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Cancer cells use multiple mechanisms to evade the effects of glutamine metabolism inhibitors. The pathways that govern responses to alterations in glutamine availability within the tumor may represent therapeutic targets for combinatorial strategies with these inhibitors. Here, we showed that targeting glutamine utilization stimulated Yes-associated protein (YAP) signaling in cancer cells by reducing cyclic adenosine monophosphate (cAMP)/protein kinase A (PKA)-dependent phosphorylation of large tumor suppressor (LATS). Elevated YAP activation induced extracellular matrix (ECM) deposition by increasing secretion of connective tissue growth factor (CTGF) that promoted production of fibronectin and collagen by surrounding fibroblasts. Consequently, inhibiting YAP synergized with inhibition of glutamine utilization to effectively suppress tumor growth in vivo, along with a concurrent decrease in ECM deposition. Blocking ECM remodeling also augmented the tumor suppressive effects of the glutamine utilization inhibitor. Collectively, these data reveal mechanisms by which targeting glutamine utilization increases ECM accumulation and identify potential strategies to reduce ECM levels and increase the efficacy of glutamine metabolism inhibitors.
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Histone H2B monoubiquitination (H2Bub1) is a dynamic posttranslational modification which are linked to DNA damage and plays a key role in a wide variety of regulatory transcriptional programs. Cancer cells exhibit a variety of epigenetic changes, particularly any aberrant H2Bub1 has frequently been associated with the development of tumors. Nevertheless, our understanding of the mechanisms governing the histone H2B deubiquitination and their associated functions during stem cell differentiation remain only partially understood. In this study, we wished to investigate the role of deubiquitinating enzymes (DUBs) on H2Bub1 regulation during stem cell differentiation. In a search for potential DUBs for H2B monoubiquitination, we identified Usp7, a ubiquitin-specific protease that acts as a negative regulator of H2B ubiquitination during the neuronal differentiation of mouse embryonic carcinoma cells. Loss of function of the Usp7 gene by a CRISPR/Cas9 system during retinoic acid-mediated cell differentiation contributes to the increase in H2Bub1. Furthermore, knockout of the Usp7 gene particularly elevated the expression of neuronal differentiation related genes including astryocyte-specific markers and oligodendrocyte-specific markers. In particular, glial lineage cell-specific transcription factors including oligodendrocyte transcription factor 2, glial fibrillary acidic protein, and SRY-box transcription factor 10 was significantly upregulated during neuronal differentiation. Thus, our findings suggest a novel role of Usp7 in gliogenesis in mouse embryonic carcinoma cells.
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Several fabrication methods have been developed for label-free detection in various fields. However, fabricating high-density and highly ordered nanoscale architectures by using soluble processes remains a challenge. Herein, we report a biosensing platform that integrates deep learning with surface-enhanced Raman scattering (SERS), featuring large-area, close-packed three-dimensional (3D) architectures of molybdenum disulfide (MoS2)-assisted gold nanoparticles (AuNPs) for the on-site screening of coronavirus disease (COVID-19) using human tears. Some AuNPs are spontaneously synthesized without a reducing agent because the electrons induced on the semiconductor surface reduce gold ions when the Fermi level of MoS2 and the gold electrolyte reach equilibrium. With the addition of polyvinylpyrrolidone, a two-dimensional large-area MoS2 layer assisted in the formation of close-packed 3D multistacked AuNP structures, resembling electroless plating. This platform, with a convolutional neural network-based deep learning model, achieved outstanding SERS performance at subterascale levels despite the microlevel irradiation power and millisecond-level acquisition time and accurately assessed susceptibility to COVID-19. These results suggest that our platform has the potential for rapid, low-damage, and high-throughput label-free detection of exceedingly low analyte concentrations.
