Decomposition-Reassembly Synthesis of a Silverton-Type Polyoxometalate 3D Framework: Semiconducting Properties and Photocatalytic Applications.

Polyoxometalate-based all-inorganic three-dimensional (3D) frameworks have recently attracted attention as a unique class of materials due to their unique physicochemical properties and a wide field of application with excellent prospects. We herein synthesized a novel all-inorganic 3D framework material based on cobalt-substituted Silverton-type polyoxometalate, H6{Co6W10O42[Co(H2O)4]3}·2H2O (Co9W10), which was successfully constructed using Na12[WCo3II(H2O)2(CoIIW9O34)2]·46-48H2O (Co5W19) and Co(NO3)2·6H2O as starting materials in a hydrothermal reaction via a decomposition-reassembly route together with the rational adjustment of pH values. Co9W10 has been structurally characterized using single-crystal X-ray diffraction. Photocurrent response, band-gap (Eg) value, and the VB-XPS spectrum have been measured to reveal the semiconducting property of Co9W10. Furthermore, we synthesized x% PTh/Co9W10 composites (PTh = polythiophene, x = 0.5, 1, 2, 5) for photodegradation of tetracycline hydrochloride (TH) to evaluate the photocatalytic activities of title composites. Due to the optimal molar ratio of hybrids and matching energy levels, 2% PTh/Co9W10 composites show the best photocatalytic activities among these composites.

pH-Controlled assembly of [ZnW12O40]6--based hybrids from a 0D dimer to a 2D network: synthesis, crystal structure, and photocatalytic performance in transformation of toluene into benzaldehyde.

Polyoxometalate-based organic-inorganic hybrids have attracted considerable attention due to their fascinating structures and wide application prospects. In this work, using the same building blocks, ligands and metal ions (ZnW12O406-(ZnW12), 2,2'-bipyridine (2,2'-bipy), and Cu2+), we synthesized three new POM-based hybrids by controlling the pH values of the reaction systems. These three compounds {(Zn0.6(H2)0.4W12O40)[Cu(2,2'-bipy)(H2O)][Cu(2,2'-bipy)(H2O)2][Cu(2,2'-bipy)(H2O)3]}2·6H2O (1), (Me4N)2{ZnW12O40[Cu(2,2'-bipy)(H2O)][Cu(2,2'-bipy)(H2O)3]}·5H2O (2), and {(Zn0.5(H2)0.5W12O40)[Cu(2,2'-bipy)][Cu(2,2'-bipy)(H2O)][Cu(2,2'-bipy)(H2O)2]}·5H2O (3) have been structurally characterized by single-crystal X-ray diffraction. Compound 1 appears as a dimeric cluster structure, while compounds 2 and 3 appear as a 1D chain structure and a 2D network, respectively. The semiconducting properties of compounds 1-3 are different, which was demonstrated by band gap (Eg) and photocurrent response measurements. Compound 3 can efficiently catalyze the photooxidation of toluene to benzaldehyde with high selectivity using molecular oxygen as the oxidant component. Moreover, compound 3 was recycled and reused three times without significant degradation in conversion and selectivity. In addition, the mechanism of the photocatalytic reaction was also investigated.

An unprecedented polyoxometalate-based 1D double chain compound with opposite charges enables conductivity improvement.

A POM-based one-dimensional (1D) chain compound, {BW12O40[Cu(2,2'-bipy)2]2[Cu(2,2'-bipy)(H2O)]}{BW12O40[Cu(2,2'-bipy)2][Cu(2,2'-bipy)(H2O)2]}·7H2O, has been synthesized and structurally characterized, which represents an unprecedented 1D double chain structure with opposite charges. In contrast to common POMs, this compound exhibits a relatively high electrical conductivity of 1.17 × 10-9 S cm-1 at 25 °C. In addition, its semiconducting properties have also been investigated by application of photoelectrochemical sensing of H2O2.

Exploring the Coordination Modes of a Keggin-Type [ZnW12O40]6- Anionic Cluster: Bonding Patterns, Crystal Structure, and Semiconducting Properties.

