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The development of effective oxygen evolution reaction (OER) and urea oxidation reaction (UOR) on heterostructure electrocatalysts with specific interfaces and characteristics provides a distinctive character. In this study, heterostructure nanocubes (NCs) comprising inner cobalt oxysulfide (CoOS) NCs and outer CoFe (CF) layered double hydroxide (LDH) are developed using a hydrothermal methodology. During the sulfidation process, the divalent sulfur ions (S2-) are released from the breakdown of the sulfur source and react with the Co-precursors on the surface leading to the transformation of CoOH nanorods into CoOS nanocubes. Further, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analyses reveal that the interactions at the interface of the CF@CoOS NCs significantly altered the electronic structure, thus enhancing the electrocatalytic performance. The optimal catalysts exhibited effective OER and UOR activities, the attained potentials are 1.51 and 1.36 V. This remarkable performance is attributable to the induction of electron transfer from the CoFe LDH to CoOS, which reduces the energy barrier of the intermediates for the OER and UOR. Furthermore, an alkaline water and urea two-cell electrolyzer assembled using CF@CoOS-2 NCs and Pt/C as the anode and cathode requires a cell voltage of 1.63 and 1.56 V along with a durability performance.
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Layered 2D transition metal dichalcogenides (TMDs) have been suggested as efficient substitutes for Pt-group metal electrocatalysts in the hydrogen evolution reaction (HER). However, poor catalytic activities in neutral and alkaline electrolytes considerably hinder their practical applications. Furthermore, the weak adhesion between TMDs and electrodes often impedes long-term durability and thus requires a binder. Here, a universal platform is reported for robust dual-atom doped 2D electrocatalysts with superior HER performance over a wide pH range media. V:Co-ReS2 on a wafer scale is directly grown on oxidized Ti foil by a liquid-phase precursor-assisted approach and subsequently used as highly efficient electrocatalysts. The catalytic performance surpasses that of Pt group metals in a high current regime (≥ 100 mA cm-2) at pH ≥ 7, with a high durability of more than 70 h in all media at 200 mA cm-2. First-principles calculations reveal that V:Co dual doping in ReS2 significantly reduces the water dissociation barrier and simultaneously enables the material to achieve the thermoneutral Gibbs free energy for hydrogen adsorption.
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HOX transcript antisense intergenic RNA (HOTAIR) is an oncogenic non-coding RNA whose expression is strongly correlated with the tumor grade and prognosis of a variety of carcinomas including breast cancer (BC). HOTAIR regulates various target genes via sponging and epigenetic mechanisms and controls various oncogenic cellular and signaling mechanisms including metastasis and drug resistance. In BC cells, HOTAIR expression is regulated by a variety of transcriptional and epigenetic mechanisms. In this review, we describe the regulatory mechanisms that govern HOTAIR expression during cancer development and explore how HOTAIR drives BC development, metastasis, and drug resistance. In the final section of this review, we focus on the role of HOTAIR in BC management, therapeutic treatment, and prognosis, highlighting its potential therapeutic applications.
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Neoplasias de la Mama , ARN Largo no Codificante , Femenino , Humanos , Neoplasias de la Mama/tratamiento farmacológico , Neoplasias de la Mama/genética , Neoplasias de la Mama/patología , Regulación Neoplásica de la Expresión Génica , Pronóstico , ARN Largo no Codificante/genéticaRESUMEN
Cancer is an outrageous disease with uncontrolled differentiation, growth, and migration to the other parts of the body. It is the second-most common cause of death both in the U.S. and worldwide. Current conventional therapies, though much improved and with better prognosis, have several limitations. Chemotherapeutic agents, for instance, are cytotoxic to both tumor and healthy cells, and the non-specific distribution of drugs at tumor sites limits the dose administered. Nanotechnology, which evolved from the coalescence and union of varied scientific disciplines, is a novel science that has been the focus of much research. This technology is generating more effective cancer therapies to overcome biomedical and biophysical barriers against standard interventions in the body; its unique magnetic, electrical, and structural properties make it a promising tool. This article reviews endogenous- and exogenous-based stimulus-responsive drug delivery systems designed to overcome the limitations of conventional therapies. The article also summarizes the study of nanomaterials, including polymeric, gold, silver, magnetic, and quantum dot nanoparticles. Though an array of drug delivery systems has so far been proposed, there remain many challenges and concerns that should be addressed in order to fill the gaps in the field. Prominence is given to drug delivery systems that employ external- and internal-based stimuli and that are emerging as promising tools for cancer therapeutics in clinical settings.
