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Intermetallic compounds, featuring atomically ordered structures, have emerged as a class of promising electrocatalysts for fuel cells. However, it remains a formidable challenge to controllably synthesize Pt-based intermetallics during the essential high-temperature annealing process as well as stabilize the nanoparticles (NPs) during the electrocatalytic process. Herein, we demonstrated a Ketjen black supported intermetallic Pt3Ti nanocatalyst coupled with amorphous TiOx species (Pt3Ti-TiOx/KB). The TiOx can not only confine Pt3Ti NPs during the synthesis and electrocatalytic process by a strong metal-oxide interaction but also promote the water dissociation for generating more OH species, thus facilitating the conversion of COad. The Pt3Ti-TiOx/KB showed a significantly enhanced mass activity (2.15 A mgPt-1) for the methanol oxidation reaction, compared with Pt3Ti/KB and Pt/C, and presented an impressively high mass activity retention (â¼71%) after the durability test. This work provides an effective strategy of coupling Pt-based intermetallics with functional oxides for developing highly performed electrocatalysts.
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Developing industrially moldable catalysts with harmonized redox performance and acidity is of great significance for the efficient disposal of chlorinated volatile organic compounds (CVOCs) in actual exhaust gasses. Here, commercial TiO2, typically used for molding catalysts, was chosen as the carrier to fabricate a series of Ce0.02Mn0-0.24TiOx materials with different Mn doping ratios and employed for chlorobenzene (CB) destruction. The introduction of Mn remarkedly facilitated the synergistic effect of each element via the electron transfer processes: Ce3++Mn4+/3+âCe4++Mn3+/2+ and Mn4+/3++Ti4+âMn3+/2++Ti3+. These synergistic interactions in Ce0.02Mn0.04-0.24TiOx, especially Ce0.02Mn0.16TiOx, significantly elevated the active oxygen species, oxygen vacancies and redox properties, endowing the superior catalytic oxidation of CB. When the Mn doping amount increased to 0.24, a separate Mn3O4 phase appeared, which in turn might weaken the synergistic effect. Furthermore, the acidity of Ce0.02Mn0.04-0.24TiOx was decreased with the Mn doping, regulating the balance of redox property and acidity. Notably, Ce0.02Mn0.16TiOx featured relatively abundant B-acid sites. Its coordinating redox ability and moderate acidity promoted the deep oxidation of CB and RCOOH- intermediates, as well as the rapid desorption of Cl species, thus obtaining sustainable reactivity. In comparison, CeTiOx owned the strongest acidity, however, its poor redox property was not sufficient for the timely oxidative decomposition of the easier adsorbed CB, resulting in its rapid deactivation. This finding provides a promising strategy for the construction of efficient commercial molding catalysts to decompose the industrial-scale CVOCs.
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Óxidos , Compuestos Orgánicos Volátiles , Titanio , Manganeso , Oxidación-Reducción , CatálisisRESUMEN
In this study, Soda Lime Glass (SLG) and Stainless Steel (SS316L) substrata coated with Titanium oxide (TiOx) were tested for their efficacy in the laboratory microcosms and in field against micro- and macrofouling. Laboratory microcosm studies were conducted for five days using natural biofilms, single-species diatom (Navicula sp.), and bacterial biofilms, whereas field observations were conducted for 30 days. The TiOx-coating induced change in the mean contact angle of the substratum and rendered SS316L more hydrophilic and SLG hydrophobic, which influenced the Navicula sp. biofilm, and bacterial community structure of the biofilm. Overall, the TiOx-coated SS316L showed minimal microfouling, whereas non-coated SLG exhibited greater efficacy in deterring/preventing macrofouling organisms. Moreover, the reduction in macrofouling could be attributed to high abundance of Actinobacteria. Unraveling the mechanism of action needs future studies emphasizing biochemical processes and pathways.
