Nature of Nitrogen Incorporation in BiVO4 Photoanodes through Chemical and Physical Methods

In recent years, BiVO4 has been optimized as a photoanode material to produce photocurrent densities close to its theoretical maximum under AM1.5 solar illumination. Its performance is, therefore, limited by its 2.4 eV bandgap. Herein, nitrogen is incorporated into BiVO4 to shift the valence band position to higher energies and thereby decreases the bandgap. Two different approaches are investigated: modification of the precursors for the spray pyrolysis recipe and post-deposition nitrogen ion implantation. Both methods result in a slight red shift of the BiVO4 bandgap and optical absorption onset. Although previous reports on N-modified BiVO4 assumed individual nitrogen atoms to substitute for oxygen, X-ray photoelectron spectroscopy on the samples reveals the presence of molecular nitrogen (i.e., N-2). Density functional theory calculations confirm the thermodynamic stability of the incorporation and reveal that N-2 coordinates to two vanadium atoms in a bridging configuration. Unfortunately, nitrogen incorporation also results in the formation of a localized state of approximate to 0.1 eV below the conduction band minimum of BiVO4, which suppresses the photoactivity at longer wavelengths. These findings provide important new insights on the nature of nitrogen incorporation into BiVO4 and illustrate the need to find alternative lower-bandgap absorber materials for photoelectrochemical energy conversion applications

The power of quantum systems on a line

We study the computational strength of quantum particles (each of finite dimensionality) arranged on a line. First, we prove that it is possible to perform universal adiabatic quantum computation using a one-dimensional quantum system (with 9 states per particle). This might have practical implications for experimentalists interested in constructing an adiabatic quantum computer. Building on the same construction, but with some additional technical effort and 12 states per particle, we show that the problem of approximating the ground state energy of a system composed of a line of quantum particles is QMA-complete; QMA is a quantum analogue of NP. This is in striking contrast to the fact that the analogous classical problem, namely, one-dimensional MAX-2-SAT with nearest neighbor constraints, is in P. The proof of the QMA-completeness result requires an additional idea beyond the usual techniques in the area: Not all illegal configurations can be ruled out by local checks, so instead we rule out such illegal configurations because they would, in the future, evolve into a state which can be seen locally to be illegal. Our construction implies (assuming the quantum Church-Turing thesis and that quantum computers cannot efficiently solve QMA-complete problems) that there are one-dimensional systems which take an exponential time to relax to their ground states at any temperature, making them candidates for being one-dimensional spin glasses.Comment: 21 pages. v2 has numerous corrections and clarifications, and most importantly a new author, merged from arXiv:0705.4067. v3 is the published version, with additional clarifications, publisher's version available at http://www.springerlink.co

Preconditioned Conjugate Gradient Algorithms for Homotopy CurveTracking

These are alogorithms for finding zeros or fixed points of nonlinear systems of equations that are globally convergent for almost all starting points, i.e., with probability one. The essence of all such algorithms is the construction of an appropriate homotopy map and then tracking some smooth curve in the zero set of this homotopy map. HOMPACK is a mathematical software package implementing globally convergent homotopy algorithms with three different techniques for tracking a homotopy zero curve, and has separate routines for dense and sparse Jacobian Matrices. The HOMPACK alogorithms for sparse Jacobian matrices use a preconditioned conjugate gradient algorithm for the computation of the kernel of the homotopy Jacobian matrix, a required linear algebra step for homotopy curve tracking. Here variants of the conjugate gradient algorithms are implemented in the context of homotopy curve tracking and compared with Craig's preconditioned conjugate gradient method used in HOMPACK. The test problems used include actual large scale, sparse structural mechanics problems

Experiments with Conjugate Gradient Algorithms for Homotopy Curve Tracking

There are algorithms for finding zeros or fixed points of nonlinear systems of equations that are globally convergent for almost all starting points, i.e., with probability one. The essence of all such algorithms is the construction of an appropriate homotopy map and then tracking some smooth curve in the zero set of this homotopy map. HOMPACK is a mathematical software package implementing globally convergent homotopy algorithms with three different techniques for tracking a homotopy zero curve, and has separate routines for dense and sparse Jacobian matrices. The HOMPACK algorithms for sparse Jacobian matrices use a preconditioned conjugate gradient algorithm for the computation of the kernal of the homotopy Jacobian matrix, a required linear algebra step for homotopy curve tracking. Here variants of the conjugate gradient algorithm are implemented in the context of homotopy curve tracking and compared with Craig's preconditioned conjugate gradient method used in HOMPACK. The test problems used include actual large scale, sparse structural mechanics problems

Distinct Hypothalamic Neurons Mediate Estrogenic Effects on Energy Homeostasis and Reproduction

