Proximity-Enabled Photochemical C-H Functionalization using a Covalent Organic Framework-Confined Fe2IV-µ-oxo Species in Water.

Water has been recognized as an excellent solvent for maneuvering both the catalytic activity and selectivity, especially in the case of heterogeneous catalysis. However, maintaining the active catalytic species in their higher oxidation states (IV/V) while retaining the catalytic activity and recyclability in water is an enormous challenge. Herein, we have developed a solution to this problem using covalent organic frameworks (COFs) to immobilize the (Et4N)2[FeIII(Cl)bTAML] molecules, taking advantage of the COF's morphology and surface charge. By using the visible light and [CoIII(NH3)5Cl]Cl2 as a sacrificial electron acceptor within the COF, we have successfully generated and stabilized the [(bTAML)FeIV-O-FeIV(bTAML)]- species in water. The COF backbone simultaneously acts as a porous host and a photosensitizer. This is the first time that the photochemically generated Fe2IV-µ-oxo radical cation species has demonstrated high catalytic activity with moderate to high yield for the selective oxidation of the unactivated C-H bonds, even in water. To enhance the catalytic activity and achieve good recyclability, we have developed a TpDPP COF film by transforming the TpDPP COF nanospheres. We have achieved the regio- and stereoselective functionalization of unactivated C-H bonds of alkanes and alkenes (3°:2° = 102:1 for adamantane with the COF film), which is improbable in homogeneous conditions. The film exhibits C-H bond oxidation with higher catalytic yield (32-98%) and a higher degree of selectivity (cis/trans = 74:1; 3°:2° = 100:1 for cis-decalin).

The Double-Edged Sword of AI in Biomedical Engineering: ChatGPT's Controversial Impact on Research and Collaboration Paradigms.

As artificial intelligence (AI) permeates various fields, ChatGPT emerges as a contentious force in biomedical engineering, stirring both excitement and concern. This letter explores the disruptive potential and controversial implications of ChatGPT on research, collaboration, and the future of the field. By presenting thought-provoking questions and confronting divisive issues, we aim to spark a lively debate on the responsible integration of AI technology in biomedical engineering while safeguarding the essence of human expertise.

AI Tackles Pandemics: ChatGPT's Game-Changing Impact on Infectious Disease Control.

Unleashing the power of artificial intelligence (AI), this letter delves into the potential applications of ChatGPT, a cutting-edge language model, in the management and control of infectious diseases. By examining ChatGPT's contributions to information dissemination, diagnosis, treatment, and research, the article underscores its revolutionary impact on the field while acknowledging existing limitations and envisioning future advancements for optimized medical applications.

Landscaping Covalent Organic Framework Nanomorphologies.

The practical utilization of covalent organic frameworks (COFs) with manipulation at the atomic and molecular scale often demands their assembly on the nano-, meso-, and macroscale with precise control. Consequently, synthetic approaches that establish the ability to control the nucleation and growth of COF crystallites and their self-assembly to desired COF nanomorphologies have drawn substantial attention from researchers. On the basis of the dimensionality of the COF morphologies, we can categorize them into zero- (0-D), one- (1-D), two- (2-D), and three-dimensional (3-D) nanomorphologies. In this perspective, we summarize the reported synthetic strategies that enable precise control of the COF nanomorphologies' size, shape, and dimensionality and reveal the impact of the dimensionalities in their physicochemical properties and applications. The aim is to establish a synergistic optimization of the morphological dimensionality while keeping the micro- or mesoporosity, crystallinity, and chemical functionalities of the COFs in perspective. A detailed knowledge along the way should help us to enrich the performance of COFs in a variety of applications like catalysis, separation, sensing, drug delivery, energy storage, etc. We have discussed the interlinking between the COF nanomorphologies via the transmutation of the dimensionalities. Such dimensionality transmutation could lead to variation in their properties during the transition. Finally, the concept of constructing COF superstructures through the combination of two or more COF nanomorphologies has been explored, and it could bring up opportunities for developing next-generation innovative materials for multidisciplinary applications.

Surface-fill hydrogel attenuates the oncogenic signature of complex anatomical surface cancer in a single application.