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Biopelículas , Diatomeas , Bacterias , Acero Inoxidable , Interacciones Hidrofóbicas e HidrofílicasRESUMEN
Spermatogenesis is a complex cell differentiation process that includes marked genetic, cellular, functional and structural changes. It requires tight regulation, because disturbances in any of the spermatogenic processes would lead to fertility deficiencies as well as disorders in offspring. To increase our knowledge of signal transduction during sperm development, we carried out a large-scale identification of the phosphorylation events that occur in the human male gonad. Metal oxide affinity chromatography using TiO2 combined with LC-MS/MS was conducted to profile the phosphoproteome of adult human testes with full spermatogenesis. A total of 8187 phosphopeptides derived from 2661 proteins were identified, resulting in the most complete report of human testicular phosphoproteins to date. Phosphorylation events were enriched in proteins functionally related to spermatogenesis, as well as to highly active processes in the male gonad, such as transcriptional and translational regulation, cytoskeleton organization, DNA packaging, cell cycle and apoptosis. Moreover, 174 phosphorylated kinases were identified. The most active human protein kinases in the testis were predicted both by the number of phosphopeptide spectra identified and the phosphorylation status of the kinase activation loop. The potential function of cyclin-dependent kinase 12 (CDK12) and p21-activated kinase 4 (PAK4) has been explored by in silico, protein-protein interaction analysis, immunodetection in testicular tissue, and a functional assay in a human embryonal carcinoma cell line. The colocalization of CDK12 with Golgi markers suggests a potential crucial role of this protein kinase during sperm formation. PAK4 has been found expressed in human spermatogonia, and a role in embryonal carcinoma cell response to apoptosis has been observed. Together, our protein discovery analysis confirms that phosphoregulation by protein kinases is highly active in sperm differentiation and opens a window to detailed characterization and validation of potential targets for the development of drugs modulating male fertility and tumor behavior.
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Fosfoproteínas/metabolismo , Proteínas Quinasas/metabolismo , Proteoma/metabolismo , Espermatogénesis , Neoplasias Testiculares/metabolismo , Testículo/metabolismo , Anciano , Anciano de 80 o más Años , Apoptosis , Carcinoma Embrionario/patología , Ontología de Genes , Humanos , Masculino , Persona de Mediana Edad , Anotación de Secuencia Molecular , Mapeo de Interacción de Proteínas , Neoplasias Testiculares/patología , Testículo/patologíaRESUMEN
Hot carriers in semiconductor or metal nanostructures are relevant, for instance, to enhance the activity of oxide-supported metal catalysts or to achieve efficient photodetection using ultrathin semiconductor layers. Moreover, rapid collection of photoexcited hot carriers can improve the efficiency of solar cells, with a theoretical maximum of 85%. Because of the long lifetime of secondary excited electrons, graphene is an especially promising two-dimensional material to harness hot carriers for solar-to-electricity conversion. However, the photoresponse of thus far realized graphene photoelectric devices is mainly governed by thermal effects, which yield only a very small photovoltage. Here, we report a Gr-TiOx-Ti heterostructure wherein the photovoltaic effect is predominant. By doping the graphene, the open circuit voltage reaches values up to 0.30 V, 2 orders of magnitude larger than for devices relying upon the thermoelectric effect. The photocurrent turned out to be limited by trap states in the few-nanometer-thick TiOx layer. Our findings represent a first valuable step toward the integration of graphene into third-generation solar cells based upon hot carrier extraction.
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We demonstrate a lithium (Li) imbued TiOx iontronic device that exhibits synapse-like short-term plasticity behavior without requiring a forming process beforehand or a compliance current during switching. A solid-state electrolyte lithium phosphorus oxynitride (LiPON) behaves as the ion source, and the embedding and releasing of Li ions inside the cathodic like TiOx renders volatile conductance responses from the device and offers a natural platform for hardware simulating neuron functionalities. Besides, these devices possess high uniformity and great endurance as no conductive filaments are present. Different short-term pulse-based phenomena, including paired pulse facilitation, post-tetanic potentiation, and spike rate-dependent plasticity, were observed with self-relaxation characteristics. Based on the voltage excitation period, the time scale of the volatile memory can be tuned. Temperature measurement reveals the ion displacement-induced conductance channels become frozen below 220 K. In addition, the volatile analog devices can be configured into nonvolatile memory units with multibit storage capabilities after an electroforming process. Therefore, on the same platform, we can configure volatile units as nonlinear dynamic reservoirs for performing neuromorphic training and the nonvolatile units as the weight storage layer. We proceed to use voice recognition as an example with the tunable time constant relationship and obtain 94.4% accuracy with a minimal training data set. Thus, this iontronic platform can effectively process and update temporal information for reservoir and neuromorphic computing paradigms.