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Aprendizado Profundo , Dissulfetos , Ouro , Nanopartículas Metálicas , Molibdênio , Análise Espectral Raman , Ouro/química , Molibdênio/química , Análise Espectral Raman/métodos , Dissulfetos/química , Nanopartículas Metálicas/química , Humanos , Propriedades de Superfície , COVID-19/virologia , Técnicas Biossensoriais/métodos , SARS-CoV-2/isolamento & purificação , Tamanho da PartículaRESUMO
Bortezomib-induced neuropathic pain (BINP) poses a challenge in multiple myeloma (MM) treatment. Genetic factors play a key role in BINP susceptibility, but research has predominantly focused on Caucasian populations. This research explored novel genetic risk loci and pathways associated with BINP development in Korean MM patients while evaluating the reproducibility of variants from Caucasians. Clinical data and buffy coat samples from 185 MM patients on bortezomib were collected. The cohort was split into discovery and validation cohorts through random stratification of clinical risk factors for BINP. Genome-wide association study was performed on the discovery cohort (n = 74) with Infinium Global Screening Array-24 v3.0 BeadChip (654,027 single nucleotide polymorphism [SNPs]). Relevant biological pathways were identified using the pathway scoring algorithm. The top 20 SNPs were validated in the validation cohort (n = 111). Previously reported SNPs were validated in the entire cohort (n = 185). Pathway analysis of the genome-wide association study results identified 31 relevant pathways, including immune systems and endosomal vacuolar pathways. Among the top 20 SNPs from the discovery cohort, 16 were replicated, which included intronic variants in ASIC2 and SMOC2, recently implicated in nociception, as well as intergenic variants or long noncoding RNAs. None of the 17 previously reported SNPs remained significant in our cohort (rs2274578, P = .085). This study represents the first investigation of novel genetic loci and biological pathways associated with BINP occurrence. Our findings, in conjunction with existing Caucasian studies, expand the understanding of personalized risk prediction and disease mechanisms. PERSPECTIVE: This article is the first to explore novel genetic loci and pathways linked to BINP in Korean MM patients, offering novel insights beyond the existing research focused on Caucasian populations into personalized risk assessment and therapeutic strategies of BINP.
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Remotely sensed products are often used in watershed modeling as additional constraints to improve model predictions and reduce model uncertainty. Remotely sensed products also enabled the spatial evaluation of model simulations due to their spatial and temporal coverage. However, their usability is not extensively explored in various regions. This study evaluates the effectiveness of incorporating remotely sensed evapotranspiration (RS-ET) and leaf area index (RS-LAI) products to enhance watershed modeling predictions. The objectives include reducing parameter uncertainty at the watershed scale and refining the model's capability to predict the spatial distribution of ET and LAI at sub-watershed scale. Using the Soil and Water Assessment Tool (SWAT) model, a systematic calibration procedure was applied. Initially, solely streamflow data was employed as a constraint, gradually incorporating RS-ET and RS-LAI thereafter. The results showed that while 14 parameter sets exhibit satisfactory performance for streamflow and RS-ET, this number diminishes to six with the inclusion of RS-LAI as an additional constraint. Furthermore, among these six sets, only three effectively captured the spatial patterns of ET and LAI at the sub-watershed level. Our findings showed that leveraging multiple remotely sensed products has the potential to diminish parameter uncertainty and increase the credibility of intra-watershed process simulations. These results contributed to broadening the applicability of remotely sensed products in watershed modeling, enhancing their usefulness in this field.
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Neurotropic alphaherpesviruses, including herpes simplex virus type 1 (HSV-1), recruit microtubule motor proteins to invade cells. The incoming viral particle traffics to nuclei in a two-step process. First, the particle uses the dynein-dynactin motor to sustain transport to the centrosome. In neurons, this step is responsible for long-distance retrograde axonal transport and is an important component of the neuroinvasive property shared by these viruses. Second, a kinesin-dependent mechanism redirects the particle from the centrosome to the nucleus. We have reported that the kinesin motor used during the second step of invasion is assimilated into nascent virions during the previous round of infection. Here, we report that the HSV-1 pUL37 tegument protein suppresses the assimilated kinesin-1 motor during retrograde axonal transport. Region 2 (R2) of pUL37 was required for suppression and functioned independently of the autoinhibitory mechanism native to kinesin-1. Furthermore, the motor domain and proximal coiled coil of kinesin-1 were sufficient for HSV-1 assimilation, pUL37 suppression, and nuclear trafficking. pUL37 localized to the centrosome, the site of assimilated kinesin-1 activation during infection, when expressed in cells in the absence of other viral proteins; however, pUL37 did not suppress kinesin-1 in this context. These results indicate that the pUL37 tegument protein spatially and temporally regulates kinesin-1 via the amino-terminal motor region in the context of the incoming viral particle.
