Mechanochemical Synthesis of Cuprous Complexes for X-ray Scintillation and Imaging.

Cuprous complex scintillators show promise for X-ray detection with abundant raw materials, diverse luminescent mechanisms, and adjustable structures. However, their synthesis typically requires a significant amount of organic solvents, which conflict with green chemistry principles. Herein, we present the synthesis of two high-performance cuprous complex scintillators using a simple mechanochemical method for the first time, namely [CuI(PPh3)2R] (R = 4-phenylpyridine hydroiodide (PH, Cu-1) and 4-(4-bromophenyl)pyridine hydroiodide (PH-Br, Cu-2). Both materials demonstrated remarkable scintillation performances, exhibiting radioluminescence (RL) intensities 1.52 times (Cu-1) and 2.52 times (Cu-2) greater than those of Bi4Ge3O12 (BGO), respectively. Compared to Cu-1, the enhanced RL performance of Cu-2 can be ascribed to its elevated quantum yield of 51.54%, significantly surpassing that of Cu-1 at 37.75%. This excellent luminescent performance is derived from the introduction of PH-Br, providing a more diverse array of intermolecular interactions that effectively constrain molecular vibration and rotation, further suppressing the nonradiative transition process. Furthermore, Cu-2 powder can be prepared into scintillator film with excellent X-ray imaging capabilities. This work establishes a pathway for the rapid, eco-friendly, and cost-effective synthesis of high-performance cuprous complex scintillators.

Association of saturated fatty acids with cancer risk: a systematic review and meta-analysis.

OBJECTIVE: Extensive research has explored the link between saturated fatty acids (SFAs) and cardiovascular diseases, alongside other biological dysfunctions. Yet, their association with cancer risk remains a topic of debate among scholars. The present study aimed to elucidate this association through a robust meta-analysis. METHODS: PubMed, Embase, Cochrane Library, and Web of Science databases were searched systematically to identify relevant studies published until December 2023. The Newcastle-Ottawa Scale was used as the primary metric for evaluating the quality of the included studies. Further, fixed- or random-effects models were adopted to determine the ORs and the associated confidence intervals using the Stata15.1 software. The subsequent subgroup analysis revealed the source of detection and the cancer types, accompanied by sensitivity analyses and publication bias evaluations. RESULTS: The meta-analysis incorporated 55 studies, comprising 38 case-control studies and 17 cohort studies. It revealed a significant positive correlation between elevated levels of total SFAs and the cancer risk (OR of 1.294; 95% CI: 1.182-1.416; P-value less than 0.001). Moreover, elevated levels of C14:0, C16:0, and C18:0 were implicated in the augmentation of the risk of cancer. However, no statistically significant correlation of the risk of cancer was observed with the elevated levels of C4:0, C6:0, C8:0, C10:0, C12:0, C15:0, C17:0, C20:0, C22:0, and C24:0. Subgroup analysis showed a significant relationship between excessive dietary SFA intake, elevated blood SFA levels, and heightened cancer risk. Increased total SFA levels correlated with higher risks of breast, prostate, and colorectal cancers, but not with lung, pancreatic, ovarian, or stomach cancers. CONCLUSION: High total SFA levels were correlated with an increased cancer risk, particularly affecting breast, prostate, and colorectal cancers. Higher levels of specific SFA subtypes (C14:0, C16:0, and C18:0) are also linked to an increased cancer risk. The findings of the present study would assist in providing dietary recommendations for cancer prevention, thereby contributing to the development of potential strategies for clinical trials in which diet-related interventions would be used in combination with immunotherapy to alter the levels of SFAs in patients and thereby improve the outcomes in cancer patients. Nonetheless, further high-quality studies are warranted to confirm these associations.

Novel Semiconductive Ternary Hybrid Heterostructures for Artificial Optoelectronic Synapses.