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A high-density neuromorphic computing memristor array based on 2D materials paves the way for next-generation information-processing components and in-memory computing systems. However, the traditional 2D-materials-based memristor devices suffer from poor flexibility and opacity, which hinders the application of memristors in flexible electronics. Here, a flexible artificial synapse array based on TiOx /Ti3 C2 Tx film is fabricated by a convenient and energy-efficient solution-processing technique, which realizes high transmittance (≈90%) and oxidation resistance (>30 days). The TiOx /Ti3 C2 Tx memristor shows low device-to-device variability, long memory retention and endurance, a high ON/OFF ratio, and fundamental synaptic behavior. Furthermore, satisfactory flexibility (R = 1.0 mm) and mechanical endurance (104 bending cycles) of the TiOx /Ti3 C2 Tx memristor are achieved, which is superior to other film memristors prepared by chemical vapor deposition. In addition, high-precision (>96.44%) MNIST handwritten digits recognition classification simulation indicates that the TiOx /Ti3 C2 Tx artificial synapse array holds promise for future neuromorphic computing applications, and provides excellent high-density neuron circuits for new flexible intelligent electronic equipment.
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In this work, we analyze a resistive switching random access memory (RRAM) device with the metal-insulator-metal structure of Al/αTiOx/Al. The transport mechanism of our RRAM device is trap-controlled space-charge limited conduction, which does not change during the endurance test. As the number of resistive switching (RS) cycles increases, the current in the low-resistance state (LRS) does not change significantly. In contrast, degradation in the high-resistance state (HRS) is noticeably evident. According to the RS cycle, the current shift fits well with the stretched-exponential equation. The normalized noise power spectral density (Si/I2) measured in the HRS is an order of magnitude higher than that in the LRS owing to the difference in the degree of trap occupancy, which is responsible for the transition of resistance states. During the consecutive RS, the Si/I2 in the HRS rapidly decreases for approximately 100 cycles and then saturates. In contrast, in the LRS, the Si/I2 does not change significantly. Here we propose a model associated with the endurance degradation of the experimental device, and the model is verified with a 1/f noise measurement.
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In this study, a new anodic oxidation with a step-bias increment is proposed to evaluate oxidized titanium (Ti) nanostructures on transparent fluorine-doped tin oxide (FTO) on glass. The optimal Ti thickness was determined to be 130 nm. Compared to the use of a conventional constant bias of 25 V, a bias ranging from 5 V to 20 V with a step size of 5 V for 3 min per period can be used to prepare a titanium oxide (TiOx) layer with nanohollows that shows a large increase in current of 142% under UV illumination provided by a 365 nm LED at a power of 83 mW. Based on AFM and SEM, the TiOx grains formed in the step-bias anodic oxidation were found to lead to nanohollow generation. Results obtained from EDS mapping, HR-TEM and XPS all verified the TiOx composition and supported nanohollow formation. The nanohollows formed in a thin TiOx layer can lead to a high surface roughness and photon absorbance for photocurrent generation. With this step-bias anodic oxidation methodology, TiOx with nanohollows can be obtained easily without any extra cost for realizing a high current under photoelectrochemical measurements that shows potential for electrochemical-based sensing applications.
