Light-harvesting in carbonyl-terminated phenylacetylene dendrimers: The role of delocalized excited States and the scaling of light-harvesting efficiency with dendrimer size

The photophysics of a family of conjugated phenylacetylene (PA) light-harvesting dendrimers are studied using steady-state and time-resolved optical spectroscopy. The dendrimers consist of a substituted PA core surrounded by meta-branched PA arms. The total number of PA moieties ranges from 3 (first generation) to 63 (fifth generation). By using an alcohol/ketone substituent at the dendrimer core, we avoid through-space Forster transfer from the peripheral PA donors to the core acceptor (in this case, the carbonyl group), which simplifies the analysis of these molecules relative to the perylene-terminated molecules studied previously. The delocalized excited states previously identified in smaller dendrons are seen in these larger dendrimers as well, and their influence on the intersite electronic energy transfer (EET) is analyzed in terms of a point-dipole Forster model. We find that these new delocalized states can both enhance EET (by decreasing the spatial separation between donor and acceptor) and degrade it (by lowering the emission cross section and shifting the energy, resulting in poorer spectral overlap between donor and acceptor). The combination of these two effects leads to a calculated intersite transfer time of 6 ps, in reasonable agreement with the 5-17 ps range obtained from experiment. In addition to characterizing the electronic states and intersite energy transfer times, we also examine how the overall light-harvesting efficiency scales with dendrimer size. After taking the size dependence of other nonradiative processes, such as excimer formation, into account, the overall dendrimer quenching rate k(Q) is found to decrease exponentially with dendrimer size over the first four generations. This exponential decrease is predicted by simple theoretical considerations and by kinetic models, but the dependence on generation is steeper than expected based on those models, probably due to increased disorder in the larger dendrimers. We discuss the implications of these results for dendrimeric light-harvesting structures based on PA and other chemical motifs.     

Comparative photophysical properties of free-base, bis-Zn(II), bis-Cu(II), and bis-Co(II) doubly N-confused hexaphyrins(1.1.1.1.1.1)

We have comparatively investigated the photophysics of a series of bis-metal doubly N-confused hexaphyrins(1.1.1.1.1.1) using time-resolved fluorescence, femtosecond transient absorption, two-photon absorption measurements, and geometry-optimized ab initio calculations. Bis-Zn(II) and free-base doubly N-confused hexaphyrins exhibit well-resolved and red-shifted B- and Q-like absorption bands compared with porphyrins. Their allowed transitions are (pi,pi) transitions of the hexaphyrin ring, as confirmed by the HOMO and LUMO frontier orbitals based on ab initio calculations at the B3LYP/6-31G level. On the other hand, the absorption spectra of bis-Cu(II) and bis-Co(II) doubly N-confused hexaphyrins are relatively broad, presumably due to large couplings between the metal d-orbitals and pi-electrons of the hexaphyrin ring. Owing to these couplings, bis-Cu(II) and bis-Co(II) doubly N-confused hexaphyrins have much shorter excited-state lifetimes of 9.4 +/- 0.3 ps and 670 fs, respectively, than those (267 +/- 16 and 62.4 +/- 1.2 ps, respectively) of bis-Zn(II) and free-base doubly N-confused hexaphyrins. The two-photon absorption cross section (sigma(2)) values, which are believed to depend strongly on the ring planarity (pi-conjugation), are in line with the excited-state lifetime trends.     

Global weak solutions to a generalized Benjamin-Bona-Mahony-Burgers equation

The existence of global weak solutions for a generalized Benjamin-Bona-MahonyBurgers equation is established in the space C([0, ∞) × R) ∩ L~∞([0, ∞); H1(R)) under the condition that its initial value belongs to the space H1(R). A one-sided super bound estimate and a space-time higher-norm estimate on the first order derivatives of the solution with respect to the space variable are derived to prove the existence.     