SummaryEstrogens regulate body weight and reproduction primarily through actions on estrogen receptor-α (ERα). However, ERα-expressing cells mediating these effects are not identified. We demonstrate that brain-specific deletion of ERα in female mice causes abdominal obesity stemming from both hyperphagia and hypometabolism. Hypometabolism and abdominal obesity, but not hyperphagia, are recapitulated in female mice lacking ERα in hypothalamic steroidogenic factor-1 (SF1) neurons. In contrast, deletion of ERα in hypothalamic pro-opiomelanocortin (POMC) neurons leads to hyperphagia, without directly influencing energy expenditure or fat distribution. Further, simultaneous deletion of ERα from both SF1 and POMC neurons causes hypometabolism, hyperphagia, and increased visceral adiposity. Additionally, female mice lacking ERα in SF1 neurons develop anovulation and infertility, while POMC-specific deletion of ERα inhibits negative feedback regulation of estrogens and impairs fertility in females. These results indicate that estrogens act on distinct hypothalamic ERα neurons to regulate different aspects of energy homeostasis and reproduction

Exponential Decay of Correlations Implies Area Law

We prove that a finite correlation length, i.e. exponential decay of correlations, implies an area law for the entanglement entropy of quantum states defined on a line. The entropy bound is exponential in the correlation length of the state, thus reproducing as a particular case Hastings proof of an area law for groundstates of 1D gapped Hamiltonians. As a consequence, we show that 1D quantum states with exponential decay of correlations have an efficient classical approximate description as a matrix product state of polynomial bond dimension, thus giving an equivalence between injective matrix product states and states with a finite correlation length. The result can be seen as a rigorous justification, in one dimension, of the intuition that states with exponential decay of correlations, usually associated with non-critical phases of matter, are simple to describe. It also has implications for quantum computing: It shows that unless a pure state quantum computation involves states with long-range correlations, decaying at most algebraically with the distance, it can be efficiently simulated classically. The proof relies on several previous tools from quantum information theory - including entanglement distillation protocols achieving the hashing bound, properties of single-shot smooth entropies, and the quantum substate theorem - and also on some newly developed ones. In particular we derive a new bound on correlations established by local random measurements, and we give a generalization to the max-entropy of a result of Hastings concerning the saturation of mutual information in multiparticle systems. The proof can also be interpreted as providing a limitation on the phenomenon of data hiding in quantum states.Comment: 35 pages, 6 figures; v2 minor corrections; v3 published versio

Plasmonic excitations in noble metals: The case of Ag

The delicate interplay between plasmonic excitations and interband transitions in noble metals is described by means of {\it ab initio} calculations and a simple model in which the conduction electron plasmon is coupled to the continuum of electron-hole pairs. Band structure effects, specially the energy at which the excitation of the $d$-like bands takes place, determine the existence of a subthreshold plasmonic mode, which manifests itself in Ag as a sharp resonance at 3.8 eV. However, such a resonance is not observed in the other noble metals. Here, this different behavior is also analyzed and an explanation is provided.Comment: 9 pages, 8 figure

Association of patients' sex with treatment outcomes after intravesical bacillus Calmette-Guérin immunotherapy for T1G3/HG bladder cancer.

Purpose: To investigate the association of patients' sex with recurrence and disease progression in patients treated with intravesical bacillus Calmette-Guérin (BCG) for T1G3/HG urinary bladder cancer (UBC). Materials and methods: We analyzed the data of 2635 patients treated with adjuvant intravesical BCG for T1 UBC between 1984 and 2019. We accounted for missing data using multiple imputations and adjusted for covariate imbalance between males and females using inverse probability weighting (IPW). Crude and IPW-adjusted Cox regression analyses were used to estimate the hazard ratios (HR) with their 95% confidence intervals (CI) for the association of patients' sex with HG-recurrence and disease progression. Results: A total of 2170 (82%) males and 465 (18%) females were available for analysis. Overall, 1090 (50%) males and 244 (52%) females experienced recurrence, and 391 (18%) males and 104 (22%) females experienced disease progression. On IPW-adjusted Cox regression analyses, female sex was associated with disease progression (HR 1.25, 95%CI 1.01-1.56, p = 0.04) but not with recurrence (HR 1.06, 95%CI 0.92-1.22, p = 0.41). A total of 1056 patients were treated with adequate BCG. In these patients, on IPW-adjusted Cox regression analyses, patients' sex was not associated with recurrence (HR 0.99, 95%CI 0.80-1.24, p = 0.96), HG-recurrence (HR 1.00, 95%CI 0.78-1.29, p = 0.99) or disease progression (HR 1.12, 95%CI 0.78-1.60, p = 0.55). Conclusion: Our analysis generates the hypothesis of a differential response to BCG between males and females if not adequately treated. Further studies should focus on sex-based differences in innate and adaptive immune system and their association with BCG response