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Ammonia is a key chemical feedstock for industry as well as future carbon-free fuel and transportable vector for renewable energy. Photoelectrochemical (PEC) ammonia synthesis from NOx reduction reaction (NOx RR) provides not only a promising alternative to the energy-intensive Haber-Bosch process through direct solar-to-ammonia conversion, but a sustainable solution for balancing the global nitrogen cycle by restoring ammonia from wastewater. In this work, selective ammonia synthesis from PEC NOx RR by a kesterite (Cu2 ZnSnS4 [CZTS]) photocathode through loading defect-engineered TiOx cocatalyst on a CdS/CZTS photocathode (TiOx /CdS/CZTS) is demonstrated. The uniquely designed photocathode enables selective ammonia production from NOx RR, yielding up to 89.1% Faradaic efficiency (FE) (0.1 V vs reversible hydrogen electrode (RHE)) with a remarkable positive onset potential (0.38 V vs RHE). By tailoring the amount of surface defective Ti3+ species, the adsorption of reactant NO3 - and * NO2 intermediate is significantly promoted while the full coverage of TiOx also suppresses NO2 - liberation as a by-product, contributing to high ammonia selectivity. Further attempts on PEC ammonia synthesis from simulated wastewater show good FE of 64.9%, unveiling the potential of using the kesterite-based photocathode for sustainably restoring ammonia from nitrate-rich wastewater.
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Short-term plasticity (STP) is an important synaptic characteristic in the hardware implementation of artificial neural networks (ANN), as it enables the temporal information processing (TIP) capability. However, the STP feature is rather challenging to reproduce from a single nonvolatile resistive random-access memory (RRAM) element, as it requires a certain degree of volatility. In this work, a Pt/TiOx/Pt exponential selector is introduced not only to suppress the sneak current but also to enable the TIP feature in a one selector-one RRAM (1S1R) synaptic device. Our measurements reveal that the exponential selector exhibits the STP characteristic, while a Pt/HfOx/Ti RRAM enables the long-term memory capability of the synapse. Thereafter, we experimentally demonstrated pulse frequency-dependent multilevel switching in the 1S1R device, exhibiting the TIP capability of the developed 1S1R synapse. The observed STP of the selector is strongly influenced by the bottom metal-oxide interface, in which Ar plasma treatment on the bottom Pt electrode resulted in the annihilation of the STP feature in the selector. A mechanism is thus proposed to explain the observed STP, using the local electric field enhancement induced at the metal-oxide interface coupled with the drift-diffusion model of mobile O2- and Ti3+ ions. This work therefore provides a reliable means of producing the STP feature in a 1S1R device, which demonstrates the TIP capability sought after in hardware-based ANN.
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Nanofiller/polymer nanocomposites are promising dielectrics for energy harvesting to be applied in wearable and flexible electronics. The structural design of the nanofillers plays a vital role to improve the energy storage performance of the related nanocomposites. Here, we fabricate a flexible device based on nonsolid titanium oxide (TiOx) nanoparticles/poly(vinylidene fluoride) (PVDF) to achieve enhanced energy storage performance at low loading. The room-temperature oxidation method is used to oxidize two-dimensional MXene (Ti3C2Tx) flakes to form partially hollow TiOx nanoparticles. Taking advantage of this structure, the flexible TiOx nanoparticles/PVDF nanocomposite with an ultralow loading content of 1 wt % nanofillers shows high energy storage performance, including a dielectric constant of ≈22 at 1 kHz, a breakdown strength of ≈480 MV m-1, and an energy storage density of 7.43 J cm-3. The finite element simulation further reveals that the optimization of the energy storage performance is ascribed to the lower electric potential among the partially hollow TiOx nanoparticles, which enhances the breakdown strength of the nanocomposites. This work opens a new avenue to structurally design and fabricate low-loading polymer-based nanocomposites for energy storage applications in next-generation flexible electronics.
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Titanium oxide is widely applied as a photocatalyst. However, its low efficiency and narrow light absorption range are two main disadvantages that severely impede its practical application. In this work, black TiOx films with different chemical compositions were fabricated by tuning target voltage and controlling O2 flow during reactive DC magnetron sputtering. The optimized TiOx films with mixed phases (TiO, Ti2O3, Ti3O5, and TiO2) exhibited fantastic photothermal and photocatalytic activity by combining high light-absorptive Ti2O3 and Ti3O5 phases with the photocatalytic TiO2 phase. The sample prepared with oxygen flow at 5.6 ± 0.2 sccm and target voltage near 400 V exhibited excellent optical absorbance of 89.29% under visible light, which could improve surface temperature to 114 °C under sunlight. This film could degrade Rhodamine-B up to 74% after 150 min of UV irradiation. In a word, this work provides a guideline for fabricating black TiOx films with photothermal-assisted photocatalytic activity by reactive DC magnetron sputtering, which could avoid the usage of hydrogen and is convenient for quantity preparation.