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Herpesvirus Humano 1 , Cinesinas , Proteínas Estruturais Virais , Cinesinas/metabolismo , Herpesvirus Humano 1/fisiologia , Herpesvirus Humano 1/metabolismo , Humanos , Animais , Transporte Axonal/fisiologia , Chlorocebus aethiops , Centrossomo/metabolismo , Neurônios/metabolismo , Neurônios/virologia , Células Vero , Núcleo Celular/metabolismo , Núcleo Celular/virologiaRESUMO
A sterically encumbered trans-A2B-corrole possessing a perylenediimide (PDI) scaffold in close proximity to the macrocycle has been synthesized via a straightforward route. Electronic communication as probed via steady-state absorption or cyclic voltammetry is weak in the ground state, in spite of the corrole ring and PDI being bridged by an o-phenylene unit. The TDDFT excited-state geometry optimization suggests after excitation the interchromophoric distance is markedly reduced, thus enhancing the through-space electronic coupling between the corrole and the PDI. This is corroborated by the strong deviation of the emission spectrum originating from both PDI and corrole in the dyad. Selective excitation of both donor and acceptor units triggers efficient sub-picosecond electron transfer and hole transfer, respectively, followed by fast charge recombination. In comparison to previously studied corrole-PDI dyads, both charge separation and charge recombination occur faster, because of the structural relaxation in the excited state.
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Tumor-associated macrophages (TAMs) are vital contributors to the growth, metastasis, and therapeutic resistance of various cancers, including hepatocellular carcinoma (HCC). However, the exact phenotype of TAMs and the mechanisms underlying their modulation for therapeutic purposes have not been determined. Here, we present compelling evidence that glutamine-derived aspartate in TAMs stimulates spermidine production through the polyamine synthesis pathway, thereby increasing the translation efficiency of HIF-1α via eIF5A hypusination. Consequently, augmented translation of HIF-1α drives TAMs to undergo an increase glycolysis and acquire a metabolic phenotype distinct from that of M2 macrophages. Finally, eIF5A levels in tumor stromal lesions were greater than those in nontumor stromal lesions. Additionally, a higher degree of tumor stromal eIF5A hypusination was significantly associated with a more advanced tumor stage. Taken together, these data highlight the potential of inhibiting hypusinated eIF5A by targeting glutamine metabolism in TAMs, thereby opening a promising avenue for the development of novel therapeutic approaches for HCC.
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Ácido Aspártico , Carcinoma Hepatocelular , Fator de Iniciação de Tradução Eucariótico 5A , Glutamina , Subunidade alfa do Fator 1 Induzível por Hipóxia , Neoplasias Hepáticas , Fatores de Iniciação de Peptídeos , Proteínas de Ligação a RNA , Macrófagos Associados a Tumor , Fatores de Iniciação de Peptídeos/metabolismo , Fatores de Iniciação de Peptídeos/genética , Subunidade alfa do Fator 1 Induzível por Hipóxia/metabolismo , Humanos , Proteínas de Ligação a RNA/metabolismo , Proteínas de Ligação a RNA/genética , Carcinoma Hepatocelular/metabolismo , Carcinoma Hepatocelular/patologia , Macrófagos Associados a Tumor/metabolismo , Macrófagos Associados a Tumor/imunologia , Neoplasias Hepáticas/metabolismo , Neoplasias Hepáticas/patologia , Glutamina/metabolismo , Ácido Aspártico/metabolismo , Ácido Aspártico/análogos & derivados , Biossíntese de Proteínas , Animais , Linhagem Celular Tumoral , Camundongos , Glicólise , Lisina/análogos & derivadosRESUMO
Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented. It displays antiaromatic characteristics on the fused side and nonaromatic behavior on the unfused side. A newly synthesized tetraphenylene (TPE) linked bis-dibenzihomoporphyrin 8 and a previously reported dibenzo[g,p]chrysene (DBC) linked bis-dicarbacorrole 9 were prepared as controls. Comprehensive analyses, including 1H NMR spectral studies, single crystal X-ray diffraction analyses, and DFT calculations, validate the mixed character of 5. A further feature of the Janus pseudo-dimer 5 is that it may be transformed into a heterometallic complex, with one side coordinating a Cu(III) center and the other stabilizing a BODIPY complex. This disparate regiochemical reactivity underscores the potential of carbaporphyrin dimers as versatile frameworks, with electronic features and site-specific coordination chemistry controlled through asymmetry. These findings position carbaporphyrin dimers as promising candidates for advances in electronic structure studies, coordination chemistry, materials science, and beyond.