Synaptic devices that mimic biological synapses are considered as promising candidates for brain-inspired devices, offering the functionalities in neuromorphic computing. However, modulation of emerging optoelectronic synaptic devices has rarely been reported. Herein, a semiconductive ternary hybrid heterostructure is prepared with a D-D'-A configuration by introducing polyoxometalate (POM) as an additional electroactive donor (D') into a metalloviologen-based D-A framework. The obtained material features an unprecedented porous 8-connected bcu-net that accommodates nanoscale [α-SiW12 O40 ]4- counterions, displaying uncommon optoelectronic responses. Besides, the fabricated synaptic device based on this material can achieve dual-modulation of synaptic plasticity due to the synergetic effect of electron reservoir POM and photoinduced electron transfer. And it can successfully simulate learning and memory processes similar to those in biological systems. The result provides a facile and effective strategy to customize multi-modality artificial synapses in the field of crystal engineering, which opens a new direction for developing high-performance neuromorphic devices.

Aggregation-Induced Near-Infrared Emission and Electrochemiluminescence of an Iridium(III) Complex for Ampicillin Sodium Sensing.

A new iridium(III) complex was synthesized and characterized. Its photophysical properties and aggregation-induced emission and electrochemiluminescence in the near-infrared range were studied. The large conjugated cyclometallic ligand 1,2-phenylbenzoquinoline (pbq) was selected to form the Ir-C bond with the metal iridium(III) center and provide near-infrared emission of the complex. The auxiliary ligand 4,4'-diamino-2,2'-bipyridine (dabpy) can form hydrogen bonds, which was beneficial for the generation of aggregation-induced emission. The complex was aggregated into small spherical nanoparticles in 80% water and fascinating nanorings in 90% water. The sensing of ampicillin sodium (AMP) antibiotic by the iridium(III) complex were also investigated by photoluminescent and electrochemiluminescent methods. The complex showed a good selectivity toward AMP antibiotic compared to sodium phenylacetate and other eight antibiotics. The detection limits for AMP antibiotic was 0.76 µg/mL. This work provided a new strategy for the design of iridium(III) complex-based aggregation-induced emission and electrochemiluminescence probes for the sensing application.

Naphthalenediimide/Iodobismuthate Hybrid Heterostructures: Water Resistance and Long-Lived Charge-Separated States.

Organic-inorganic hybrid iodobismuthate perovskites have become promising semiconductive materials for their environmentally friendly and light-harvesting characteristics. However, their low-dimensional bismuth-iodide skeletons result in poor charge-separation efficiency, limiting their application in optoelectronic devices. To address this issue, the donor-acceptor (D-A) heterostructures have been introduced to the iodobismuthate hybrid materials by incorporating an electron-deficient N,N'-bis(4-aminoethyl)-1,4,5,8-naphthalene diimide (NDIEA) as the electron acceptor and organic counterpart. Five naphthalenediimide/iodobismuthate hybrid heterostructures, named (H2NDIEA)1.5·Bi2I9·3DMF (1), H2NDIEA·[Bi2I8(DMF)2]·2DMF (2), (H2NDIEA)2·Bi4I16·2H2O·4MeOH (3), (H2NDIEA)2·Bi4I16·8H2O (4), and [(H2NDIEA)2·Bi6I22]n·4nH2O (5) (DMF = N,N-dimethylformamide), were synthesized. Their crystal structures, water stabilities, charge-separated behaviors, and electrical properties have been studied through experimental and computational investigations. The results revealed that hybrids 3-5 exhibited high water resistance attributed to their tightly packed structures and robust H-bonds between solvent molecules and organic-inorganic supramolecular frameworks. Density functional theory calculations confirmed characteristic type-IIa band alignments of all the five hybrids, facilitating to the photoinduced charge separation. Moreover, the closer contact caused by the strong anion-π interactions between electron donors and acceptors in hybrid 5 leads to the long-lived charge-separated states and improved electrical properties compared to the other hybrids.

Three Semiconductive 1D Naphthalene Diimide/Iodoplumbate Perovskites with High Moisture Tolerance and Long-Lived Charge Separation States.

Low-dimensional inorganic-organic hybrid perovskites with high moisture tolerance and long-lived charge separation states have captured significant attention in the field of optoelectronic devices. To further achieve the relationship between crystal structures and stability, as well as charge separation behaviors, three one-dimensional hybrid perovskites containing electron-deficient naphthalene diimide ammonium (NDIEA) and electron-rich iodoplumbate chains, [(H2NDIEA)Pb2I6]·2DMF (1), [(H2NDIEA)2Pb5I14·(DMF)2]·4DMF (2), and [(HNDIEA)2Pb2I6]·3H2O (3), were synthesized. Crystal structure determinations revealed various synthesis conditions leading to different stacking modes, especially the inorganic lead iodide fraction, which resulted in different water resistances and charge-separated behaviors. The comprehensive analysis found that strong intermolecular interactions (anion-π interactions and π-π interactions), and matching energy levels between protonated NDIEA and iodoplumbate chains, can facilitate the generation of long-lived charge separation states and extraordinary moisture stability, even in the water environment. In addition, the conductivity behavior of 3 was also explored in detail.