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The undesirable sneak current path is one of the key challenges in high-density memory integration for the emerging cross-bar memristor arrays. This work demonstrates a new heterojunction design of oxide multilayer stacking with different oxygen vacancy contents to manipulate the oxidation state. We show that the bipolar resistive switching (BRS) behavior of the Pt/TiOx/Pt cross-bar structure can be changed to complementary resistive switching (CRS) by introducing a thin TiO2 layer in the middle of the TiOx layer to obtain a Pt/TiOx/TiO2/TiOx/Pt device architecture with a double-junction active matrix. In contrast to the BRS in a single-layer TiOx matrix, the device with a double-junction matrix remains in a high-resistance state in the voltage range below the SET voltage, which makes it an efficient structure to overcome the sneak path constraints of undesired half-selected cells that lead to incorrect output reading. This architecture is capable of eliminating these half-selected cells between the nearby cross-bar cells in a smaller programming voltage range. A simplified model for the switching mechanism can be used to account for the observed high-quality switching performance with excellent endurance and current retention properties.
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The oxygen vacancies in the TiOx active layer play the key role in determining the electrical characteristics of TiOx-based memristors such as resistive-switching behaviour. In this paper, we investigated the effect of a multi-layer stacking sequence of TiOx active layers on the resistive-switching characteristics of memristor devices. In particular, the stacking sequence of the multi-layer TiOx sub-layers, which have different oxygen contents, was varied. The optimal stacking sequence condition was confirmed by measuring the current-voltage characteristics, and also the retention test confirmed that the characteristics were maintained for more than 10,000 s. Finally, the simulation using the Modified National Institute of Standards and Technology handwriting recognition data set revealed that the multi-layer TiOx memristors showed a learning accuracy of 89.18%, demonstrating the practical utilization of the multi-layer TiOx memristors in artificial intelligence systems.
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The most frequently used n-type electron transport layer (ETL) in high-efficiency perovskite solar cells (PSCs) is based on titanium oxide (TiO2) films, involving a high-temperature sintering (>450 °C) process. In this work, a dense, uniform, and pinhole-free compact titanium dioxide (TiOx) film was prepared via a facile chemical bath deposition process at a low temperature (80 °C), and was applied as a high-quality ETL for efficient planar PSCs. We tested and compared as-deposited substrates sintered at low temperatures (< 150 °C) and high temperatures (> 450 °C), as well as their corresponding photovoltaic properties. PSCs with a high-temperature treated TiO2 compact layer (CL) exhibited power conversion efficiencies (PCEs) as high as 15.50%, which was close to those of PSCs with low-temperature treated TiOx (14.51%). This indicates that low-temperature treated TiOx can be a potential ETL candidate for planar PSCs. In summary, this work reports on the fabrication of low-temperature processed PSCs, and can be of interest for the design and fabrication of future low-cost and flexible solar modules.
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In this study, by inserting a buffer layer of TiOx between the SiOx:Ag layer and the bottom electrode, we have developed a memristor device with a simple structure of Ag/SiOx:Ag/TiOx/p++-Si by a physical vapor deposition process, in which the filament growth and rupture can be efficiently controlled during analog switching. The synaptic characteristics of the memristor device with a wide range of resistance change for weight modulation by implementing positive or negative pulse trains have been investigated extensively. Several learning and memory functions have been achieved simultaneously, including potentiation/depression, paired-pulse-facilitation (PPF), short-term plasticity (STP), and STP-to-LTP (long-term plasticity) transition controlled by repeating pulses more than a rehearsal operation, and spike-time-dependent-plasticity (STDP) as well. Based on the analysis of logarithmic I-V characteristics, it has been found that the controlled evolution/dissolution of conductive Ag-filaments across the dielectric layers can improve the performance of the testing memristor device.