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Multiexciton in singlet exciton fission represents a critical quantum state with significant implications for both solar cell applications and quantum information science. Two distinct fields of interest explore contrasting phenomena associated with the geminate triplet pair: one focusing on the persistence of long-lived correlation and the other emphasizing efficient decorrelation. Despite the pivotal nature of multiexciton processes, a comprehensive understanding of their dependence on the structural and spin properties of materials is currently lacking in experimental realizations. To address this gap in knowledge, molecular engineering was employed to modify the TIPS-tetracene structures, enabling an investigation of the structure-property relationships in spin-related multiexciton processes. In lieu of the time-resolved electron paramagnetic resonance technique, two time-resolved magneto-optical spectroscopies were implemented for quantitative analysis of spin-dependent multiexciton dynamics. The utilization of absorption and fluorescence signals as complementary optical readouts, in the presence of a magnetic field, provided crucial insights into geminate triplet pair dynamics. These insights encompassed the duration of multiexciton correlation and the involvement of the spin state in multiexciton decorrelation. Furthermore, simulations based on our kinetic models suggested a role for quintet dilution in multiexciton dynamics, surpassing the singlet dilution principle established by the Merrifield model. The integration of intricate model structures and time-resolved magneto-optical spectroscopies served to explicitly elucidate the interplay between structural and spin properties in multiexciton processes. This comprehensive approach not only contributes to the fundamental understanding of these processes but also aligns with and reinforces previous experimental studies of solid states and theoretical assessments.
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Highly organized π-aggregate architectures can strongly affect electronic couplings, leading to important photophysical behaviors. With the escalating interest in two-dimensional (2D) materials attributed to their exceptional electronic and optical characteristics, there is growing anticipation that 2D radial-π-stacks built upon radial π-conjugation nanorings, incorporating intra- and inter-ring electronic couplings within the confines of a 2D plane, will exhibit superior topological attributes and distinct properties. Despite their immense potential, the design and synthesis of 2D π-stacks have proven to be a formidable challenge due to the insufficient π-π interactions necessary for stable stacking. In this study, we present the successful preparation of single-layer 2D radial-π-stacks in a solution. Pillar-shaped radially π-conjugated [4]cyclo-naphthodithiophene diimide ([4]C-NDTIs) molecules were tetragonally arranged via in-plane intermolecular π-π interactions. These 2D π-stacks have a unique topology that differs from that of conventional 1D π-stacks and exhibit notable properties, such as acting as a 2D template capable of absorbing C60 guest molecules and facilitating the formation of 2D radial-π-stacks comprising [4]C-NDTI-C60 complexes, rapid exciton delocalization across the 2D plane, and efficient excitation energy funneling towards a trap.
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Artificial sweeteners, which contain no or few calories, have been widely used in various foods and beverages, and are regarded as safe alternatives to sugar by the Food and Drug Administration. While several studies suggest that artificial sweeteners are not related to cancer development, some research has reported their potential association with the risk of cancers, including hepatocellular carcinoma (HCC). Here, we investigated whether acesulfame potassium (Ace K), a commonly used artificial sweetener, induces immune evasion of HCC cells by upregulating programmed death ligand-1 (PD-L1). Ace K elevated the protein levels of PD-L1 in HCC cells without increasing its mRNA levels. The upregulation of PD-L1 protein levels in HCC cells by Ace K was induced by attenuated autophagic degradation of PD-L1, which was mediated by the Ace K-stimulated ERK1/2-mTORC1 signaling pathway. Ace K-induced upregulation of PD-L1 attenuated T cell-mediated death of HCC cells, thereby promoting immune evasion of HCC cells. In summary, the present study suggests that Ace K promotes HCC progression by upregulating the PD-L1 protein level.
