Modulation of the Band Gap and Redox Properties by Mixed Addenda in Sandwich Polyoxometalates.

Due to the wide range of applications of band-gap engineering in optoelectronics and photocatalysis, the rational design of polyoxometalate (POM) frameworks is highly desired. Here, we have successfully synthesized a series of mixed addenda (Mo and W) sandwich POMs by systematically varying pH, concentrations of salts, and counterions in Weakley-type sandwich POMs by incorporating Mo into the framework of tetrasubstituted sandwich POMs. Crystallographic analysis reveals the centrosymmetric structure; with variation in the Mo to W ratio, Mo preferentially binds to µ2 oxygen connected to transition metals in the sandwich position. UV-visible spectroscopy, electrochemical, and theoretical modeling rationalize the band-gap modulations. Theoretical studies and cyclic voltammograms indicate that during the reduction, the incoming electrons preferentially go to substituted transition metals followed by Mo. Flat band potential calculated from the Mott-Schottky enables tuning of the electronic properties of composites based on these sandwich POMs. Moreover, the dioxygen binding and activation studies of these polyoxometalates have been highlighted.

Physico- and Electrochemical Properties of First-Row Transition-Metal-Substituted Sandwich Polyoxometalates.

The physico- and electrochemical behaviors of a series of [WZn3(H2O)2(ZnW9O34)2]12- (Zn-WZn3) and its first-row transition-metal-substituted analogues [WZn(TM)2(H2O)2(ZnW9O34)2]12- (Zn-WZn(TM)2; TM = MnII, CoII, FeIII, NiII and CuII) are reported. Various spectroscopic studies, including Fourier transform infrared (FTIR) spectroscopy, UV-visible spectroscopy, electrospray ionization (ESI)-mass spectrometry, and Raman spectroscopy, show similar spectral patterns in all sandwich polyoxometalates (POMs) because of their isostructural geometry and constancy of the overall negative charge (-12). However, the electronic properties highly depend on the transition metals at the "sandwich core" and correlate well with the density functional theory (DFT) study. Further, depending on the substituted TM atoms, there is a decrease in the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) band-gap energy in these transition-metal-substituted POM (TMSP) complexes wrt Zn-WZn3, as confirmed by diffuse reflectance spectroscopy and DFT study. Cyclic voltammetry reveals that the electrochemistry of these sandwich POMs (Zn-WZn3 and TMSPs) is highly dependent on the pH of the solution. Moreover, the dioxygen binding/activation studies of these polyoxometalates show that Zn-WZn3 and Zn-WZnFe2 have better efficiency toward dioxygen binding, as confirmed by FTIR spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA), which is also reflected in their catalytic activity toward imine synthesis.

Stabilization and activation of polyoxometalate over poly(vinyl butylimidazolium) cations towards electrocatalytic water oxidation in alkaline media.

Sandwich polyoxometalate [WCo3(H2O)2(CoW9O34)2]12- (Co-WCo3) heterogenized with poly(vinyl butyl imidazolium) cations (PVIM+) acts as a stable electrochemical water oxidation catalyst in 1 M KOH with 0.28 V@10 mA cm-2 overpotential and TOF of 6.16 s-1. Various in situ spectroelectrochemical studies and control experiments provide the details of the catalytic activities and long-term stability of the catalyst.

Selective Electrochemical Conversion of N2 to NH3 in Neutral Media Using B, N-Containing Carbon with a Nanotubular Morphology.

Electrochemical dinitrogen reduction (NRR) has riveted substantial attention as a greener method to synthesize ammonia (NH3) under ambient conditions. Here, B, N-containing carbon catalysts with a discrete morphology were synthesized from the metal-organic framework-ionic liquid (MOF-IL) composite for NRR in a neutral electrolyte medium (pH = 7). Morphology-dependent activity is witnessed, wherein C-BN@600 with a nanotubular morphology is able to achieve a high NH3 yield rate of 204 µg h-1 mgcat-1 and an F.E. of 16.7% with a TOF value of 0.2 h-1 at -0.2 V vs RHE. Further, a rigorous protocol is put forward for true NH3 estimation by tracing/eliminating any source of contamination in catalysts, electrolytes, or gas supply via ultraviolet-visible (UV-vis) spectroscopy, gas-purification methods, and isotope labeling experiments. Density functional theory predicts BN to be the favorable active site for N2 adsorption with a reduced energy barrier in the first reduction step and sequential stabilization of the B-N bond by an adjacent carbon atom.

A novel NiVP/Pi-based flexible sensor for direct electrochemical ultrasensitive detection of cholesterol.

A novel non-enzymatic electrochemical sensor was constructed to achieve a highly selective and ultrasensitive detection of cholesterol to address the problems related to serious coronary heart disease. The NiVP/Pi-based sensor exhibited ultra-high sensitivity of 5510.18 µA µM-1 cm-2 and 36.8 µA µM-1 cm-2 for 1 nM to 10 µM and 100 µM to 10 mM of cholesterol, respectively, with an ultra-low detection limit of 1 aM, along with superior selectivity for cholesterol when exposed to various interferents such as ascorbic acid, glucose and uric acid. Also, a novel NiVP/Pi-based flexible sensor coated onto Whatman filter paper was developed and displayed superior sensitivity, even with a human blood serum sample at physiological pH.