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Antineoplásicos/administración & dosificación , Sistemas de Liberación de Medicamentos , Nanomedicina , Nanopartículas/administración & dosificación , Nanoestructuras/química , Neoplasias/tratamiento farmacológico , Animales , Humanos , Nanopartículas/química , Neoplasias/patologíaRESUMEN
Colorectal cancer (CRC) is one of the deadliest diseases worldwide due to a lack of early detection methods and appropriate drug delivery strategies. Conventional imaging techniques cannot accurately distinguish benign from malignant tissue, leading to frequent misdiagnosis or diagnosis at late stages of the disease. Novel screening tools with improved accuracy and diagnostic precision are thus required to reduce the mortality burden of this malignancy. Additionally, current therapeutic strategies, including radio- and chemotherapies carry adverse side effects and are limited by the development of drug resistance. Recent advances in nanotechnology have rendered it an attractive approach for designing novel clinical solutions for CRC. Nanoparticle-based formulations could assist early tumor detection and help to overcome the limitations of conventional therapies including poor aqueous solubility, nonspecific biodistribution and limited bioavailability. In this review, we shed light on various types of nanoparticles used for diagnosis and drug delivery in CRC. In addition, we will explore how these nanoparticles can improve diagnostic accuracy and promote selective drug targeting to tumor sites with increased efficiency and reduced cytotoxicity against healthy colon tissue.
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Antineoplásicos/administración & dosificación , Neoplasias Colorrectales/diagnóstico , Neoplasias Colorrectales/tratamiento farmacológico , Sistemas de Liberación de Medicamentos , Imagen Multimodal/métodos , Nanopartículas/administración & dosificación , Nanotecnología/métodos , Animales , Neoplasias Colorrectales/diagnóstico por imagen , Humanos , Nanopartículas/químicaRESUMEN
Developing highly efficient noble-metal-free electrocatalysts with a scalable and environmentally friendly synthesis approach remains a challenge in the field of electrocatalytic water splitting. To overcome this problem, self-supported fluorine-modified 2D ultrathin nickel hydroxide (F-Ni(OH)2 ) nanosheets (NSs) for the oxygen evolution reaction (OER) and urea oxidation reaction (UOR) are prepared with a scalable and ascendant one-step synthesis route. The enhanced redox activity, electrical conductivity and a great number of exposed active sites of the heterogeneous catalysts improve charge migration for the electrocatalytic reactions. The density of states of the d orbitals of the Ni atoms significantly increases near the Fermi level, thereby indicating that the Ni atoms near the F-dopants promote electrical conduction in the Ni(OH)2 monolayer. The F-Ni(OH)2 electrocatalyst exhibits notable OER and UOR activity with onset potentials of 1.43 and 1.16 V versus RHE, respectively required to reach 10 mA cm-2 , which are comparable to those of commercial noble-metal-based electrocatalysts. With RuCo-OH nanospheres, the settled F-Ni(OH)2 ||RuCo-OH cell requires merely 1.55 and 1.37 V to reach 10 mA cm-2 with superb durability for 24 h in overall water and urea electrolysis, respectively. Overall, high-quality, and efficient noble-metal-free electrocatalysts for overall water and urea electrolysis can be prepared with a simple, scalable, and reproducible preparation method.
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Transition metal selenides (TMSs) have enthused snowballing research and industrial attention due to their exclusive conductivity and redox activity features, holding them as great candidates for emerging electrochemical devices. However, the real-life utility of TMSs remains challenging owing to their convoluted synthesis process. Herein, a versatile in situ approach to design nanostructured TMSs for high-energy solid-state hybrid supercapacitors (HSCs) is demonstrated. Initially, the rose-nanopetal-like NiSe@Cu2 Se (NiCuSe) positive electrode and FeSe nanoparticles negative electrode are directly anchored on Cu foam via in situ conversion reactions. The complementary potential windows of NiCuSe and FeSe electrodes in aqueous electrolytes associated with the excellent electrical conductivity results in superior electrochemical features. The solid-state HSCs cell manages to work in a high voltage range of 0-1.6 V, delivers a high specific energy density of 87.6 Wh kg-1 at a specific power density of 914.3 W kg-1 and excellent cycle lifetime (91.3% over 10 000 cycles). The innovative insights and electrode design for high conductivity holds great pledge in inspiring material synthesis strategies. This work offers a feasible route to develop high-energy battery-type electrodes for next-generation hybrid energy storage systems.