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The majority of high-performance perovskite and polymer solar cells consist of a TiO2 electron transport layer (ETL) processed at a high temperature (>450 °C). Here, we demonstrate that low-temperature (80 °C) ETL thin film of TiOx:Zn1-xCdxS can be used as an effective ETL and its band energy can be tuned by varying the TiOx:Zn1-xCdxS ratio. At the optimal ratio of 50:50 (vol%), the MAPbIxCl1-x perovskite and PCBTBT:PC70BM polymer solar cells achieved 9.79% and 4.95%, respectively. Morphological and optoelectronic analyses showed that tailoring band edges and homogeneous distribution of the local surface charges could improve the solar cells efficiency by more than 2%. We proposed a plausible mechanism to rationalize the variation in morphology and band energy of the ETL.
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Since 1970, TiO2 photocatalysis has been considered a possible alternative for sustainable water treatment. This is due to its material stability, abundance, nontoxicity and high activity. Unfortunately, its wide band gap (≈3.2 eV) in the UV portion of the spectrum makes it inefficient under solar illumination. Recently, so-called "black TiO2" has been proposed as a candidate to overcome this issue. However, typical synthesis routes require high hydrogen pressure and long annealing treatments. In this work, we present an industrially scalable synthesis of TiO2-based material based on laser irradiation. The resulting black TiO x shows a high activity and adsorbs visible radiation, overcoming the main concerns related to the use of TiO2 under solar irradiation. We employed a commercial high repetition rate green laser in order to synthesize a black TiO x layer and we demonstrate the scalability of the present methodology. The photocatalyst is composed of a nanostructured titanate film (TiO x ) synthetized on a titanium foil, directly back-contacted to a layer of Pt nanoparticles (PtNps) deposited on the rear side of the same foil. The result is a monolithic photochemical diode with a stacked, layered structure (TiO x /Ti/PtNps). The resulting high photo-efficiency is ascribed to both the scavenging of electrons by Pt nanoparticles and the presence of trap surface states for holes in an amorphous hydrogenated TiO x layer.
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The superior bulk properties (corrosion resistance, high strength to weight ratio, relatively low cost and easy processing) of hydrocarbon based polymers such as polypropylene (PP) have contributed significantly to the development of new biomedical applications such as artificial organs and cell scaffolds. However, low cell affinity is one of the main draw backs for PP due to its poor surface properties. In tissue engineering, physico-chemical surface properties such as hydrophilicity, polar functional groups, surface charge and morphology play a crucial role to enrich the cell proliferation and adhesion. In this present investigation TiOx based biocompatible coatings were developed on the surface of PP films via DC excited glow discharge plasma, using TiCl4/Ar+O2 gas mixture as a precursor. Various TiOx-based coatings are deposited on the surface of PP films as a function of discharge power. The changes in hydrophilicity of the TiOx/PP film surfaces were studied using contact angle analysis and surface energy calculations by Fowke's approximation. X-ray photo-electron spectroscopy (XPS) was used to investigate the surface chemical composition of TiOx/PP films. The surface morphology of the obtained TiOx/PP films was investigated by scanning electron and transmission electron microscopy (SEM &TEM). Moreover, the surface topography of the material was analyzed by atomic force microscopy (AFM). The cytocompatibility of the TiOx/PP films was investigated via in vitro analysis (cell viability, adhesion and cytotoxicity) using NIH3T3 (mouse embryonic fibroblast) cells. Furthermore the antibacterial activities of TiOx/PP films were also evaluated against two distinct bacterial models namely Gram positive Staphylococcus aureus (S.aureus) and Gram negative Escherichia coli DH5α. (E.coli) bacteria. XPS results clearly indicate the successful incorporation of TiOx and oxygen containing polar functional groups on the surface of plasma treated PP films. Moreover the surface of modified PP films exhibited nano structured morphology, as confirmed by SEM, TEM and AFM. The physico-chemical changes have improved the hydrophilicity of the PP films. The in-vitro analysis clearly confirms that the TiOx coated PP films performs as good as the standard tissue culture plates and also are unlikely to impact the bacterial cell viability.