Polyethylene glycol crosslinked decellularized single liver lobe scaffolds with vascular endothelial growth factor promotes angiogenesis in vivo.

BACKGROUND: Improving the mechanical properties and angiogenesis of acellular scaffolds before transplantation is an important challenge facing the development of acellular liver grafts. The present study aimed to evaluate the cytotoxicity and angiogenesis of polyethylene glycol (PEG) crosslinked decellularized single liver lobe scaffolds (DLSs), and establish its suitability as a graft for long-term liver tissue engineering. METHODS: Using mercaptoacrylate produced by the Michael addition reaction, DLSs were first modified using N-succinimidyl S-acetylthioacetate (SATA), followed by cross-linking with PEG as well as vascular endothelial growth factor (VEGF). The optimal concentration of agents and time of the individual steps were identified in this procedure through biomechanical testing and morphological analysis. Subsequently, human umbilical vein endothelial cells (HUVECs) were seeded on the PEG crosslinked scaffolds to detect the proliferation and viability of cells. The scaffolds were then transplanted into the subcutaneous tissue of Sprague-Dawley rats to evaluate angiogenesis. In addition, the average number of blood vessels was evaluated in the grafts with or without PEG at days 7, 14, and 21 after implantation. RESULTS: The PEG crosslinked DLS maintained their three-dimensional structure and were more translucent after decellularization than native DLS, which presented a denser and more porous network structure. The results for Young's modulus proved that the mechanical properties of 0.5 PEG crosslinked DLS were the best and close to that of native livers. The PEG-VEGF-DLS could better promote cell proliferation and differentiation of HUVECs compared with the groups without PEG cross-linking. Importantly, the average density of blood vessels was higher in the PEG-VEGF-DLS than that in other groups at days 7, 14, and 21 after implantation in vivo. CONCLUSIONS: The PEG crosslinked DLS with VEGF could improve the biomechanical properties of native DLS, and most importantly, their lack of cytotoxicity provides a new route to promote the proliferation of cells in vitro and angiogenesis in vivo in liver tissue engineering.

Baicalein attenuates bleomycin-induced lung fibroblast senescence and lung fibrosis through restoration of Sirt3 expression.

CONTEXT: Fibroblast senescence was reported to contribute to the pathological development of idiopathic pulmonary fibrosis (IPF), and baicalein is reported to attenuate IPF. OBJECTIVE: This study explores whether baicalein attenuates lung fibrosis by regulating lung fibroblast senescence. MATERIALS AND METHODS: Institute of Cancer Research (ICR) mice were randomly assigned to control, bleomycin (BLM), baicalein and BLM + baicalein groups. Lung fibrosis was established by a single intratracheal dose of BLM (3 mg/kg). The baicalein group received baicalein orally (100 mg/kg/day). Sirtuin 3 (Sirt3) siRNA (50 µg) was injected through the tail vein once a week for 2 weeks to explore its effect on the anti-pulmonary fibrosis of baicalein. RESULTS: BLM-treated mice exhibited obvious lung fibrosis and fibroblast senescence by showing increased levels of collagen deposition (27.29% vs. 4.14%), hydroxyproline (208.05 vs. 40.16 ng/mg), collagen I (25.18 vs. 9.15 µg/mg), p53, p21, p16, MCP-1, PAI-1, TNF-α, MMP-10 and MMP-12 in lung tissues, which were attenuated by baicalein. Baicalein also mitigated BLM-mediated activation of TGF-ß1/Smad signalling pathway. Baicalein restored the BLM-induced downregulation of Sirt3 expression in lung tissues and silencing of Sirt3 abolished the inhibitory role of baicalein against BLM-induced lung fibrosis, fibroblast senescence and activation of TGF-ß1/Smad signalling pathway. CONCLUSIONS: Baicalein preserved the BLM-induced downregulation of lung Sirt3 expression, and thus the suppression of TGF-ß1/Smad signalling pathway and lung fibrosis, which might provide an experimental basis for treatment of IPF.