Tumours growing in a sheet-like manner on the surface of organs and tissues with complex topologies represent a difficult-to-treat clinical scenario. Their complete surgical resection is difficult due to the complicated anatomy of the diseased tissue. Residual cancer often responds poorly to systemic therapy and locoregional treatment is hindered by the limited accessibility to microscopic tumour foci. Here we engineered a peptide-based surface-fill hydrogel (SFH) that can be syringe- or spray-delivered to surface cancers during surgery or used as a primary therapy. Once applied, SFH can shape change in response to alterations in tissue morphology that may occur during surgery. Implanted SFH releases nanoparticles composed of microRNA and intrinsically disordered peptides that enter cancer cells attenuating their oncogenic signature. With a single application, SFH shows efficacy in four preclinical models of mesothelioma, demonstrating the therapeutic impact of the local application of tumour-specific microRNA, which might change the treatment paradigm for mesothelioma and possibly other surface cancers.

A systematic review and meta-analysis on correlation of weather with COVID-19.

This study presents a systematic review and meta-analysis over the findings of significance of correlations between weather parameters (temperature, humidity, rainfall, ultra violet radiation, wind speed) and COVID-19. The meta-analysis was performed by using 'meta' package in R studio. We found significant correlation between temperature (0.11 [95% CI 0.01-0.22], 0.22 [95% CI, 0.16-0.28] for fixed effect death rate and incidence, respectively), humidity (0.14 [95% CI 0.07-0.20] for fixed effect incidence) and wind speed (0.58 [95% CI 0.49-0.66] for fixed effect incidence) with the death rate and incidence of COVID-19 (p < 0.01). The study included 11 articles that carried extensive research work on more than 110 country-wise data set. Thus, we can show that weather can be considered as an important element regarding the correlation with COVID-19.

Heterogeneous C-H Functionalization in Water via Porous Covalent Organic Framework Nanofilms: A Case of Catalytic Sphere Transmutation.

Heterogeneous catalysis in water has not been explored beyond certain advantages such as recyclability and recovery of the catalysts from the reaction medium. Moreover, poor yield, extremely low selectivity, and active catalytic site deactivation further underrate the heterogeneous catalysis in water. Considering these facts, we have designed and synthesized solution-dispersible porous covalent organic framework (COF) nanospheres. We have used their distinctive morphology and dispersibility to functionalize unactivated C-H bonds of alkanes heterogeneously with high catalytic yield (42-99%) and enhanced regio- and stereoselectivity (3°:2° = 105:1 for adamantane). Further, the fabrication of catalyst-immobilized COF nanofilms via covalent self-assembly of catalytic COF nanospheres for the first time has become the key toward converting the catalytically inactive homogeneous catalysts into active and effective heterogeneous catalysts operating in water. This unique covalent self-assembly occurs through the protrusion of the fibers at the interface of two nanospheres, transmuting the catalytic spheres into films without any leaching of catalyst molecules. The catalyst-immobilized porous COF nanofilms' chemical functionality and hydrophobic environment stabilize the high-valent transient active oxoiron(V) intermediate in water and restricts the active catalytic site's deactivation. These COF nanofilms functionalize the unactivated C-H bonds in water with a high catalytic yield (45-99%) and with a high degree of selectivity (cis:trans = 155:1; 3°:2° = 257:1, for cis-1,2-dimethylcyclohexane). To establish this approach's "practical implementation", we conducted the catalysis inflow (TON = 424 ± 5) using catalyst-immobilized COF nanofilms fabricated on a macroporous polymeric support.

Multiphase Assembly of Small Molecule Microcrystalline Peptide Hydrogel Allows Immunomodulatory Combination Therapy for Long-Term Heart Transplant Survival.

Combination therapies that target multiple pathways involved in immune rejection of transplants hold promise for patients in need of restorative surgery. Herein, a noninteracting multiphase molecular assembly approach is developed to crystallize tofacitinib, a potent JAK1/3 inhibitor, within a shear-thinning self-assembled fibrillar peptide hydrogel network. The resulting microcrystalline tofacitinib hydrogel (MTH) can be syringe-injected directly to the grafting site during surgery to locally deliver the small molecule. The rate of drug delivered from MTH is largely controlled by the dissolution of the encapsulated microcrystals. A single application of MTH, in combination with systemically delivered CTLA4-Ig, a co-stimulation inhibitor, affords significant graft survival in mice receiving heterotopic heart transplants. Locoregional studies indicate that the local delivery of tofacitinib at the graft site enabled by MTH is required for the observed enhanced graft survival.