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Autofagia , Antígeno B7-H1 , Carcinoma Hepatocelular , Neoplasias Hepáticas , Tiazinas , Regulação para Cima , Antígeno B7-H1/metabolismo , Antígeno B7-H1/genética , Humanos , Carcinoma Hepatocelular/metabolismo , Carcinoma Hepatocelular/patologia , Carcinoma Hepatocelular/genética , Autofagia/efeitos dos fármacos , Regulação para Cima/efeitos dos fármacos , Tiazinas/farmacologia , Neoplasias Hepáticas/metabolismo , Neoplasias Hepáticas/patologia , Neoplasias Hepáticas/genética , Linhagem Celular Tumoral , Edulcorantes/farmacologia , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Alvo Mecanístico do Complexo 1 de Rapamicina/metabolismo , Sistema de Sinalização das MAP Quinases/efeitos dos fármacosRESUMO
Efficient exciton transport is essential for high-performance optoelectronics. Considerable efforts have been focused on improving the exciton mobility in organic materials. While it is feasible to improve mobility in organic systems by forming well-ordered stacks, the formation of trap states, particularly the lower-lying states referred to as excimers, remains a significant challenge to enhancing mobility. The mobility of excimer excitons intricately depends on the strength of excitonic coupling in terms of Förster-type diffusive exciton transfer processes. Given that the formation and mobility of excimer excitons are highly sensitive to molecular arrangements (packing geometries), conducting comprehensive investigations into the structure-property relationship in organic systems is crucial. In this study, we prepared three types of polycrystalline films of perylene bisimide (PBI) by varying substituents at the imide and bay positions, which allowed us to tailor the properties of excimer excitons and their mobility based on packing geometries and excitonic coupling strengths. By utilizing femtosecond transient absorption spectroscopy, we observed ultrafast excimer formation in the higher coupling regime, while in the lower coupling regime, the transition from Frenkel to excimer excitons occurs with a time constant of 500 fs. Under high pump-fluence, exciton-exciton annihilation processes occur, indicating the diffusion of excimer excitons. Intriguingly, employing a three-dimensional diffusion model, we derived a diffusion constant that is 3000 times greater in the high coupling regime than in the low coupling regime. To investigate the optoelectronic properties in the form of a bulk system, we fabricated n-type organic field effect transistors and obtained 8000 times higher mobility in the high coupling regime. Furthermore, photocurrent measurements enable us to investigate the charge carrier transport by mobile excimer excitons, suggesting a 230-fold improvement in external quantum efficiency with tightly packing PBI molecules compared to the low coupling regime. These findings not only offer valuable insights into optimizing organic materials for optoelectronic devices but also unveil the intriguing potential of exciton migration within excimers.
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Lake Sinai Virus (LSV) is an emerging pathogen known to affect the honeybee (Apis mellifera). However, its prevalence and genomic characteristics in the Republic of Korea (ROK) remain unexplored. This study aimed to assess the prevalence of and analyze the LSVs by examining 266 honeybee samples from the ROK. Our findings revealed that LSV exhibited the highest infection rate among the pathogens observed in Korean apiaries, particularly during the reported period of severe winter loss (SWL) in A. mellifera apiaries in 2022. Three LSV genotypes- 2, 3, and 4 -were identified using RNA-dependent RNA polymerase gene analysis. Importantly, the infection rates of LSV2 (65.2%) and LSV3 (73.3%) were significantly higher in colonies experiencing SWL than in those experiencing normal winter loss (NWL) (p < 0.03). Furthermore, this study provides the first near-complete genome sequences of the Korean LSV2, LSV3, and LSV4 strains, comprising 5,759, 6,040, and 5,985 nt, respectively. Phylogenetic analysis based on these near-complete genome sequences demonstrated a close relationship between LSVs in the ROK and China. The high LSV infection rate in colonies experiencing a heightened mortality rate during winter suggests that this pathogen might contribute to SWL in ROK. Moreover, the genomic characteristic information on LSVs in this study holds immense potential for epidemiological information and the selection of specific genes suitable for preventing and treating LSV, including the promising utilization of RNA interference medicine in the future.