Hyperpolarization-activated cyclic nucleotide-gated channels working as pacemaker channels in colonic interstitial cells of Cajal.

Hyperpolarization-activated cyclic nucleotide-gated (HCN) channels function as pacemaker channels in spontaneously active cells. We studied the existence of HCN channels and their functional roles in the interstitial cells of Cajal (ICC) from the mouse colon using electrophysiological, immunohistochemical and molecular techniques. HCN1 and HCN3 channels were detected in anoctamin-1 (Ca2+ -activated Cl- channel; ANO1)-positive cells within the muscular and myenteric layers in colonic tissues. The mRNA transcripts of HCN1 and HCN3 channels were expressed in ANO1-positive ICC. In the deletion of HCN1 and HCN3 channels in colonic ICC, the pacemaking potential frequency was reduced. Basal cellular adenylate cyclase activity was decreased by adenylate cyclase inhibitor in colonic ICC, whereas cAMP-specific phosphodiesterase inhibitors increased it. 8-Bromo-cyclic AMP and rolipram increased spontaneous intracellular Ca2+ oscillations. In addition, Ca2+ -dependent adenylate cyclase 1 (AC1) mRNA was detected in colonic ICC. Sulprostone, a PGE2 -EP3 agonist, increased the pacemaking potential frequency, maximum rate of rise of resting membrane in pacemaker potentials and basal cellular adenylate cyclase activity in colonic ICC. These results indicate that HCN channels exist in colonic ICC and participate in generating pacemaking potentials. Thus, HCN channels may be therapeutic targets in disturbed colonic motility disorders.

Donor-Acceptor Hybrid Heterostructures: An Emerging Class of Photoactive Materials with Inorganic and Organic Semiconductive Components.

Just as the heterojunctions in physics, donor-acceptor (D-A) heterostructures are an emerging class of photoactive materials fabricated from two semiconductive components at the molecular level. Among them, D-A hybrid heterostructures from organic and inorganic semiconductive components have attracted extensive attention in the past decades due to their combined advantages of high stability for the inorganic semiconductors and modifiability for the organic semiconductors, which are particularly beneficial to efficiently achieve photoinduced charge separation and transfer upon irradiations. In this review, by analogy with the heterojunctions in physics, a definition of the D-A heterostructures and their general design and synthetic strategies are given. Meanwhile, the D-A hybrid heterostructures are focused on and their recent advances in potential applications of photochromism, photomodulated luminescence, and photocatalysis summarized.

A Three-Component Donor-Acceptor Hybrid Framework with Low-Power X-ray-Induced Photochromism.

Donor-acceptor (D-A) hybrid frameworks with visual X-ray photochromism at room temperature are fascinating because of their promising applications as X-ray detectors. Herein, a 3-fold interpenetrated D-A hybrid framework, [Eu(bcbp)1.5(DMF)(H2O)2][Co(CN)6]·4H2O·CH3OH (1), has been obtained by incorporating electron-rich Co(CN)63- into the electron-deficient europium viologen framework, which interestingly exhibits ultraviolet and low-power X-ray dual photochromism with a remarkable color change from brown to green. Experimental and theoretical studies revealed that the X-ray photochromic behavior of hybrid 1 could be attributed to its D-A hybrid structural feature increasing the extent of photoinduced electron transfer and thus photogenerated radical species upon X-ray irradiation. Meanwhile, due to the introduction of emissive lanthanide cations in the D-A system, hybrid 1 exhibits photomodulated luminescence properties.

Photochromic Polyoxometalate/Perylenediimide Donor-Acceptor Hybrid Crystals with Interesting Luminescent Properties.

The self-assembly of electron-deficient protonated N, N'-dipyridyltetrachloroperylenediimide (4Cl-DPPDI) and electron-rich polyoxometalate acids HnXM12O40 (POMs; X = P or Si; M = W or Mo) resulted in four isomorphous donor-acceptor hybrid crystals 1-4 with segregated POM anions and one-dimensional racemic hydrogen-bonded 4Cl-DPPDI networks as electron-donor and -acceptor components, respectively. Because of the compact contacts between the POM anions and 4Cl-DPPDI tectons induced by anion-π interactions, besides enhanced photochromism, these four unique isostructural hybrids exhibited unusual room-temperature phosphorescence (RTP) emissions. More interestingly, owing to the facial compact contacts of two racemic 4Cl-DPPDI tectons induced by lone pair-π-assisted π-π interactions, they also showed unprecedented photon upconversion by triplet-triplet annihilation (TTA).

