21-day culture period while displaying no signs of PPy delamination. The presence of anisotropic topographical cues led to increased cellular organization and sarcomere development, and electroconductive cues promoted a significant improvement in the expression and polarization of connexin 43 (Cx43), a critical regulator of cell-cell electrical coupling. The combination of biomimetic topography and electroconductivity also increased the expression of genes that encode key proteins involved in regulating the contractile and electrophysiological function of mature human cardiac tissue.

In present study, a sensitive and effective electrochemical microRNA (miRNA) sensing platform is successfully developed by integrating gold nanoparticles/polypyrrole-reduced graphene oxide (Au/PPy-rGO), catalyzed hairpin assembly (CHA) and hybridization chain reaction (HCR) multiple signal amplification strategy. Firstly, Au/PPy-rGO was employed onto a bare GCE by electrodeposition that can greatly enhanced conductivity and effectively immobilize probes. Then, the thiolated capture probes (SH-CP) were self-assembled on the Au/PPy-rGO modified GCE via Au-S bond. The target miRNA triggered the dynamic assembly of the two hairpin substrates (H1 and H2), leading to the cyclicality of the target miRNA and the formation of H1-H2 complexes without the assistance of enzyme. Subsequently, the newly emerging DNA fragment of H2 triggered the HCR when a mixture solution (hairpins H3 and H4) and produced dsDNA polymers. Finally, a substantial amount of methylene blue (MB) as signal indicator was intercalated into the minor groove of the long dsDNA polymers to achieve detected electrochemical signal. The fabricated sensor is able to detect miRNA-16 (model target) with concentration range from 10 fM to 5 nM with a low detection limit (LOD) of 1.57 fM (S/N = 3). Current research suggests that the developed multiple signal amplification platform has a great potential for the applications in the field of biomedical research and clinical analysis.

The parapyramidal (ppy) region targets primarily the intermediolateral cell column and is probably involved in breathing and thermoregulation. In the present study, we tested whether ppy serotonergic neurons respond to activation of central and peripheral chemoreceptors. Bulbospinal ppy neurons (n=30) were recorded extracellularly along with the phrenic nerve activity in urethane/α-chloralose-anesthetized, paralyzed, intact (n=7) or carotid body denervated (n=6) male Wistar rats. In intact animals, most of the ppy neurons were inhibited by hypoxia (n=14 of 19) (8% O2, 30s) (1.5 ± 0.03 vs. control: 2.4 ± 0.2 Hz) or hypercapnia (n=15 of 19) (10% CO2) (1.7 ± 0.1 vs. control: 2.2 ± 0.2 Hz), although some neurons were insensitive to hypoxia (n=3 of 19) or hypercapnia (n=4 of 19). Very few neurons (n=2 of 19) were activated after hypoxia, but not after hypercapnia. In carotid body denervated rats, all the 5HT-ppy neurons (n=11) were insensitive to hypercapnia (2.1 ± 0.1 vs. control: 2.3 ± 0.09 Hz). Biotinamide-labeled cells that were recovered after histochemistry were located in the ppy region. Most labeled cells (90%) showed strong tryptophan hydroxylase immunocytochemical reactivity, indicating that they were serotonergic. The present data reveal that peripheral chemoreceptors reduce the activity of the serotonergic premotor neurons located in the ppy region. It is plausible that the serotonergic neurons of the ppy region could conceivably regulate breathing automaticity and be involved in autonomic regulation.