Polyoxometalate-based organic-inorganic hybrid compounds (POIHCs) have been greatly developed due to their wide application prospects, but the pursuit of their directed synthesis via molecular design still remains a challenge. Herein, we demonstrate that the coordination modes of the Keggin-type [ZnW12O40]6- anion can be tuned, which leads to different semiconductor characteristics. Using the same building block, ligand, and metal ion (ZnW12, phen, Cu2+), we synthesized three new POIHCs with different bonding patterns by means of different coordination modes of ZnW12. The three POIHCs (H2phen){ZnW12O40[Cu(phen)2]2}·3H2O (1), {ZnW12O40[Cu(phen)(H2O)2]2[Cu(phen)(H2O)]}n·3H2O (2), and (Me4N)2{ZnW12O40[Cu(phen)(H2O)]2}n·5H2O (3) (phen = 1,10-phenanthroline) have been structurally characterized by single-crystal X-ray diffraction. Compound 1 appears as a zero-dimensional coordination complex cluster, while compounds 2 and 3 are both 1D chain structures with different Cu2+ bridge linkages. Although these three POIHCs possess the same chemical components, their semiconductor properties are different, which is demonstrated by measurements of transient photocurrent and band gap (Eg) values. Furthermore, we carried out comparative experiments on the photoconductivity performance of compounds 1-3 and their photocatalytic reduction from O2 to H2O2, indicating the significant influence of the energy level matching on the photocatalytic activity.

Real-world impact of postmastectomy radiotherapy in T1-2 breast cancer with one to three positive lymph nodes.

BACKGROUND: The utility of postmastectomy radiotherapy (PMRT) in breast cancer patients with T1-2 (tumor size ≤5 cm) and N1 (one to three lymph nodes involved) disease remains controversial. The aim of this population-based study was to investigate the effectiveness of PMRT in this patient subset in the current clinical practice. METHODS: We included T1-2N1 breast cancer patients treated with mastectomy from 2004 to 2012 using the data form the Surveillance, Epidemiology, and End Results program. The association of PMRT administration with breast cancer-specific survival was determined using multivariable Cox analysis. RESULTS: We identified 10,248 patients of this study, including 3,725 (36.3%) received PMRT and 6,523 (63.7%) patients did not receive PMRT. Use of PMRT showed increase from 2008 onward; the percentage of patients receiving PMRT was 30.6% in 2004 and was 47.1% in 2012 (P<0.001). Patients diagnosis after 2008, aged <50 years, high tumor grade, T2 stage, and ≥2 positive lymph nodes were independently related to PMRT receipt. Multivariate analysis indicated that PMRT was not related to better breast cancer-specific survival compared to those without PMRT both before (P=0.186) and after propensity score matching (P=0.137). CONCLUSIONS: In breast cancer with T1-2N1 disease, PMRT does not appear to improve survival in the era of modern systemic therapy.

From a blue to white to yellow emitter: a hexanuclear copper iodide nanocluster.

Highly emissive copper(i) halide nanoclusters showing thermally activated delayed fluorescence (TADF) have been paid much attention, but rarely reported so far. Herein, a hexanuclear copper(i) iodide cluster containing a tridentate N∧P∧N ligand, [Cu6I6(ppda)2] {ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline}, was synthesized. All six copper atoms are four-coordinate, including four CuPNI2 and two CuI4 units. This complex exhibits intense white emission in the powder state at room temperature and shows a peak at a wavelength of 535 nm (ΦPL = 0.36) with a microsecond lifetime (τ = 4.4 µs). Emission colors can be largely tuned from blue to white to yellow, from the crystal to powder to film state at 297 K. The emission of [Cu6I6(ppda)2] originates from a combination of MLCT and XLCT transitions. This complex showed good thermal stability. A solution-processed, nondoped device of complex [Cu6I6(ppda)2] exhibits stable yellow emission with the CIE coordinates (x, y) of (0.43, 0.51). [Cu6I6(ppda)2] also shows reasonable photocatalytic H2 evolution activity under visible-light irradiation.