A comparative analysis of experienced uncertainties in relation to risk communication during COVID19: a four-country study.

BACKGROUND: During outbreaks, uncertainties experienced by affected communities can influence their compliance to government guidance on public health. Communicators and authorities are, hence, encouraged to acknowledge and address such uncertainties. However, in the midst of public health crises, it can become difficult to define and identify uncertainties that are most relevant to address. We analyzed data on COVID-19-related uncertainties from four socio-economic contexts to explore how uncertainties can influence people's perception of, and response to Risk Communication and Community Engagement (RCCE) strategies. RESULTS: This qualitative study, which adopts an interpretative approach, is based on data from a documentary review, key informant interviews (KII), and focus group discussions (FGD) with members of the general public and people with barriers to information from Germany, Guinea, Nigeria, and Singapore. Transcripts from the KII and FGD were coded and analyzed thematically. We interviewed a total of 155 KIs and conducted 73 FGD. Our analysis uncovered a divergence between uncertainties deemed relevant by stakeholders involved in policy making and uncertainties that people reportedly had to navigate in their everyday lives and which they considered relevant during the pandemic. We identified four types of uncertainties that seemed to have influenced people's assessment of the disease risk and their trust in the pandemic control strategies including RCCE efforts: epidemiological uncertainties (related to the nature and severity of the virus), information uncertainties (related to access to reliable information), social uncertainties (related to social behavior in times of heightened risk), and economic uncertainties (related to financial insecurities). CONCLUSION: We suggest that in future outbreaks, communicators and policy makers could improve the way in which affected communities assess their risk, and increase the trust of these communities in response efforts by addressing non-epidemiological uncertainties in RCCE strategies.

Epidemiology of Birth Defects in Eastern China and the Associated Risk Factors.

BACKGROUND This study aimed to survey the overall situation of birth defects (BDs) among citizens of Hangzhou, China, and the risk factors of different BD types. MATERIAL AND METHODS We collected the data of 4349 perinatal infants with BDs in Hangzhou. The potentially associated risk factors of BDs were recorded and logistic regression analysis was used to predict the high incidence of BDs. RESULTS Among all perinatal infants with BDs, there were 4105 (94.3%) single births, 225 (5.2%) twin births, and 10 (0.2%) multiple births. In clinical outcomes, there were 2477 (57.0%) live births, 1806 (41.5%) dead fetuses, and 11 (0.3%) stillbirths. Down syndrome ranked first, accounting for 30.7% of the total births, followed by cleft lip and polydactyly. Low family income, nulliparity, high parity, high education level, and taking contraceptives in early pregnancy were found to be risk factors of Down syndrome. Low parity, low education level, and pesticide exposure were found to be risk factors of cleft lip. For polydactyly, young age of the mother and a parity above 0 were identified as risk factors. CONCLUSIONS Different risks factors can influence BD development and potentially help to predict specific BD types, such as demographic features and harmful exposure in early pregnancy.

Chromatographic fingerprint combined with quantitative analysis of multi-components by single-marker for quality control of total lignans from Fructus arctii by high-performance liquid chromatography.

INTRODUCTION: The total lignans from Fructus arctii (TLFA) is a mixture of a series of lignans isolated from dried ripe fruit of Arctium lappa L. We previously reported on the pharmacological activity of TLFA that is related to diabetes. An accurate and practical TLFA quantitative analysis method for utilising it needs to be established. OBJECTIVE: This study aimed to develop an effective quantitative analysis method for assessing the TLFA quality. METHODS: A total of 11 marker components were confirmed by analysing the high-performance liquid chromatography fingerprints of 24 batches of TLFA samples. The samples were prepared from TLFA and structurally identified as lappaol H, lappaol C, arctiin, arctignan D, arctignan E, matairesinol, arctignan G, isolappaol A, lappaol A, arctigenin, and lappaol F. In the quantitative analysis of multi-components by the single-marker (QAMS) method and with arctiin as an internal reference substance, the content of these lignans in TLFA was simultaneously determined according to their relative correction factors with arctiin. RESULTS: There was no significant difference between results measured by the QAMS and traditional external standard methods. Hierarchical cluster and principal component analyses were performed to evaluate 24 TLFA batches based on the contents of 10 marker components. The results revealed that QAMS method combined with chemometric analyses could accurately measure and clearly distinguish the different quality samples of TLFA. CONCLUSION: The QAMS method is a reliable and promising quality control method for TLFA. It can provide a reference for promoting quality control of complex multi-component systems, especially for traditional Chinese medicine.