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The distribution and diffusion of water molecules are playing important roles in determining self-assembly and transport properties of polymeric systems. Small-angle neutron scattering (SANS) experiments and molecular dynamics (MD) simulation have been applied to understand the distribution of water molecules and their dynamics in the lamellar membrane formed by Pluronic L62 block copolymers. Penetration of water molecules into the polyethylene oxide (PEO) layers of the membranes has been estimated using scattering length density (SLD) profiles obtained from SANS measurements, which agree well with the molecular distribution observed from MD simulations. The water diffusion coefficient at different regions of the lamellar membrane was further investigated using MD simulation. The diffusion characteristic shows a transition from normal to anomalous diffusion as the position of the water molecule changes from the bulk to PEO and to the polypropylene oxide (PPO) layer. We find that water molecules within the PEO or PPO layers follow subdiffusive dynamics, which can be interpreted by the model of fractional Brownian motion.
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We have investigated the molecular exchange of sodium dodecyl sulfate (SDS) micelles in aqueous solution by time-resolved small angle neutron scattering (TR-SANS) measurements as a function of the surfactant and salt concentration. Starting with deuterated (d-SDS) and protonated (h-SDS) SDS micelles, surfactant exchange across the micelles leads to a randomized distribution of d-SDS and h-SDS within each micelle. By employing the contrast matching technique, we have studied this randomization process which is a direct measure of the molecular exchange of this system. Our results show that the randomization of the pure h-SDS and d-SDS micelles occurs in two steps: first, an almost instantaneous drop in the scattering intensity is observed where â¼80% of the micelles are randomized (contrast matched). After this, micelle randomization progresses slowly spanning over â¼100 hours. Importantly, we show that the kinetics in the second step are dominated by the formation of domains rich in either h-SDS, d-SDS and randomized (50 : 50 h-SDS : d-SDS). The slow exchange step is modeled via a phenomenological approach by drawing analogy to the Langmuir adsorption theory. Finally, the effects of the surfactant and salt concentrations on the instantaneous, and the time dependent randomization of SDS micelles are discussed.
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The tumor microenvironment (TME) plays a key role in cancer development and emergence of drug resistance. TME modulation has recently garnered attention as a potential approach for reprogramming the TME and resensitizing resistant neoplastic niches to existing cancer therapies such as immunotherapy or chemotherapy. Nano-based solutions have important advantages over traditional platform and can be specifically targeted and delivered to desired sites. This review explores novel nano-based approaches aimed at targeting and reprogramming aberrant TME components such as macrophages, fibroblasts, tumor vasculature, hypoxia and ROS pathways. We also discuss how nanoplatforms can be combined with existing anti-tumor regimens such as radiotherapy, immunotherapy, phototherapy or chemotherapy to enhance clinical outcomes in solid tumors.
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Nanopartículas , Neoplasias , Humanos , Factores Inmunológicos , Inmunoterapia , Macrófagos , Neoplasias/tratamiento farmacológico , Microambiente TumoralRESUMEN
Understanding how the natural products structural diversity interacts with cellular metabolism and infectious disease targets remains a challenge. Inflammation is an important process in the human healing response in which the tissues respond to injuries induced by many agents, including pathogens. In recent years, several drugs derived from plant products have been developed, and current drug research is actively investigating the pharmacotherapeutic role of natural products in advanced multimodal inflammatory disease targeting. Sugiol, a diterpenoid, can act as an antimicrobial, antioxidant, anti-inflammatory, anti-carcinoma, antiviral, and cardiovascular agent. Until now, there have been no updates on the pharmacotherapeutic advancement of sugiol. Herein, we correlate the diverse molecular pathways in disease prevention involving sugiol. We also discuss the origins of its structural diversity and summarize new research directions toward exploring its novel effective future uses. Despite much evidence of its efficacy and safety, the sugiol has not yet been approved as a therapeutic agent due to its low bioavailability, and insolubility in an aqueous environment. The aim of this review is to renew and update noteworthy information on the pharmacotherapeutic characteristics of sugiol to approach different advanced strategies employed in the context of natural nurturing-based biomedicine.