RISK FACTORS FOR RESIDUAL DISEASE AT RE-TUR IN T1G3 BLADDER CANCER

INTRODUCTION AND OBJECTIVES: Goals of transurethral resection of a bladder tumour (TUR) are to completely resect the lesions and to make a correct diagnosis in order to adequately stage the patient. It is well known that the presence of detrusor muscle in the specimen is a prerequisite to minimize the risk of under staging. Persistent disease after resection of bladder tumours is not uncommon and is the reason why the European Guidelines recommended a reTUR for all T1 tumours. It was recently published that when there is muscle in the specimen, re-TUR does not influence progression or cancer specific survival. We present here the patient and tumour factors that may influence the presence of residual disease at re-TUR. METHODS: In our retrospective cohort of 2451 primary T1G3 patients initially treated with BCG, pathology results for 934 patients (38.1%) who underwent re-TUR are available. 75.4% had multifocal tumours, 42.7% of tumours were more than 3 cm in diameter and 25.8% had concomitant CIS. We analyse this subgroup of patients who underwent re-TUR: there was no residual disease in 267 patients (28.6%) and residual disease in 667 patients (71.4%): Ta in 378 (40.5%) and T1 in 289 (30.9%) patients. Age, gender, tumour status (primary/recurrent), previous intravesical therapy, tumour size, tumour multi-focality, presence of concomitant CIS, and muscle in the specimen were analysed in order to evaluate risk factors of residual disease at re-TUR, both in univariate analyses and multivariate logistic regressions. RESULTS: The following were not risk factors for residual disease: age, gender, tumour status and previous intravesical chemotherapy. The following were univariate risk factors for presence of residual disease: no muscle in TUR, multiple tumours, tumours > 3 cm, and presence of concomitant CISDue to the correlation between tumor multi-focality and tumor size, the multivariate model retained either the number of tumors or the tumor diameter (but not both), p < 0.001. The presence of muscle in the specimen was no longer significant, p ¼ 0.15, while the presence of CIS only remained significant in the model with tumor size, p < 0.001. CONCLUSIONS: The most significant factors for a higher risk of residual disease at re-TUR in T1G3 patients are multifocal tumours and tumours more than 3 cm. Patients with concomitant CIS and those without muscle in the specimen also have a higher risk of residual disease

Active surveillance in renal transplant patients with prostate cancer: a multicentre analysis

Introduction: Due to medical improvements leading to increased life expectancy after renal transplantation and widened eligibility criteria allowing older patients to be transplanted, incidence of (low-risk) prostate cancer (PCa) is increasing among renal transplant recipients (RTR). It remains to be established whether active surveillance (AS) for PCa represents a safe treatment option in this setting. Therefore, we aim to compare AS discontinuation and oncological outcomes of AS for PCa of RTR vs. non-transplant patients. Methods: Multicentre study including RTR diagnosed with PCa between 2008 and 2018 in whom AS was initiated. A subgroup of non-RTR from the St. Antonius hospital AS cohort was used as a control group. Comparison of RTR vs. non-RTR was performed by 2:1 propensity score matched survival analysis. Outcome measures included tumour progression-free survival, treatment-free survival, metastasis rates, biochemical recurrence rates and overall survival. Patients were matched based on age, year of diagnosis, PSA, biopsy ISUP grade group, relative number of positive biopsy cores and clinical stage. Results: A total of 628 patients under AS were evaluated, including 17 RTRs and 611 non-RTRs. A total of 13 RTR cases were matched with 24 non-RTR cases. Median overall follow-up for the RTR and non-RTR matched cases was, respectively, 5.1 (IQR 3.2–8.7) years and 5.7 (IQR 4.8–8.1) years. There were no events of metastasis and biochemical recurrence among matched cases. The matched-pair analysis results in a 1-year and 5-year survival of the RTR and non-RTR patients were, respectively, 100 vs. 92%, and 39 vs. 76% for tumour progression, 100 vs. 91% and 59 vs. 76% for treatment-free survival and, respectively, 100 vs. 100% and 88 vs. 100% for overall survival. No significant differences in tumour progression-free survival (p = 0.07) and treatment-free survival were observed (p = 0.3). However, there was a significant difference in overall survival comparing both groups (p = 0.046). Conclusions: AS may be carefully considered in RTR with low-risk PCa. In our preliminary analysis, no major differences were present in AS outcomes between RTR and non-RTR. Overall mortality was significantly higher in the RTR subgroup