Potential Effect of Tobacco Consumption through Smoking and Chewing Tobacco on IL1beta Protein Expression in Chronic Periodontitis Patients: In Silico Molecular Docking Study.

Detrimental effect of bad oral habits, such as smoking and chewing tobacco, on chronic periodontitis (CP) manifest chronic inflammation of gingival tissues which majorly results in gum bleeding, and teeth loss. A genetic association study of Interleukin 1 beta (IL1ß) has been conducted in CP patients having smoking and chewing tobacco habits in regular life style. A molecular docking study has been consequently done to analyze the effect of tobacco on CP progression in depth. All statistical evaluation has been done by using SPSS v16.0. The findings of the study show the significant association of IL1ß gene polymorphisms with CP increased susceptibility in combination of oral habits as mentioned earlier. The docking profile has showed the highest binding affinity of IL1ß protein with the Nicotine derived Nitrosamine Ketone (NNK), one of the derivatives of nicotine which is in-taken through the habits associated with smoking and chewing tobacco. Nicotine, N-nitrosoanabasine, and N-nitrosonornicotine, the other derivatives, have also demonstrated significant impact over the IL1ß protein-caused altered expression. Thus, this study concluded that the harmful effect of tobacco may increase the inflammation in periodontia by inducing the inflammatory active site of the IL1ß protein in the CP patients.

Telomere Length Inheritance and Shortening in Trisomy 21.

Objective: Trisomy 21 is a genetic disorder that shows premature aging symptoms. As an aging marker, telomere length is therefore of importance in trisomy families. Methods: We included 63 maternally originated trisomy 21 and 77 control families with infants in the first data set; 48 trisomy 21 and 60 control children in the second set; and 14 paternally originated trisomy 21 families in the third data set. We used Southern blot to measure the telomere length. Results: (1) Offsprings' telomere length increased with parents' age (p < .0001). (2) Trisomy 21 infants had longer telomere than the controls (p < .0001). (3) Post-birth, the telomere attrition rate was higher in cases than in controls (58 bps/year vs. 38 bps/year). Conclusion: (1) Our data supports the older parents-longer gamete telomere hypothesis. (2) Trisomy 21 patients are born with longer telomeres, (3) with advancing trisomy 21 age, the telomere shortens more quickly than euploids.

Interleukin gene polymorphisms in chronic periodontitis: A case-control study in the Indian population.

OBJECTIVE: The aim of the present study was to investigate the possible association between seven Interleukin (IL) gene polymorphisms and their interaction with the chronic inflammatory oral disease, chronic periodontitis in Indian population. DESIGN: A total of 357 study subjects (157 with chronic periodontitis and 200 with healthy control) were genotyped for IL1A -889C/T (rs1800587), IL1B -31C/T (rs1143627), IL1B -511A/G (rs16944), IL1B + 3954C/T (rs1143634), IL2 -330 T/G (rs2069762), IL4 -33C/T (rs2070874), IL6 -597 G/A (rs1800797), IL8 -251A/T (rs4073), IL10 -819C/T (rs1800871), IL10 -592A/C (rs1800872) and IL13 -1111C/T (rs1800925). Statistical analysis was performed using the statistical software package SPSS v16. SNPassoc and Multifactor Dimensionality Reduction algorithm v3.0.2. RESULTS: We found that the statistically significant association of IL1A-889C/T (rs1800587), IL1B -31C/T (rs1143627), IL1B -511A/G (rs16944) and IL1B + 3954C/T (rs1143634) gene polymorphisms with increased susceptibility of chronic periodontitis. The best gene-gene interaction model was IL1B(-31C/T) X IL1B(+3954C/T) X IL10(-819C/T) with 10/10 cross validation consistency. The variant allele of IL1A, IL1B, IL10 and IL13 were seemed to be linked with chronic periodontitis increased susceptibility. The results of this study also indicate that epidemiological factors especially oral habits also play an important role in the development of chronic periodontitis. CONCLUSIONS: This study concludes IL1A -889C/T (rs1800587), IL1B -31C/T (rs1143627), IL1B -511A/G (rs16944), IL1B + 3954C/T (rs1143634), IL10 -819C/T (rs1800871), IL10 -592A/C (rs1800872) and IL13 -1111C/T (rs1800925) gene polymorphisms are significantly associated with chronic periodontitis. This work also infers that the best interactive model comprised of IL1B and IL10 polymorphisms cumulatively increase the risk of chronic periodontitis.