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Vírus de RNA , Vírus , Abelhas , Animais , Filogenia , Prevalência , Vírus de RNA/genética , República da Coreia/epidemiologiaRESUMO
Bisphenol A (BPA), an exogenous endocrine-disrupting chemical, is widely used to produce polycarbonate plastics. The widely used BPA has been detected in human urine samples, raising public anxiety about the detrimental effects of BPA on the bladder. In this study, we explored regulatory mechanisms for the adverse effects of BPA in human bladder BdFC and T24 cells. BPA induced extrinsic and intrinsic apoptosis and G2/M cell cycle arrest caused by the ATM-CHK1/CHK2-CDC25c-CDC2 signaling, which ultimately inhibited the growth of human bladder cells. We also found that BPA decreased the binding activity of AP-1 and NF-κB transcription factors in human bladder cells, which inhibited migration and invasion through matrix metallopeptidase-2 and -9 inactivation. Phosphorylation of MAPKs was implicated with BPA-mediated detrimental effects in human bladder cells. Collectively, our results provide a novel explanation for the underlying molecular mechanisms that BPA induces cytotoxicity in human bladder cells.
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Compostos Benzidrílicos , Fenóis , Fatores de Transcrição , Bexiga Urinária , Humanos , Fosforilação , Apoptose , Pontos de Checagem da Fase G2 do Ciclo Celular , Linhagem Celular Tumoral , Ciclo CelularRESUMO
The burgeoning demand for commercializing self-luminescing quantum dot (QD) light-emitting diodes (LEDs) has stimulated extensive research into environmentally friendly and efficient QD materials. Hydrofluoric acid (HF) additive improves photoluminescence (PL) properties of blue-emitting ZnSeTe QDs, ultimately reaching a remarkable quantum yield (QY) of 97% with an ultranarrow peak width of 14 nm after sufficient HF addition. The improvement in optical properties of the QDs is accompanied by a morphology change of the particles, forming cubic-shaped defect-free ZnSeTe QDs characterized by a zinc blende (ZB) crystal structure. This treatment improves the QD-emitting properties by facilitating facet-specific growth, selectively exposing stabilized (100) facets, and reducing the lattice disorders. The facet-specific growth process gives rise to defect-free monodispersed cubic dots that exhibit remarkably narrow and homogeneous PL spectra. Meticulous time-resolved spectroscopic studies allow an understanding of the correlation between ZnSeTe QDs' particle shape and performance following HF addition. These investigations shed light on the intricacies of the growth mechanism and the factors influencing the PL efficiency of the resulting QDs. The findings significantly contribute to understanding the role of HF treatment in tailoring the optical properties of ZnSeTe QDs, thereby bringing it closer to the realization of highly efficient and bright QD-LEDs for various practical applications.
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Rapid and precise acute myocardial infarction (AMI) diagnosis is essential for preventing patient death. In addition, the complementary roles of creatine kinase muscle brain (CK-MB) and cardiac troponin I (cTnI) cardiac biomarkers in the early and late stages of AMI demand their simultaneous detection, which is difficult to implement using conventional fluorescence and electrochemical technologies. Here, a nanotechnology-based one-stop immuno-surface-enhanced Raman scattering (SERS) detection platform is reported for multiple cardiac indicators for the rapid screening and progressive tracing of AMI events. Optimal SERS is achieved using optical property-based, excitation wavelength-optimized, and high-yield anisotropic plasmonic gold nanocubes. Optimal immunoassay reaction efficiencies are achieved by increasing immobilized antibodies. Multiple simultaneous detection strategies are implemented by incorporating two different Raman reports with narrow wavenumbers corresponding to two indicators and by establishing a computational SERS mapping process to accurately detect their concentrations, irrespective of multiple enzymes in the human serum. The SERS platform precisely estimated AMI onset and progressive timing in human serum and made rapid AMI identification feasible using a portable Raman spectrometer. This integrated platform is hypothesized to significantly contribute to emergency medicine and forensic science by providing timely treatment and observation.