Intramolecular Energy and Solvent-Dependent Chirality Transfer within a BINOL-Perylene Hetero-Cyclophane.

Multichromophoric macrocycles and cyclophanes are important supramolecular architectures for the elucidation of interchromophoric interactions originating from precise spatial organization. Herein, by combining an axially chiral binaphthol bisimide (BBI) and a bay-substituted conformationally labile twisted perylene bisimide (PBI) within a cyclophane of well-defined geometry, we report a chiral PBI hetero-cyclophane (BBI-PBI) that shows intramolecular energy and solvent-regulated chirality transfer from the BBI to the PBI subunit. Excellent spectral overlap and spatial arrangement of BBI and PBI lead to efficient excitation energy transfer and subsequent PBI emission with high quantum yield (80-98 %) in various solvents. In contrast, chirality transfer is strongly dependent on the respective solvent as revealed by circular dichroism (CD) spectroscopy. The combination of energy and chirality transfer affords a bright red circularly polarized luminescence (CPL) from the PBI chromophore by excitation of BBI.

Enantioselective Recognition of Helicenes by a Tailored Chiral Benzo[ghi]perylene Trisimide π-Scaffold.

Enantioselective molecular recognition of chiral molecules that lack specific interaction sites for hydrogen bonding or Lewis acid-base interactions remains challenging. Here we introduce the concept of tailored chiral π-surfaces toward the maximization of shape complementarity. As we demonstrate for helicenes it is indeed possible by pure van-der-Waals interactions (π-π interactions and CH-π interactions) to accomplish enantioselective binding. This is shown for a novel benzo[ghi]perylene trisimide (BPTI) receptor whose π-scaffold is contorted into a chiral plane by functionalization with 1,1'-bi-2-naphthol (BINOL). Complexation experiments of enantiopure (P)-BPTI with (P)- and (M)-[6]helicene afforded binding constants of 10 700 M-1 and 550 M-1 , respectively, thereby demonstrating the pronounced enantiodifferentiation by the homochiral π-scaffold of the BPTI host. The enantioselective recognition is even observable by the naked eye due to a specific exciplex-type emission originating from the interacting homochiral π-scaffolds of electron-rich [6]helicene and electron-poor BPTI.

Lessons learnt from easing COVID-19 restrictions: an analysis of countries and regions in Asia Pacific and Europe.

The COVID-19 pandemic is an unprecedented global crisis. Many countries have implemented restrictions on population movement to slow the spread of severe acute respiratory syndrome coronavirus 2 and prevent health systems from becoming overwhelmed; some have instituted full or partial lockdowns. However, lockdowns and other extreme restrictions cannot be sustained for the long term in the hope that there will be an effective vaccine or treatment for COVID-19. Governments worldwide now face the common challenge of easing lockdowns and restrictions while balancing various health, social, and economic concerns. To facilitate cross-country learning, this Health Policy paper uses an adapted framework to examine the approaches taken by nine high-income countries and regions that have started to ease COVID-19 restrictions: five in the Asia Pacific region (ie, Hong Kong [Special Administrative Region], Japan, New Zealand, Singapore, and South Korea) and four in Europe (ie, Germany, Norway, Spain, and the UK). This comparative analysis presents important lessons to be learnt from the experiences of these countries and regions. Although the future of the virus is unknown at present, countries should continue to share their experiences, shield populations who are at risk, and suppress transmission to save lives.

College of American Pathologists Tumor Regression Grading System for Long-Term Outcome in Patients with Locally Advanced Rectal Cancer.