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Diterpenos/farmacología , Diterpenos/uso terapéutico , Animales , Antiinfecciosos/farmacología , Antiinfecciosos/uso terapéutico , Antiinflamatorios/farmacología , Antiinflamatorios/uso terapéutico , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico , Antioxidantes/farmacología , Antioxidantes/uso terapéutico , HumanosRESUMEN
Phthalates are pervasive compounds, and due to the ubiquitous usage of phthalates, humans or even children are widely exposed to them. Since phthalates are not chemically bound to the plastic matrix, they can easily leach out to contaminate the peripheral environment. Various animal and human studies have raised vital health concern including developmental and reproductive toxicity of phthalate exposure. The present review is based upon the available literature on phthalates with respect to their reproductive toxic potential. Common reproductive effects such as declined fertility, reduced testis weight, variations in accessory sex organs and several female reproductive disorders appeared to be largely associated with the transitional phthalates. Among the higher molecular weight phthalates (≥ C7), di-isononyl phthalate (DINP) produces some minor effects on development of male reproductive tract and among low molecular weight phthalates (≤C3), di-methyl (DMP) and di-isobutyl (DIBP) phthalate produce some adverse effects on male reproductive system. Whereas transitional phthalates such as di-butyl phthalate, benzyl butyl phthalate, and di-(2-ethylhexyl) phthalate have shown adverse effects on female reproductive system. Owing to these, non-toxic alternatives to phthalates may be developed and use of phthalates could be rationalized as an important issue where human reproduction system is involved. Though, more epidemiological studies are needed to substantiate the reported findings on phthalates.
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Contaminantes Ambientales/toxicidad , Ácidos Ftálicos/toxicidad , Reproducción/efectos de los fármacos , Animales , Femenino , Fertilidad/efectos de los fármacos , Humanos , Infertilidad/inducido químicamente , MasculinoRESUMEN
Fenitrothion (FT) is a toxic phosphorothioate insecticide that can easily contaminate aquatic environments, leading to a detrimental effect on the aquatic species and harmful endocrine disrupter effects on human health. Therefore, it is vital to develop a reliable methodology for the accurate and precise real-time sensing of carcinogenic FT in water samples at trace concentration to ensure environmental safety. We aim to fabricate the low-cost VS2-attached reduced graphene oxide (RGO) sheets via a simple hydrothermal approach. It was further applied for the rapid and accurate sensing of toxic FT. The VS2/RGO-composite delivers a more favorable microenvironment for the rapid electrocatalytic sensing performance towards toxic FT reduction than the VS2 and RGO modified electrodes. The electron transfer rate constant (ks) and the saturating absorption capacity (Γ) value of FT was evaluated to be 1.52 s-1 and 2.18 × 10-10 mol cm-2, respectively. The constructed sensor exhibits a wide linear relationship after amperometry between the cathodic current densities and the concentrations of FT in the range of 5-90 nM and high sensitivity (5.569 µA nM-1 cm-2); moreover, the detection limit was 0.07 nM (S/N = 3). The fabricated sensor has excellent anti-interference ability and reproducibility for the direct sensing of FT in river water, seawater, and lake water samples with acceptable recoveries. It is a promising sensing device for in-situ quantification of FT in agricultural products and ecological systems.