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Infarto do Miocárdio , Humanos , Creatina Quinase Forma MB , Infarto do Miocárdio/diagnóstico , Troponina I , Biomarcadores , ImunoensaioRESUMO
Cyclic azobenzene-BODIPY hybrids were synthesized via cyclization by 1) acid-catalysed condensation of azobenzene-bridged dipyrroles with 3,5-di-tert-butylbenzaldehyde, 2) oxidation with DDQ, and 3) metalation with BF3 â Et2 O. The structures of many cyclic hybrids have been confirmed by single crystal X-ray analysis. The absorption spectra of the hybrids reveal the effective cyclic conjugation. The ultrafast measurements reveal that the photoexcited decays of these cyclic hybrids depend upon the ring size and connectivity.
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The nose is a prominent feature for facial recognition and reconstruction. To investigate the relationship of the nasal shape with the piriform aperture in Korean adults and juveniles, we performed regression analysis. By regression analysis, prediction equations for nasal shape were obtained in relation to the shape of the piriform aperture considering sex and age groups. Three-dimensional skull and face models, rendered from computed tomography images, were assessed (331 males and 334 females). Juveniles (<20 years) were divided into three age groups according to the development of the dentition. Adults were divided into three age groups of two decades each, according to their age. To measure the nasal area, nine landmarks and nine measurements were chosen, while seven landmarks and five measurements were selected to measure the piriform aperture area. Four measurements were defined to explain the direct relationship between the nasal aperture and nasal shape. First, descriptive statistical analyses were performed according to sex and age groups. Subsequently, the correlation of nasal soft tissue measurements with piriform measurements was analyzed. Last, we performed a linear regression analysis of the measurements with higher correlations, considering sex and age groups as variables. Prediction equations were used to estimate the nasal bridge length, height, protrusion, and width. Equations considering sex and age groups showed better explanation ability. Measurements related to the height of the nasal bridge presented improvement. This study may assist in the more accurate approximation of nasal shape in facial reconstruction.
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Antropologia Forense , Imageamento Tridimensional , Adulto , Masculino , Feminino , Humanos , Antropologia Forense/métodos , Nariz/diagnóstico por imagem , Nariz/anatomia & histologia , Análise de Regressão , Crânio/anatomia & histologiaRESUMO
A nanographene-fused expanded carbaporphyrin (5) and its BF2 complex (6) were synthesized. Single-crystal X-ray structures revealed that 5 and 6 are connected by two hexa-peri-hexabenzocoronene (HBC) units and two dipyrromethene or BODIPY units, respectively. As prepared, 5 and 6 both show nonaromatic character with figure-of-eight carbaoctaphyrin (1.1.1.0.1.1.1.0) cores and adopt tweezers-like conformations characterized by a partially confined space between the two constituent HBC units. The distance between the HBC centers is >10 Å, while the dihedral angles between the two HBC planes are 30.5 and 35.2° for 5 and 6, respectively. The interactions between 5 and 6 and fullerene C60 were studied both in organic media and in the solid state. Proton NMR spectral titrations of 5 and 6 with C60 revealed a 1:1 binding mode for both macrocycles. In toluene-d8, the corresponding binding constants were determined to be 1141 ± 17 and 994 ± 10 M-1 for 5 and 6, respectively. Single-crystal X-ray diffraction structural analyses confirmed the formation of 1:1 fullerene inclusion complexes in the solid state. The C60 guests in both complexes are found within triangular pockets composed of two HBC units from the tweezers-like receptor most closely associated with the bound fullerene, as well as an HBC unit from an adjacent host. Femtosecond transient absorption measurements revealed subpicosecond ultrafast charge separation between 5 (and 6) and C60 in the complexes. To the best of our knowledge, the present report provides the first example wherein a nanographene building block is incorporated into the core of a porphyrinic framework.