Photocatalytic CO2 Reduction to Solar Fuels by a Chemically Stable Bimetallic Porphyrin-Based Framework.

Porphyrin-based photocatalysts have emerged as promising candidates for facilitating carbon dioxide (CO2) reduction due to their exceptional light-harvesting properties. However, their performance is hindered by complex synthesis procedures, limited structural stability, inadequate CO2 activation capabilities, and a lack of comprehensive structure-property relationships. This study investigates the performance of a porphyrin-based bimetallic framework, [Cu(TPP)Cu2Mo3O11] (TPP = tetrapyridylporphyrin), termed MoCu-1 for photocatalytic CO2 reduction. In addition to its straightforward one-pot synthesis method, the framework shows remarkable chemical stability, particularly notable in alkaline reaction conditions, making it a compelling option for sustainable catalytic applications. By harnessing the superior photoabsorption properties of the porphyrin linker and the abundance of catalytic sites provided by the bimetallic structure, this framework exhibits the potential for enhancing CO2 reduction efficiency. MoCu-1 demonstrates excellent activity in converting CO2 into CO, achieving a maximum yield of 3.21 mmol g-1 with a selectivity of ∼93%. We unravel the intricate interplay of structural features and catalytic activity through systematic characterization techniques and an in situ diffuse reflectance Fourier transform study, which provided insights into the mechanism governing CO2 conversion and was supported by density functional theory calculations. This work contributes to advancing our understanding of photocatalytic processes and offers guidance for designing robust materials for CO2 utilization in renewable energy applications.

Assessment of Plasma Cystatin C as a Marker of Acute Renal Injury in Patients Undergoing Extracorporeal Shock Wave Lithotripsy for Renal Stone Disease.

Introduction This study aimed to assess plasma cystatin C (CysC) as a marker of acute kidney injury (AKI) in patients undergoing extracorporeal shock wave lithotripsy (ESWL). We compared serum levels of CysC, C-reactive protein (CRP), and creatinine before and after ESWL. The study results may have implications for early detection of AKI and prevention of progression to chronic kidney disease. Methodology This prospective observational study included 105 adult participants and was conducted from August 2022 to July 2024. ESWL was the only modality of treatment. Results Forty-eight (46%) patients developed AKI after ESWL. Patients with AKI had significantly higher post-ESWL mean plasma CysC levels than patients without AKI (121 ± 0.25 vs. 0.94 ± 0.22 mg/dL, respectively; P = 0.001). The mean serum CRP levels after ESWL were significantly higher in patients who developed AKI compared with those who did not (4.36 ± 1.63 vs. 2.64 ± 0.95 mg/dL, respectively; P = 0.001). Conclusions In patients with renal stone disease, serum creatinine, serum CRP, and plasma CysC can be used as markers of acute renal injury after ESWL.

Photocatalytic decarboxylation of free carboxylic acids and their functionalization.

Visible light mediated decarboxylative functionalization of carboxylic acids and their derivatives has recently emerged as a novel and powerful toolkit for small molecule activation in diverse carbon-carbon and carbon-hetero bond forming reactions. Naturally abundant highly functionalized bench-stable carboxylic acid analogs have been employed as promising alternatives to non-trivial organometallic reagents for mild and eco-benign synthetic transformation with traceless CO2 by-products. In this highlight article, we focus on the development of various photodecarboxylative functionalization strategies along with intra/inter-molecular cyclization via concerted single electron transfer (SET) or energy transfer (ET) pathways. Moreover, widely explored carboxylic acids are systematically classified here into four categories; i.e., α-keto, aliphatic, α,ß-unsaturated, and aromatic analogs for a concise overview to the readership. The association of decarboxylative radical species with coupling partners to construct C-C and C-N/O/S/P/X bonds for each analogous acid has been presented in brief.

Low Serum Testosterone as a Poor Prognostic Marker in Urethral Stricture: A Single-Center Prospective Longitudinal Study.