Histological Tumor Type is Associated with One-Year Cause-Specific Survival in Women with Stage III-IV Epithelial Ovarian Cancer: A Surveillance, Epidemiology, and End Results (SEER) Database Population Study, 2004-2014.

BACKGROUND The prognosis of epithelial ovarian cancer (EOC) remains poor. Cause-specific survival (CSS) is an overall survival measure of cancer survival that excludes other causes of death. This retrospective population study used the Surveillance, Epidemiology, and End Results (SEER) database to evaluate prognostic factors associated with one-year CSS in women with stage III-IV EOC between 2004-2014. MATERIAL AND METHODS Data from the SEER program included a cohort of patients with stage III-IV EOC between 2004-2014. Binomial logistic regression analysis, Kaplan-Meier survival curves, and multivariate Cox proportional hazards models were used for analysis of patient outcome, including the one-year CSS. RESULTS There were 14,798 patients with stage III-IV EOC identified from SEER between 2004-2014, including 13,134 (88.8%), 892 (6.0%), 448 (3.0%), and 324 (2.2%) patients with serous, endometrioid, clear cell, and mucinous ovarian cancer, respectively. The overall one-year CSS was 91.2%. One-year CSS was 92.5%, 92.2%, 74.0%, and 62.5% in patients with serous, endometrioid, clear cell, and mucinous ovarian cancer, respectively (P<0.001). Histological tumor type was an independent prognostic factor of one-year CSS. Patients with mucinous EOC (HR, 8.807; 95% CI, 6.563-9.965; P<0.001) and clear cell EOC (HR, 4.581; 95% CI, 3.774-5.560; P<0.001) had a significantly lower one-year CSS compared with patients with endometrioid and serous EOC who had comparable one-year CSS (HR, 1.247; 95% CI, 0.978-1.590; P=0.075). CONCLUSIONS A retrospective population study of the SEER database between 2004-2014 identified that histological tumor type was associated with one-year CSS in women with stage III-IV EOC.

Omission of adjuvant radiotherapy following breast-conserving surgery for elderly women with early-stage pure mucinous breast carcinoma.

BACKGROUND: We aimed to ascertain population-based practice patterns and survival outcomes of postoperative radiotherapy following breast conserving-surgery (BCS) in elderly women (aged ≥65 years) with early-stage pure mucinous breast carcinoma (PMBC). METHODS: Patients aged ≥65 years diagnosed with T1-2N0 and hormone receptor-positive PMBC between 1990 and 2010 were identified from the Surveillance, Epidemiology, and End Results database. Binomial logistic regression, Kaplan-Meier method, Multivariate Cox proportional hazards models, and propensity score matching (PSM) were used for statistical analysis. RESULTS: We enrolled 3416 patients, including 1225 (35.9%) and 2191 (64.1%) in the no-radiotherapy and radiotherapy cohorts, respectively. The percentage of patients receiving postoperative radiotherapy following BCS was significantly lower after 2004 (59.5% between 2004 and 2010), relative to that before 2004 (71.1% between 1990 and 2003; P < 0.001). Before PSM, the 10-year breast cancer-specific survival (BCSS) rates were 98.1 and 93.2% for patients with and without postoperative radiotherapy (log-rank test, P < 0.001), respectively. In the PSM cohort, receiving postoperative radiotherapy was associated with better BCSS rates, with 10-year BCSS rates of 97.6 and 94.5% in patients with and without postoperative radiotherapy, respectively (log-rank test, P = 0.001). Multivariate Cox proportional analysis indicated that receiving postoperative radiotherapy was an independent factor associated with better BCSS before (P < 0.001) and after PSM (P = 0.001), relative to those not receiving postoperative radiotherapy. CONCLUSIONS: This study shows a decreasing utilization of postoperative radiotherapy following BCS of elderly PMBC patients over time. However, postoperative radiotherapy following BCS should be administered for elderly women with PMBC owing to independent association with better survival.

21-Gene Recurrence Score Assay Could Not Predict Benefit of Post-mastectomy Radiotherapy in T1-2 N1mic ER-Positive HER2-Negative Breast Cancer.