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Unique Ni2CoS4-carbon nanofiber (CNF) composite nanostructures were fabricated using a simple electrospinning-assisted hydrothermal route and used for the rapid and accurate electrochemical oxidation of glucose in real samples at the trace level. Electrochemical impedance spectroscopy and cyclic voltammetry of unmodified and modified electrodes revealed low charge-transfer resistance and the excellent electrocatalytic sensing of glucose when using the Ni2CoS4-CNF at a low potential due to the combined benefits of the highly conductive Ni2Co2S4 anchored to the large surface area of the CNFs. Amperometric analysis of the fabricated sensor has shown an extremely low limit of detection (0.25 nM) and a large linear range (5-70 nM) for glucose at a working potential of 0.54 V (vs. Hg/HgO). The practicability of the Ni2CoS4-CNF for use in glucose determination was tested withl human saliva, blood plasma, and fruit juice samples. The Ni2CoS4-CNF/GCE showed acceptable recovery values for human saliva (99.1-100.8%), blood plasma (98.6-101.5%), and fruit juice (95.1-105.7%) samples. The proposed sensor also exhibited outstanding electroanalytical characteristics for glucose oxidation in these samples, including reusability, repeatability, and interference resistance, even in the presence of other biological substances and organic and inorganic metal ions.
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Glucemia/análisis , Técnicas Electroquímicas/métodos , Nanocompuestos/química , Nanofibras/química , Glucemia/química , Carbono/química , Cobalto/química , Técnicas Electroquímicas/instrumentación , Electrodos , Jugos de Frutas y Vegetales/análisis , Humanos , Límite de Detección , Níquel/química , Oxidación-Reducción , Reproducibilidad de los Resultados , Saliva/química , Sulfuros/químicaRESUMEN
An ultrasensitive electrochemical immunosensor has been prepared using an immunofunctionalized zirconium (Zr)-based metal-organic framework (MOF) with gold (Au) decoration Au@UiO-66(NH2) composite-coated glassy carbon electrode (GCE) for the determination of infectious hepatitis B surface antigen (HBsAg). We fabricated GCE with specific composite via immune-functionalization using anti-HBsAg with Au nanoparticles embedded in UiO-66(NH2). The electrochemical sensing performance of the immunofunctionalized Au@UiO-66(NH2)/GCE with HBsAg was characterized by cyclic voltammetry and differential pulse voltammetry. Under optimized conditions, there was a linear dynamic relationship in the buffer system between the electrical signal and HBsAg levels over the range 1.13 fg mL-1-100 ng mL-1 (R2 = 0.999) with a detection limit of 1.13 fg mL-1. The total analysis time was 15 min per sample. Further validations were performed with HBsAg-spiked human serum samples, and similar detection limits as in the buffer system were observed with reduced signal intensities at lower concentrations of HBsAg (1, 10, and 100 fg mL-1) and minimal interference. The HBsAg electrochemical immunosensing assay had good selectivity and excellent reproducibility, thereby indicating its significant potential in the super-fast diagnosis of hepatitis B.
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Estructuras MetalorgánicasRESUMEN
The development of pseudocapacitive materials for energy-oriented applications has stimulated considerable interest in recent years due to their high energy-storing capacity with high power outputs. Nevertheless, the utilization of nanosized active materials in batteries leads to fast redox kinetics due to the improved surface area and short diffusion pathways, which shifts their electrochemical signatures from battery-like to the pseudocapacitive-like behavior. As a result, it becomes challenging to distinguish "pseudocapacitive" and "battery" materials. Such misconceptions have further impacted on the final device configurations. This Review is an earnest effort to clarify the confusion between the battery and pseudocapacitive materials by providing their true meanings and correct performance metrics. A method to distinguish battery-type and pseudocapacitive materials using the electrochemical signatures and quantitative kinetics analysis is outlined. Taking solid-state supercapacitors (SSCs, only polymer gel electrolytes) as an example, the distinction between asymmetric and hybrid supercapacitors is discussed. The state-of-the-art progress in the engineering of active materials is summarized, which will guide for the development of real-pseudocapacitive energy storage systems.
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Plant beneficial rhizobacteria (PBR) is a group of naturally occurring rhizospheric microbes that enhance nutrient availability and induce biotic and abiotic stress tolerance through a wide array of mechanisms to enhance agricultural sustainability. Application of PBR has the potential to reduce worldwide requirement of agricultural chemicals and improve agro-ecological sustainability. The PBR exert their beneficial effects in three major ways; (1) fix atmospheric nitrogen and synthesize specific compounds to promote plant growth, (2) solubilize essential mineral nutrients in soils for plant uptake, and (3) produce antimicrobial substances and induce systemic resistance in host plants to protect them from biotic and abiotic stresses. Application of PBR as suitable inoculants appears to be a viable alternative technology to synthetic fertilizers and pesticides. Furthermore, PBR enhance nutrient and water use efficiency, influence dynamics of mineral recycling, and tolerance of plants to other environmental stresses by improving health of soils. This report provides comprehensive reviews and discusses beneficial effects of PBR on plant and soil health. Considering their multitude of functions to improve plant and soil health, we propose to call the plant growth-promoting bacteria (PGPR) as PBR.