Ultrasensitive electrochemical biosensors for dopamine and cholesterol: recent advances, challenges and strategies.

The rapid and accurate determination of the dopamine (neurotransmitter) and cholesterol level in bio-fluids is significant because they are crucial bioanalytes for several lethal diseases, which require early diagnosis. The level of DA in the brain is modulated by the dopamine active transporter (DAT), and is influenced by cholesterol levels in the lipid membrane environment. Accordingly, electrochemical biosensors offer rapid and accurate detection and exhibit unique features such as low detection limits even with reduced volumes of analyte, affordability, simple handling, portability and versatility, making them appropriate to deal with augmented challenges in current clinical and point-of-care diagnostics for the determination of dopamine (DA) and cholesterol. This feature article focuses on the development of ultrasensitive electrochemical biosensors for the detection of cholesterol and DA for real-time and onsite applications that can detect targeted analytes with reduced volumes and sub-picomolar concentrations with quick response times. Furthermore, the development of ultrasensitive biosensors via cost-effective, simple fabrication procedures, displaying high sensitivity, selectivity, reliability and good stability is significant in the impending era of electrochemical biosensing. Herein, we emphasize on recent advanced nanomaterials used for the ultrasensitive detection of DA and cholesterol and discuss in depth their electrochemical activities towards ultrasensitive responses. Key points describing future perspectives and the challenges during detection with their probable solutions are discussed, and the current market is also surveyed. Further, a comprehensive review of the literature indicates that there is room for improvement in the miniaturization of cholesterol and dopamine biosensors for lab-on-chip devices and overcoming the current technical limitations to facilitate full utilization by patients at home.

Nickel Iron Phosphide/Phosphate as an Oxygen Bifunctional Electrocatalyst for High-Power-Density Rechargeable Zn-Air Batteries.

The evolution of an effective oxygen electrocatalyst is of great importance for the widespread application of Zn-air batteries but remains an immense challenge. Thus, an efficient catalyst toward the oxygen evolution reaction and oxygen reduction reaction (OER and ORR) is highly essential for high-performance Zn-air batteries. Here, we have reported bifunctional nickel iron phosphide/phosphate (NiFeP/Pi) catalysts with various Ni/Fe ratios toward oxygen electrocatalysis in alkaline media. These catalysts are highly active toward OER and ORR, wherein NiFe(1:2)P/Pi exhibits a low OER overpotential of 0.21 V at 10 mA cm-2 and a high ORR onset potential (0.98 V vs RHE) with the lowest potential difference (ΔE = E10 - E1/2) of 0.62 V, which surpasses that of the benchmark Pt/C and RuO2 catalyst as well as those of most previously reported bifunctional catalysts. Furthermore, the NiFe(1:2)P/Pi-based Zn-air battery demonstrates a very high power density of 395 mW cm-2 and outstanding discharge capacity of 900 mAh g-1@10 mA cm-2 along with steady cyclability, maintaining 98% of the round trip efficiency over 300 cycles. These results are helpful for a good understanding of the composition-activity relation with a certain band gap toward high-performance Zn-air batteries.

Highly sensitive non-enzymatic electrochemical glucose sensor surpassing water oxidation interference.

An electrochemical non-enzymatic sensor based on a NiVP/Pi material was developed for the selective and sensitive determination of glucose. The novel sensor showed a high sensitivity of 6.04 mA µM-1 cm-2 with a lowest detection limit of 3.7 nM in a wide detection range of 100 nM-10 mM. The proposed sensor exhibited a superior selectivity without any interference from the oxygen evolution reaction during glucose sensing. We also found that this glucose sensor showed negligible interference from various interferents, such as ascorbic acid, uric acid, dopamine and sodium chloride. Additionally, a novel flexible sensor was developed by coating the NiVP/Pi over Whatman filter paper, which exhibited two linear ranges of 100 nM to 1 µM and 100 µM to 10 mM with an ultra-sensitivity of 1.130 mA µM-1 cm-2 and 0.746 mA µM-1 cm-2, respectively, in 0.1 M NaOH. The proposed sensor was tested with human blood serum samples demonstrating its practical application. Our findings provide a new route by fine tuning the composition of nickel and vanadium that sheds new light on better understanding the processes. This NiVP/Pi-based sensor offers a new approach towards the electrochemical detection of glucose, enabling glucose monitoring in a convenient way.

Ultrasensitive and highly selective detection of dopamine by a NiFeP based flexible electrochemical sensor.

A ultrasensitive NiFeP based electrochemical sensor was developed for the selective electrochemical detection of dopamine to address the issue associated with neurological disorders including Parkinson's and Alzheimer's diseases. The novel sensor shows superior selectivity and sensitivity with a lowest detection limit of 0.3 nM and a wide detection range of 10 nM-500 µM and is immune to the interference of ascorbic acid at physiological pH (7.4). A novel flexible sensor was developed with NiFeP coated over Whatman filter paper, which exhibits two liner ranges of 10 nM-1µM and 10 µM-500 µM with an ultra high sensitivity of 756 µA µM-1 cm-2 and 4.6 µA µM-1 cm-2 respectively with a wide detection range of 10 nM to 500 µM.