Introduction: It is still controversial whether post-mastectomy radiotherapy (PMRT) is necessary for women with T1-2 N1mic ER-positive HER2-negative breast cancer. The 21-gene recurrence score (RS) assay has been validated in T1-2 N1 breast cancer to be prognostic of locoregional recurrence (LRR) and overall survival (OS). This study aims to evaluate the predict value of 21-gene recurrence score assay for the benefit of PMRT in T1-2 N1mic ER-positive HER2-negative breast cancer. Methods: A population-based cohort study was performed on women with T1-2 N1mic ER-positive HER2-negative breast cancer who underwent mastectomy and were evaluated using the 21-gene RS in the Surveillance, Epidemiology, and End Results (SEER) registry between 2004 and 2015. Clinical characteristics as well as OS and breast cancer-specific survival (BCSS) were compared between patients with and without PMRT in patients with a Low-, Intermediate-, and High-RS. Multivariate COX regression analysis was performed to investigate if the 21-gene RS assay could predict benefit of PMRT in this group of breast cancer patients. Results: A total of 1571 patients met the criteria of our study and were enrolled, including 970 patients in the Low-Risk group (score <18), 508 in the Intermediate-Risk group (score 18-30), and 93 patients in the High-Risk group (score >30). In the High-Risk group, there were more patients with age ≥50 (87.0 vs. 64.3%, P = 0.040) and received chemotherapy with a borderline significance (91.3 vs. 72.9%, P = 0.066) in the PMRT subgroup than in the no PMRT subgroup. In all three groups, OS was comparable between the PMRT subgroup and the no PMRT subgroup. Furthermore, multivariate analysis did not show any OS benefit for PMRT based on the 21-gene recurrence score. Conclusion: This study showed that the 21-gene RS assay was not able to predict the benefit of PMRT for OS in women with T1-2 N1mic ER-positive HER2-negative breast cancer. However, further prospective larger sample-size trials are warranted to determine if a benefit exists.

21-gene recurrence score and adjuvant chemotherapy decisions in patients with invasive lobular breast cancer.

AIM: To determine the effect of the 21-gene recurrence score (RS) on outcome and chemotherapy decision in breast invasive lobular carcinoma (ILC). MATERIALS & METHODS: We included 6467 patients with early stage and estrogen receptor-positive ILC from the Surveillance, epidemiology, and end results database. RESULTS: A total of 9.1, 31.4, and 70.1% of patients with low-, intermediate-, and high-risk RS groups received chemotherapy, respectively. A higher RS was independently associated with poor breast cancer-specific survival, and receipt of chemotherapy was not related to better breast cancer-specific survival in low-, intermediate-, or high-risk RS groups. CONCLUSION: The 21-gene RS could impact chemotherapy decision making in early-stage ILC. However, adjuvant chemotherapy does not appear to improve outcome in high-risk RS cohort.

Clinicopathologic characteristics and clinical outcomes of pure type and mixed type of tubular carcinoma of the breast: a single-institution cohort study.

INTRODUCTION: We aimed to evaluate the clinicopathologic characteristics and clinical outcomes of the mixed type versus the pure type of tubular carcinoma (TC) of the breast in a retrospective cohort study. MATERIALS AND METHODS: Patients were categorized into the following three groups: patients with pure TC of the breast (the PTC group), patients with TC and carcinoma in situ of the breast (the TC-CIS group), and patients with TC and other invasive carcinomas of the breast (the TC-IC group). We compared the clinicopathologic characteristics and treatment outcomes of the three groups. The primary end point of this study was breast cancer-specific survival (BCSS). Secondary end points included distant metastasis-free survival (DMFS) and locoregional recurrence (LRR). RESULTS: A total of 68 patients were included in this study, including 31 patients in the PTC group, 12 in the TC-CIS group, and 25 in the TC-IC group. Our data showed that PTC and TC-CIS were more likely to be smaller in size (P=0.014) and had substantially less nodal involvement (P=0.019), compared with TC-IC. The median follow-up time was 64.3 months (range, 3.78-223.2 months) for all patients. No locoregional relapse was observed in any group during the follow-up period. The 10-year BCSS of the PTC, TC-CIS, and TC-IC groups was 100%, 100%, and 95.2%, respectively, and the 10-year DMFS was 92.3%, 100%, and 96.0%, respectively. There was no significant difference in terms of BCSS (P=0.53) or DMFS (P=0.84) between the three groups. CONCLUSION: This study indicates that both the pure type and mixed type of TC of the breast show very low LRR and distant metastasis rate and have excellent survival. The TC-IC group is likely to show good prognosis similar to the PTC group. Further clinical trials with larger sample sizes as well as molecular and genetic studies are warranted.