Application of an LC–MS/MS Method for the Simultaneous Quantification of Homovanillic Acid and Vanillylmandelic Acid for the Diagnosis and Follow-Up of Neuroblastoma in 357 Patients

Homovanillic acid (HVA) and vanillylmandelic acid (VMA) are end-stage metabolites of catecholamine and are clinical biomarkers for the diagnosis of neuroblastoma. For the first time in Korea, we implemented and validated a liquid chromatography tandem mass spectrometry (LC–MS/MS) assay to measure urinary concentrations of HVA and VMA according to Clinical and Laboratory Standards Institute guidelines. Our LC–MS/MS assay with minimal sample preparation was validated for linearity, lower limit of detection (LOD), lower limit of quantification (LLOQ), precision, accuracy, extraction recovery, carryover, matrix effect, and method comparison. A total of 1209 measurements was performed to measure HVA and VMA in spot urine between October 2019 and September 2020. The relationship between the two urinary markers, HVA and VMA, was analyzed and exhibited high agreement (89.1% agreement, kappa’s k = 0.6) and a strong correlation (Pearson’s r = 0.73). To our knowledge, this is the first study to utilize LC–MS/MS for simultaneous quantitation of spot urinary HVA and VMA and analyze the clinical application of both markers on a large scale for neuroblastoma patients.     

Experimental study of the pressure drop after fractal-shaped orifices in turbulent pipe flows

Fractal-shaped orifices are thought to have a significant effect on the flow mixing properties downstream a pipe owing to their edge self-similarity shape. Here, we investigate the pressure drop after such fractal orifices and measure the pressure recovery at different stations downstream the orifice. A direct comparison is made with the pressure drop measured after regular circular orifices with the same flow area. Our results show that the fractal-shaped orifices have a significant effect on the pressure drop. Furthermore, the pressure drop measured across the fractal-shaped orifices is found to be lower than that from regular circular orifices of the same flow areas. This result could be important in designing piping systems from the point of view of losses. It looks promising to use the fractal-shaped orifices as flowmeters as they can sense the pressure drop across them accurately with lower losses than the regular circular-shaped ones.     

Adaptive H∞ Chaos Anti-synchronization

A new adaptive H∞ anti-synchronization （AHAS） method is proposed for chaotic systems in the presence of unknown parameters and external disturbances. Based on the Lyapunov theory and linear matrix inequality formulation, the AHAS controller with adaptive laws of unknown parameters is derived to not only guarantee adaptive anti-synchronization but also reduce the effect of external disturbances to an H∞ norm constraint. As an application of the proposed AHAS method, the H∞anti-synchronization problem for Genesio-Tesi chaotic systems is investigated.     

Resource allocation for end-to-end QoS provisioning in a hybrid wireless WCDMA and wireline IP-based DiffServ network

In the future UMTS network, the heterogeneous traffics of multimedia services demand various QoS provisioning. At the same time, the seamlessly conveying of information between mobile users and a hybrid network requires the networking from wireless to wireline domains. However, in both academia and industries, the end-to-end QoS provisioning in the integration of wireline and wireless networks remains a challenge. In this paper, a modeling of a hybrid wireless WCDMA and wireline IP-based DiffServ network is presented to investigate the resource allocation for end-to-end QoS provisioning for multimedia services. In the wireless domain, the mathematical modeling of the cross-layer model including the physical layer, the link layer and the network layer is built. The connection admission control scheme is implemented based on the cross-layer model to determine the amount of resource for different services. In the wireline domain, we define the mapping of QoS classes between UMTS and DiffServ networks according to different QoS requirements. We propose a bandwidth allocation scheme to provide satisfactory packet loss and delay guarantee in DiffServ networks. The final end-to-end admission control scheme combines the resource allocation and admission control in both wireless and wireline domains. The analytical and simulation results show that the proposed resource allocation and admission control schemes work cooperatively in the presented hybrid wireless and wireline networks to guarantee the end-to-end QoS requirements for multimedia services.