Introduction Androgens play a key role in modulating periurethral and preputial vascularity, cavernosal smooth muscle integrity, and penile growth. As a result, low testosterone may adversely affect the severity and outcome of urethral stricture patients. So, to find out the hormonal influence on the clinical outcome of urethral stricture we conducted a prospective longitudinal study at our institute. Methods The study was conducted at the Department of Urology, Institute of Post Graduate Medical Education & Research (IPGMER), Kolkata, India, from February 2023 to September 2023. This study was approved by the Institutional Ethics Committee at IPGMER, Kolkata with the approval number IPGMER/IEC/2023/436. Hormonal levels in patients with diagnosed non-traumatic urethral stricture were compared with patients without stricture. Patients with any overt hormonal abnormality or androgen-secreting tumor were excluded. A morning 10 cc blood sample was collected for testosterone, follicle-stimulating hormone, luteinizing hormone, and thyroid-stimulating hormone. The association of hormonal levels was measured in both groups and compared statistically. Any association of hypogonadism (testosterone <300 ng/dL) with respect to length, severity, and recurrence of urethral stricture was also studied. Results Forty patients with urethral stricture and same number of patients without stricture were included in the study. The mean testosterone level was found to be significantly low in patients with stricture (386 ng/dL vs 660 ng/dL). The age-wise distribution also showed low mean testosterone compared to patients without stricture. The incidence of hypogonadism is also found to be higher in stricture patients (47.5% vs 27.5%). It was also observed low testosterone is more prevalent in pan-anterior stricture (10/40) and long-segment stricture(>2 cm). Patients with stricture were also followed up for 6 months for recurrence of symptoms. Thirteen patients had recurrence. Patients with recurrence had significantly low serum testosterone (272 ng/dL vs 440 ng/dL). Conclusion Our study documented stricture patients with low serum testosterone have poor outcomes. Low testosterone level is strongly associated with longer stricture and increased risk of stricture recurrence.

Insights into the mechanism of peptide fibril growth on gold surface.

Understanding the formation of ß-fibrils over the gold surface is of paramount interest in nano-bio-medicinal Chemistry. The intricate mechanism of self-assembly of neurofibrillogenic peptides and their growth over the gold surface remains elusive, as experiments are limited in unveiling the microscopic dynamic details, in particular, at the early stage of the peptide aggregation. In this work, we carried out equilibrium molecular dynamics and enhanced sampling simulations to elucidate the underlying mechanism of the growth of an amyloid-forming sequence of tau fragments over the gold surface. Our results disclose that the collective intermolecular interactions between the peptide chains and peptides with the gold surface facilitate the peptide adsorption, followed by integration, finally leading to the fibril formation.

Pressure Induces Six-fold Coordination for the Lighter Pnictides Phosphorus and Arsenic Triiodide.

In this study, we employ an evolutionary algorithm in conjunction with first-principles density functional theory (DFT) calculations to comprehensively investigate the structural transitions, electronic properties, and chemical bonding behaviors of XI3 compounds, where X denotes phosphorus (P) and arsenic (As), across a range of elevated pressures. Our computational analyses reveal a distinctive phenomenon occurring under compression, wherein the initially trigonal structures of PI3 (P 63) and AsI3 (R-3) undergo an intriguing transformation, leading to the emergence of six-coordinated monoclinic phases (C2/m) at 6 GPa and 2 GPa for PI3 and AsI3, respectively. These high-pressure phases exhibit their stability up to 10 GPa for PI3 and 12 GPa for AsI3. Notably, the resulting structures at elevated pressures bear striking resemblance to the widely recognized six-coordinated octahedral BiI3 crystal configuration observed at ambient conditions. Our investigation further underscores the pivotal role of pressure-induced reactivity of the lone-pair electrons in PI3 and AsI3, facilitating their enhanced stereochemical reactivity and thereby enabling higher six-fold coordination. Complementary analyses employing electron localization function (ELF) and density of states (DOS) effectively delineate the progression towards augmented coordination in PI3 and AsI3 with increasing pressure. While the phenomenon of heightened coordination is conventionally associated with heavier pnictide iodides such as SbI3 and BiI3 under ambient conditions due to heightened ionic character and relativistic effects in bismuth (Bi) and antimony (Sb), our findings accentuate that analogous structural transformations can also be induced in lighter elements like phosphorus (P) and arsenic (As) under the influence of pressure.