Patterns of Distant Metastasis Between Histological Types in Esophageal Cancer.

Introduction: Distant metastasis remains the major cause of treatment failure in esophageal cancer, though there have been few large-scale studies of the patterns of distant metastasis in different histological types. We investigated the patterns of distant metastasis in esophageal adenocarcinoma (AC) and squamous cell carcinoma (SCC) using a population-based approach. Methods: Patients with de novo stage IV esophageal cancer at diagnosis were identified using the Surveillance, Epidemiology, and End Results database. Multivariable logistic regression was performed to identify potential risk factors for site-specific distant metastasis to the distant lymph nodes, bone, liver, brain, and lung at diagnosis. Results: We identified 1,470 patients with complete data for analysis including 1,096 (74.6%) patients with AC and 374 (25.4%) patients with SCC. A total of 2,243 sites of distant metastasis were observed, the liver was the most common site of distant metastasis (727, 32.4%), followed by the distant lymph nodes (637, 28.4%), lung (459, 20.5%), bone (344, 15.3%), and brain (76, 3.4%). Multivariable logistic regression showed that compared to patients with SCC, patients with AC were more likely to have metastasis to the brain (odds ratio [OR] 3.026, 95% confidence interval [CI] 1.441-6.357, p = 0.003) and liver (OR 1.848, 95% CI 1.394-2.451, p < 0.001), and less likely to have metastasis to the lung (OR 0.404, 95% CI 0.316-0.516, p < 0.001). Histological type had no effect on metastasis to the distant lymph nodes or bone. Conclusions: Patients with esophageal AC are more likely to present with liver and brain metastases, and less likely to present with lung metastasis than patients with esophageal SCC.

Tubular carcinomas of the breast: an epidemiologic study.

AIM: We explored the clinicopathologic characteristics, prognostic factors and outcomes in tubular carcinoma (TC) of the breast. METHODS: We retrospectively assessed 8091 TC patients using the SEER database from 2000 to 2013. RESULTS: Most patients were non-Hispanic white, well-differentiated disease, tumor size ≤2 cm, node-negative, nonmetastatic, hormone receptor-positive and HER2-negative status. The 10-year breast cancer-specific survival and overall survival were 98.1 and 82.0%, respectively. Multivariate analysis indicated that age, ethnicity, surgery procedures, radiotherapy and chemotherapy were independent predictors affecting survival outcomes. There was comparable breast cancer-specific survival between surgery and nonsurgery groups. CONCLUSION: The patients with TC has excellent survival outcomes, which may in part be due to the favorable tumor characteristics.

Long-term survival effect of the interval between mastectomy and radiotherapy in locally advanced breast cancer.

INTRODUCTION: The timing of postmastectomy radiotherapy (PMRT) may influence locoregional recurrence and survival outcomes. In this study, we assessed the long-term survival effect of the interval between surgery and PMRT in locally advanced breast cancer treated with mastectomy and adjuvant chemotherapy. METHODS: In this retrospective study, we included women with locally advanced breast cancer who underwent adjuvant chemotherapy and PMRT after mastectomy between 1999 and 2007. Based on the interval between surgery and PMRT, the patients were classified into three groups: Group 1 (≤4 vs >4 months), Group 2 (≤5 vs >5 months), and Group 3 (≤6 vs >6 months). Univariate and multivariate regression analyses were performed to determine the prognostic factors of survival outcomes. RESULTS: A total of 340 women were included in this study, and the median follow-up duration was 79.8 months. The median surgery-PMRT interval was 5 months. The surgery-PMRT interval including Group 1, Group 2, and Group 3 was not significantly associated with locoregional recurrence-free survival, distant metastasis-free survival, disease-free survival, and overall survival. In addition, in the subgroup analysis of the effect of surgery-PMRT interval on survival outcomes according to various clinicopathologic factors, the surgery-PMRT interval was also not associated with survival outcomes in different age groups, tumor stage, and breast cancer subtypes. CONCLUSION: Our findings suggest that the delay in the start of PMRT in locally advanced breast cancer does not increase the likelihood of locoregional recurrence, distant metastasis, and death.