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Agricultura/tendencias , Fenómenos Fisiológicos Bacterianos , Plantas/microbiología , Microbiología del Suelo , Bacterias/metabolismo , Nitrógeno/metabolismo , Desarrollo de la Planta , Suelo/química , Estrés FisiológicoRESUMEN
Electrochemical water splitting represents an ideal strategy for producing clean hydrogen as an energy carrier that serves as an alternative to fossil fuels. As an effective method for hydrogen production, an efficient inexpensive multifunctional electrocatalyst with high durability is designed. Herein, we describe the heterostructural design of a three-dimensional catalytic network with self-embedded CoNi2S4 nanograins grown on electrospun carbon nanofibers (CoNi2S4-CNFs) with anchored thin-layer reduced graphene oxide. This is achieved via facile electrospinning followed by carbonization, low-temperature sulfidation, and surface functionalization. As a bifunctional catalyst, CoNi2S4-CNFs exhibited robust high activity toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. The anchored ultrathin graphene oxide layer promoted the stability and durability of the catalytic network with an efficient path for the transportation of electrons. The rGO-anchored CoNi2S4-CNFs yielded overpotential values of 228 mV and 205 mV for the HER and OER, respectively, that drives a current density of 20 mA cm-2 in an alkaline medium. Notably, the excellent electrochemical properties are attributed to the functional effect of the CoNi2S4 on the CNF network. The ultrathin feature of rGO improved the durability of the catalytic network. Moreover, using the rGO-anchored CoNi2S4-CNFs as a cathode and anode in a two-electrode water splitting system required a cell voltage of only 1.55 V to reach a current density of 10 mA cm-2. These CNFs exhibited outstanding durability for 48 h. The present work offers new insight for the design of a catalytic network with a non-noble metal catalyst that exhibits excellent electrocatalytic activity and durability on the metal sulfides in overall water splitting.
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The cross-talk between apoptosis and autophagy influences anticancer drug sensitivity and cellular death in various cancer cell lines. However, the fundamental mechanisms behind this phenomenon are still unidentified. We demonstrated anti-cancerous role of cisplatin (CP) and morin hydrate (Mh) as an individual and/or in combination (CP-Mh) in hepatoma cells and tumor model. Exposure of CP resulted in the production of intracellular reactive oxygen species (ROS)-mediated cellular vacuolization, expansion of mitochondria membrane and activation of endoplasmic reticulum (ER)-stress. Consequently, Cyt c translocation led to the increase of Bax/Bcl-2 ratio, which simultaneously triggered caspase-mediated cellular apoptosis. In addition, CP-induced PARP-1 activation led to ADP-ribosylation of HMGB1, which consequently developed autophagy as evident by the LC3I/II ratio. Chemically-induced inhibition of autophagy marked by increased cell death signified a protective role of autophagy against CP treatment. CP-Mh abrogates the PARP-1 expression and significantly reduced HMGB1-cytoplasmic translocation with subsequent inhibition of the HMGB1-Beclin1 complex formation. In the absence of PARP-1, a reduced HMGB1 mediated autophagy was observed followed by induced caspase-dependent apoptosis. To confirm the role of PARP-1-HMGB1 signaling in autophagy, we used the PARP-1 inhibitor, 4-amino-1,8-naphthalimide (ANI), HMGB1 inhibitor, ethyl pyruvate (EP), autophagy inhibitors, 3-methyl adenine (3-MA) and bafilomycin (baf) and small interfering RNAs (siRNA) to target Atg5 in combination of CP and Mh. Exposure to these inhibitors enhanced the sensitivity of HepG2 cells to CP. Collectively, our findings indicate that CP-Mh in combination served as a prominent regulator of autophagy and significant inducer of apoptosis that maintains a homeostatic balance towards HepG2 cells and the subcutaneous tumor model.