Thiuram Disulfide Mediated Cu-Catalyzed Amidation of Terminal Alkynes: An Efficient Synthesis of Alkynyl Amides.

Terminal alkynes undergo a CO-free aminocarbonylation reaction mediated by thiuram disulfides. Thiuram disulfide acts as the source of the carbamoyl group in the amidation of terminal alkynes in the presence of copper-based reagent and catalyst. A series of alkynyl amides has been prepared with several structural variations following the current one-pot two-step protocol. The reaction proceeds through a mixed disulfide intermediate, which has been isolated and characterized by single-crystal XRD analysis.

Merging Photocatalytic Doubly-Decarboxylative Csp 2 -Csp 2 Cross-Coupling for Stereo-Selective (E)-α,ß-Unsaturated Ketones Synthesis.

A photocatalytic domain of doubly decarboxylative Csp 2 -Csp 2 cross coupling reaction is disclosed. Merging iridium and palladium photocatalysis manifested carbon-carbon bonds in a tandem dual-radical pathway. Present catalytic platform efficiently cross-coupled α, ß-unsaturated acids and α-keto acids to afford a variety of α, ß-unsaturated ketones with excellent (E)-selectivity and functional group tolerance. Mechanistically, photocatalyst implicated through reductive quenching cycle whereas cross coupling proceeded over one electron oxidative pallado-cycle.

Changes in renal volume post Percutaneous nephrolithotomy based on ultrasonography and its correlation with glomerular filtration rate (GFR).

INTRODUCTION: Percutaneous nephrolithotomy (PCNL) is considered to be the gold standard management for renal calculi. The purpose of this study is to comprehend the overall alterations in renal volume occurring after PCNL. The changes in the kidney's total volume in individual patients will be examined by ultrasonography pre and postoperatively, and it will be correlated with GFR. MATERIALS AND METHODS: It was a prospective observational study performed over 70 participants, conducted at the department of Urology of a tertiary care hospital in Eastern India. Each patients were evaluated with pre and post PCNL USG for kidney volume and GFR. The data was statistically evaluated by SPSS software. RESULTS: The preoperative and post operative calculated mean GFR was 96.030 ± 18.922 ml and 86.681 ± 16.938 ml,volume was 127.258 ± 25.705 and 123,678 ± 26.357 respectively . There was statistically significant decrease in GFR and volume following PCNL. It also shows that patients who underwent single puncture PCNL had significantly less decrease in GFR and kidney volume compared to multiple puncture PCNL. Moreover, the calculated mean change in GFR and volume were significantly less seen in single puncture-one step dilatation and single puncture-serial dilatation as compared to multiple puncture-one step dilatation and multiple puncture-serial dilatation. CONCLUSION: Our study showed that there was significant changes in the renal volume and GFR following PCNL . So, a sonographic estimation of renal dimensions and GFR calculation after PCNL will help in the prognosis and further follow up of patients. A Single puncture had a better operative outcome and less adverse consequences with respect to GFR, volume change and for renal function as compared to multiple puncture.

Base-Promoted Tandem Pathway for Keto-Amides: Visible Light-Mediated Room-Temperature Amidation Using Molecular Oxygen as an Oxidant.

Herein, we report metal- and photocatalyst-free room-temperature amidation for α-ketoamide synthesis from feedstock phenacyl bromides and amines using molecular oxygen as an oxidant as well as a source of oxygen in the amide segment. Visible light-mediated base-promoted one-pot sequential C-N/C═N/C═O bond formation takes place in a tandem manner to afford the desired product. Functional group tolerance (benzylic alcohol, keto, cyano, nitro, halo, etc.), a broad substrate scope, and gram-scale synthesis make this synthetic methodology more attractive. We have observed that electron-rich aromatic amines, aliphatic amines, and phenacyl bromide derivatives proceeded the present transformation with marginally superior reactivity in comparison to electron-deficient aromatic amines and phenacyl bromide derivatives. Moreover, several control experiments, in situ isolation of secondary amine and imine as key intermediates, and 18O-labeling experiments provide complete insight into the mechanism of the tandem pathway.