Omission of Postoperative Radiotherapy in Women Aged 65 Years or Older With Tubular Carcinoma of the Breast After Breast-Conserving Surgery.

INTRODUCTION: To investigate the temporal trends of postoperative radiotherapy (RT) administration and the effects of omitting postoperative RT on breast cancer-specific survival (BCSS) in women aged ≥65 years with tubular carcinoma (TC) of the breast who received breast-conserving surgery (BCS). METHODS: We included women aged ≥65 years with non-metastatic TC of the breast who underwent BCS between 2000 and 2013 using the Surveillance, Epidemiology, and End Results database. Statistical analyses were performed using chi-square tests, Kaplan-Meier analyses, Cox proportional hazards models, and a 1:1 propensity score matching (PSM). RESULTS: Before PSM, a total of 1,475 patients with tumor size ≤2 cm, node-negative disease, and estrogen receptor-positive disease were identified, including 927 (62.8%) underwent postoperative RT and 548 (37.2%) had postoperative omission of RT. The administration of postoperative RT steadily declined over the study period. Patients with younger age, larger tumor size, and other race/ethnicity were more likely to receive postoperative RT. The median follow-up duration was 85.0 months, the 5- and 10-year BCSS rates were 98.7 and 97.9%, respectively. The median BCSS was 161.9 and 165.0 months for patients with and without postoperative RT, respectively, and the corresponding 5-year BCSS rates were 98.5 and 98.8%, respectively (p = 0.134). Prognostic analysis indicated that postoperative RT was not associated with improved BCSS rates compared with RT omission (p = 0.134). After PSM, a total of 431 complete pairs were generated. In the matched population, the 5-year BCSS rates were 98.6 and 98.4% in non-postoperative RT and postoperative RT groups, respectively (p = 0.858). The univariate analyses also confirmed that the administration of postoperative RT was not associated with better BCSS (p = 0.858). CONCLUSION: The incidence of breast cancer-related death is probably sufficiently low to avoid postoperative RT in women aged ≥65 years with TC of the breast after BCS.

Lymph node ratio has prognostic value related to the number of positive lymph nodes in patients with vulvar cancer.

AIM: We investigated the value of the number of positive lymph nodes (PLNs) and lymph node ratio (LNR) on survival of vulvar cancer patients. METHODS: A total of 2332 patients with vulvar squamous cell carcinoma were included from the SEER program. RESULTS: In multivariate analysis, the number of PLNs and LNR were independent prognostic indictors of survival outcomes, a higher number of PLNs and a higher LNR had poorer survival outcomes. An LNR >0.2 was associated with poor survival outcomes according to the number of PLNs. CONCLUSION: The LNR has prognostic value related to the number of PLNs and may allow a more accurate determination of the lymph node status of vulvar cancer patients.

Widowed status increases the risk of death in vulvar cancer.

AIM: To evaluate the effect of marital status on survival of patients with vulvar cancer. MATERIALS & METHODS: A total of 4001 patients with vulvar cancer were included from the SEER database. Statistical analyses were performed using χ2 test, Kaplan-Meier method, Cox regression proportional hazards and a 1:1 propensity score-matching. RESULTS: The 8-year vulvar cancer-related survival in married, divorced, single and widowed patients were 78.6, 82.2, 78.9 and 61.6%, respectively (p < 0.001). In multivariate analysis, widows patients had significantly worse vulvar cancer survival than the nonwidowed counterparts in unmatched and matched populations. CONCLUSION: Being widowed is associated with greater risk of vulvar cancer mortality than the nonwidowed counterparts.