BACKGROUND: The National Comprehensive Cancer Network's Rectal Cancer Guideline Panel recommends American Joint Committee of Cancer and College of American Pathologists (AJCC/CAP) tumor regression grading (TRG) system to evaluate pathologic response to neoadjuvant chemoradiotherapy for locally advanced rectal cancer (LARC). Yet, the clinical significance of the AJCC/CAP TRG system has not been fully defined. MATERIALS AND METHODS: This was a multicenter, retrospectively recruited, and prospectively maintained cohort study. Patients with LARC from one institution formed the discovery set, and cases from external independent institutions formed a validation set to verify the findings from discovery set. Overall survival (OS), disease-free survival (DFS), local recurrence-free survival (LRFS), and distant metastasis-free survival (DMFS) were assessed by Kaplan-Meier analysis, log-rank test, and Cox regression model. RESULTS: The discovery set (940 cases) found, and the validation set (2,156 cases) further confirmed, that inferior AJCC/CAP TRG categories were closely /ccorrelated with unfavorable survival (OS, DFS, LRFS, and DMFS) and higher risk of disease progression (death, accumulative relapse, local recurrence, and distant metastasis) (all p < .05). Significantly, pairwise comparison revealed that any two of four TRG categories had the distinguished survival and risk of disease progression. After propensity score matching, AJCC/CAP TRG0 category (pathological complete response) patients treated with or without adjuvant chemotherapy displayed similar survival of OS, DFS, LRFS, and DMFS (all p > .05). For AJCC/CAP TRG1-3 cases, adjuvant chemotherapy treatment significantly improved 3-year OS (90.2% vs. 84.6%, p < .001). Multivariate analysis demonstrated the AJCC/CAP TRG system was an independent prognostic surrogate. CONCLUSION: AJCC/CAP TRG system, an accurate prognostic surrogate, appears ideal for further strategizing adjuvant chemotherapy for LARC. IMPLICATIONS FOR PRACTICE: The National Comprehensive Cancer Network recommends the American Joint Committee of Cancer and College of American Pathologists (AJCC/CAP) tumor regression grading (TRG) four-category system to evaluate the pathologic response to neoadjuvant treatment for patients with locally advanced rectal cancer; however, the clinical significance of the AJCC/CAP TRG system has not yet been clearly addressed. This study found, for the first time, that any two of four AJCC/CAP TRG categories had the distinguished long-term survival outcome. Importantly, adjuvant chemotherapy may improve the 3-year overall survival for AJCC/CAP TRG1-3 category patients but not for AJCC/CAP TRG0 category patients. Thus, AJCC/CAP TRG system, an accurate surrogate of long-term survival outcome, is useful in guiding adjuvant chemotherapy management for rectal cancer.

Photochromic and Room Temperature Phosphorescent Donor-Acceptor Hybrid Crystals Regulated by Core-Substituted Naphthalenediimides.

Donor-acceptor (D-A) hybrid crystals are an emerging kind of crystalline hybrid material composed of semiconductive inorganic donors and organic acceptors. Except for the intrinsic photochromism, recently we have reported that the anion-π polyoxometalate (POM)/naphthalenediimide (NDI) hybrid crystals could produce an interesting room temperature phosphorescence (RTP) quantum yield up to 7.2%. Herein, we extended into core-substituted NDIs and anticipated the regulation of their photochromic and RTP properties. Thus, two hybrid crystals, namely (H4BDMPy-Br2NDI)·(NMP)4·(HPW12O40) (1) and (H4BDMPy-I2NDI)·(HPW12O40) (2) (H2BDMPy-Br2NDI: N,N'-bis(3,5-dimethylpyrazolyl)-2,6-dibromo-1,4,5,8-naphthalenediimide and H2BDMPy-I2NDI: N,N'-bis(3,5-dimethylpyrazolyl)-2,6-diiodide-1,4,5,8-naphthalenediimide), have been synthesized from phosphotungstic anions (PW12O403-) and Br or I core-substituted NDIs. Compared to the core-unsubstituted analogues (H4BDMPy-NDI)·(NMP)4·(HPW12O40) (3), 2 with photosensitive iodine substituents is more sensitive to light, which can become discolored under natural light. As a result of the heavy-atom effect, hybrid 1 exhibits remarkable RTP with the quantum yield up to 10.2% and a lifetime of 1.14 ms.