Intratumoral PD1+CD38+Tim3+ CD8+ T Cells in Pre-BCG Tumor Tissues Are Associated with Poor Responsiveness to BCG Immunotherapy in Patients with Non-Muscle Invasive Bladder Cancer.

Intravesical immunotherapy with Bacillus Calmette-Guerin (BCG) is a standard of care therapy for non-muscle invasive bladder cancer (NMIBC), which accounts for about 75% of newly diagnosed urothelial cancer. However, given the frequent recurrence and progression, identification of a pre-treatment biomarker capable of predicting responsiveness to BCG in NMIBC is of utmost importance. Herein, using multiparametric flow cytometry, we characterized CD8+ T cells from peripheral blood and tumor tissues collected from 27 pre-BCG patients bearing NMIBC to obtain immune correlates of bladder cancer prognosis and responsiveness to BCG therapy. We observed that intratumoral CD8+ T cell subsets were highly heterogenous in terms of their differentiation state and exist at different proportions in tumor tissues. Remarkably, among the different CD8+ T cell subsets present in the tumor tissues, the frequency of the terminally exhausted-like CD8+ T cell subset, marked as PD1+CD38+Tim3+ CD8+ T cells, was inversely correlated with a favorable outcome for patients and a responsiveness to BCG therapy. Moreover, we also noted that the intratumoral abundance of the progenitor exhausted-like PD1+CD8+ T cell subset in pre-BCG NMIBC tumor tissues was indicative of better recurrence-free survival after BCG. Collectively, our study led to the identification of biomarkers that can predict the therapeutic responsiveness of BCG in NMIBC.

Pd-Catalyzed Tandem Pathway for Stereoselective Synthesis of (E)-1,3-Enyne from ß-Nitroalkenes by Using a Sacrificial Directing Group.

The involvement of nitroalkenes instead of minimal one alkyne motif for (E)-1,3-enynes synthesis through a palladium catalyzed stereoselective bond forming pathway at room temperature is presented. Implication of nitro group as a sacrificial directing group, formation of magical alkyne on a newly developed Csp 3 -Csp 3 bond with initial palladium-MBH adduct make this methodology distinctive. This protocol features an unprecedented sequential acetate addition, carbon-carbon bond formation, isomerization of double bond and nitromethane degradation in a tandem catalytic walk via dancing hybridization. Mechanistic understanding through identification of intermediates and computational calculations furnishes complete insight into the tandem catalytic pathway. Broad substrates scope and functional groups tolerance make this synthetic methodology magnificent and dynamic. This represents the first example of stereoselective 1,3-enyne synthesis exclusively from alkene substrates by introducing the concept of sacrificial directing group.

Biaxial negative thermal expansion in carbon nets - graphyne and derivatives.

Materials that shrink during heating are important for advanced applications. Graphene has shown negative thermal expansion (NTE) up to 1000 K, which drives further research towards new two-dimensional allotropes of carbon to achieve higher performance. In this article, we have shown high NTE for Graphynes having sp-sp connectivity and that are stable at high temperature. The effect of heteroatom substitution in NTE for some graphynes and their periodic trends are also studied. Quasi-harmonic approximation (QHA) calculations show that thermal expansion remains negative at least until 1000 K for some graphynes. The results are in good agreement with ab-initio molecular dynamics (AIMD) simulations. The high NTE in the graphynes is understood based on their rigid unit modes (RUMs).

Collective Variables for Crystallization Simulations-from Early Developments to Recent Advances.

Crystallization is an important physicochemical process which has relevance in material science, biology, and the environment. Decades of experimental and theoretical efforts have been made to understand this fundamental symmetry-breaking transition. While experiments provide equilibrium structures and shapes of crystals, they are limited to unraveling how molecules aggregate to form crystal nuclei that subsequently transform into bulk crystals. Computer simulations, mainly molecular dynamics (MD), can provide such microscopic details during the early stage of a crystallization event. Crystallization is a rare event that takes place in time scales much longer than a typical equilibrium MD simulation can sample. This inadequate sampling of the MD method can be easily circumvented by the use of enhanced sampling (ES) simulations. In most of the ES methods, the fluctuations of a system's slow degrees of freedom, called collective variables (CVs), are enhanced by applying a bias potential. This transforms the system from one state to the other within a short time scale. The most crucial part of such CV-based ES methods is to find suitable CVs, which often needs intuition and several trial-and-error optimization steps. Over the years, a plethora of CVs has been developed and applied in the study of crystallization. In this review, we provide a brief overview of CVs that have been developed and used in ES simulations to study crystallization from melt or solution. These CVs can be categorized mainly into four types: (i) spherical particle-based, (ii) molecular template-based, (iii) physical property-based, and (iv) CVs obtained from dimensionality reduction techniques. We present the context-based evolution of CVs, discuss the current challenges, and propose future directions to further develop effective CVs for the study of crystallization of complex systems.

Ion-Mediated Protein Stabilization on Nanoscopic Surfaces.

The emergence of nanoparticles in biomedical applications has made their interactions with proteins inevitable. Nanoparticles conjugated with proteins and peptide-based constructs form an integral part of nanotherapeutics and have recently shown promise in treating a myriad of diseases. The proper functioning of proteins is critical to achieve their biological functions. However, interface issues result in the denaturation of proteins, and the loss of orientation and steric hindrance can adversely affect the function of the conjugate. Furthermore, surface-induced denaturation also triggers protein aggregation, resulting in amyloid-like species. Understanding the mechanistic underpinnings of protein-nanoparticle interactions and controlling their interfacial characteristics are critical and challenging due to the complex nature of the conjugates. In this milieu, we demonstrate that ionic liquids can be suitable candidates for stabilizing protein-nanoparticle interactions by virtue of their excellent protein-preserving properties. We also probe the previously unexplored mechanism of ion-mediated stabilization of the protein molecules on the nanoparticle surface. The protein-nanoparticle conjugates consist of lysozyme and choline-based ionic liquids characterized by optical and electron microscopy techniques combined with surface-sensitive plasmon-enhanced Raman spectroscopy. Furthermore, atomistic molecular dynamics simulations of the conjugates delineate interfacial interactions of the protein molecules and the modulation by the ions, particularly the conformational changes and the dynamic correlation when the protein and specific ionic liquid molecules are adsorbed on the nanoparticle surface. The combined experimental and computational studies showed the synergistic behavior of the ions of the ionic liquids, specifically the orientation and coverage of the anions aided by the cations to control the surface interactions and hence the overall protein stability. These studies pave the way for using ionic liquids, particularly their biocompatible counterparts in nanoparticle-based complexes, as stabilizing agents for biomedical applications.

Merging Photocatalytic C-O Cross-Coupling for α-Oxycarbonyl-ß-ketones: Esterification of Carboxylic Acids via a Decarboxylative Pathway.

Herein, the first merged photocatalytic pathway for the C-O cross-coupled esterification of carboxylic acids to α-oxycarbonyl-ß-ketones has been demonstrated. Decarboxylation of α,ß-unsaturated acids promotes the formation of the ß-ketone fragment of the desired product. Water as the source of oxygen for the ketone segment and aerial oxygen as an oxidant make the present synthetic methodology green and sustainable. This new C═O and C-O bond-forming methodology takes place in a cascade manner under a dual Ir/Pd-catalytic pathway, with the liberation of H2O and CO2 as the only byproducts.

Sexual dysfunction in female patients of reproductive age group with recurrent urinary tract infection-a cross-sectional study.

BACKGROUND: Sexually active female patients often present with urinary tract infection. Recurrent urinary tract infections negatively affect a patient's social and sexual life, leading to deterioration of overall life quality. OBJECTIVE: This study aimed to determine the prevalence of sexual dysfunction in recurrent urinary tract infection patients of reproductive age, and the association between recurrent urinary tract infections and sexual dysfunction. STUDY DESIGN: A total of 697 women of reproductive age with urinary tract infection attending a urology outdoor patient department in a tertiary-care center in eastern India were evaluated with a comprehensive history (including a validated questionnaire), physical examination, and relevant investigations. To assess sexual dysfunction and sexual distress profiles, the Female Sexual Function Index scale and the revised Female Sexual Distress Scale were used. RESULTS: Recurrent urinary tract infection was found in 143 of 697 (20.5%) patients. Women with recurrent urinary tract infection had a lower Female Sexual Function Index score (<26.55) and a higher Female Sexual Distress Scale score (>11), suggestive of sexual dysfunction, in 59.4% and 58.1% of cases, respectively (P<.001), whereas such scores were found among 22.6% and 19.1% of patients without recurrent urinary tract infection, respectively (P<.001). Relationship status and bowel history were independent predictors of Female Sexual Distress Scale score of >11. CONCLUSION: Nearly 60% of sexually active women of reproductive age with recurrent urinary tract infection had low Female Sexual Function Index and high Female Sexual Distress Scale scores, which are suggestive of sexual dysfunction. Thus, every patient with recurrent urinary tract infection should be evaluated for sexual dysfunction to improve quality of life.

Negative Thermal Expansion Induced in Tri-graphene and T-graphene by the Rigid-Unit Modes.

Materials which contract on heating (negative thermal expansion, NTE) are of significant interest for advanced applications. Graphene has shown NTE up to 1000 K, which motivates further improvements in two-dimensional carbon to attain superior performance. In this Communication, very large negative thermal expansion coefficients (αT) are reported for tri-graphene (TrG) and T-graphene (TG). Quasi-harmonic approximation calculations show that αT remains negative until 4200 K and 2900 K for TrG and TG, respectively. The high NTE for these systems is understood on the basis of the soft phonon modes, which induce rotation of the 3-membered and the 4-membered rings in TrG and TG, respectively, and ab initio molecular dynamics simulations. The local distortions for the 3-12 rings (in TrG) and 4-8 rings (in TG) have structural resemblance with the rigid-unit modes that are usually envisioned for bulk systems.

Bilateral giant adrenal myelolipoma: A rare scenario.

Adrenal myelolipoma is a benign tumor-like growth, composed of mature fat cells and bone marrow elements. We report a case of a 44-year lady who presented with a complaint of pain in the abdomen. The only positive finding was contrast-enhanced computed tomography (CECT) whole abdomen, which was suggestive of heterogeneously enhancing hypodense lesion of size 130 mm × 105 mm with few calcifications and 103 mm × 75 mm with intralesional fat attenuation in right and left adrenals. Rest laboratory parameters were normal. Only a few cases so far have been reported for bilateral adrenal myelolipoma but what stands out in our case is its giant size and bilaterality, managed surgically without any complications.

Sexual well-being and fertility in male renal transplant recipients: A study in a tertiary care centre.

INTRODUCTION: Sexual dysfunction is a common problem among chronic kidney disease (CKD) patients. The uraemia, comorbid conditions, hormonal disturbances, autonomic neuropathy, side effects of medication and psycho-social factors contribute to sexual dysfunction. These factors also affect fertility of CKD patients. It starts early in CKD and gradually deteriorates with time. Renal transplant corrects most of the issues and leads to improvement of sexual function which ultimately leads to improved fertility outcomes. METHODS: It was a cross sectional study performed in a single institution including 135 male renal transplant recipients. A questionnaire was used to evaluate the socio-economic status, fertility and developmental condition of the off-springs. The International index of erectile dysfunction (IIEF) was used for assessment of sexual well-being of the patient. The data were statistically analysed by SPSS 25.0 version. RESULTS: The mean age at transplant was 40.9 ± 9.9 years and the duration of haemodialysis received 13.6 ± 7.43 months. Among 135 recipients 63 (46.67%) desired but only 49 were successful to father a child. Upper middle class being the largest group to receive renal transplant also had the highest fertility rate in our study. The children born had no development anomaly. Sexual function improved in 85 patients, worsened in 15 and remain unchanged among 35 patients after renal transplant. Overall there was significant improvement in all five parameters of IIEF. CONCLUSION: Renal transplant corrects most of the metabolic abnormality as well gives a psychological boost to the CKD patients. These lead to improvement of sexual functions which in turn improves the fertility in renal transplant recipients. But the overall fertility rate among the male renal transplant recipients was comparable to the general population.