PVIM-Co5POM/MNC composite as a flexible electrode for the ultrasensitive and highly selective non-enzymatic electrochemical detection of cholesterol.

To address the issues allied with cardiovascular diseases and the increased prevalence of hypertension, a novel electrochemical sensor was developed based on poly(ionic liquid) [PVIM]-cobalt polyoxometalate (Co5POM) supported on carbonaceous materials (MNCs) for the highly selective and ultrasensitive non-enzymatic detection of cholesterol. The novel composite exhibits excellent selectivity and sensitivity towards the non-enzymatic electrochemical detection of cholesterol with a low detection limit of 1 fM (1 × 10-15 M), a response time of ∼5 s, and a wide detection range of 1 fM-5 mM with two linear ranges of 1 fM-200 nM and 0.5 µM-5 mM with sensitivities of 210 and 64 µA µM-1 cm-2, respectively, even in the presence of ascorbic acid, glucose and uric acid. The proposed sensor was tested with a human blood serum sample at physiological pH in a physiologically relevant concentration range. A novel flexible sensor was developed with PVIM-Co5POM/MNC coated over Whatman filter paper and this shows a high sensitivity with a wide detection range of 1 fM-5 mM.

Stabilization of Cobalt-Polyoxometalate over Poly(ionic liquid) Composites for Efficient Electrocatalytic Water Oxidation.

The key to unlock a renewable, clean, and energy-dense hydrogen fuel lies in designing an efficient oxygen evolving catalyst exhibiting high activity, stability, and cost-effectiveness. This report addresses an improved activity toward oxygen evolution by a composite of cobalt-polyoxometalate [Co4(H2O)2(PW9O34)2]10- (CoPOM) and an ionic polymer, poly(vinyl butyl imidazolium) (PVIM), in highly alkaline media. PVIM provides a stable platform for CoPOM and acts as a conductive linker between CoPOM and the electrode surface, forming a concrete solid composite, which balances the multinegative charge of CoPOM synergistically. This improved stability and conductivity of CoPOM by PVIM in the PVIM-CoPOM composite performs remarkable electrocatalytic water oxidation with a very low overpotential of 0.20 V and a very high current density of 250 mA/cm2 (at 1.75 V vs RHE) with a turnover frequency (TOF) of 52.8 s-1 in 1 M NaOH.

Ultrasensitive and Highly Selective Electrochemical Detection of Dopamine Using Poly(ionic liquids)-Cobalt Polyoxometalate/CNT Composite.

A novel sandwich polyoxometalate (POM) Na12[WCo3(H2O)2(CoW9O34)2] and poly(vinylimidazolium) cation [PVIM+] in combination with nitrogen-doped carbon nanotubes (NCNTs) was developed for a highly selective and ultrasensitive detection of dopamine. Conductively efficient heterogenization of Co5POM catalyst by PVIM over NCNTs provides the synergy between PVIM-POM catalyst and NCNTs as a conductive support which enhances the electron transport at the electrode/electrolyte interface and eliminates the interference of ascorbic acid (AA) at physiological pH (7.4). The novel PVIM-Co5POM/NCNT composite demonstrates a superior selectivity and sensitivity with a lowest detection limit of 500 pM (0.0005 µM) and a wide linear detection range of 0.0005-600 µM even in the presence of higher concentration of AA (500 µM).

Perfluoroalkylated Calix[4]pyrroles: Fluoride Ion Extraction from an Aqueous Medium.

Octaalkenyl calix[4]pyrrole ((CH2 =CH(CH2 )2 )8 C4P) is highly useful for the postfunctionalization of different calix[4]pyrroles with desired functionalities. Functionalization with perfluoroalkyl chains [CF3 (CF2 )n ; Rfn ] gave perfluoroalkyl calix[4]pyrroles (Rfn (CH2 )4 )8 C4P; n=6, 8), having >60 % fluorine content, which created a hydrophobic environment inside the calix[4]pyrrole cavity and recognized fluoride and chloride ions in solution as well as in the solid state. The fluoride ion is extracted efficiently from aqueous CsF and TBAF solutions by using (Rf6 (CH2 )4 )8 C4P, as droplets. The fluorinated chain generated a hydrophobic environment which broke the hydration shell associated with the anion and separated out fluoride ions as droplets from aqueous medium. Furthermore, the fluoride ions competitively replaced chloride ions from the (Rf6 (CH2 )4 )8 C4P cavity.

Ether and siloxane functionalized ionic liquids and their mixtures as electrolyte for lithium-ion batteries.

The present study deals with an investigation of two novel imidazolium ionic liquids bearing ether-ether (1O2O2-Im-2O1) or ether-siloxane (1O2O2-Im-1SiOSi) functionalities with TFSI anion and their mixtures with propylene carbonate as electrolytes in lithium-ion batteries. The electrochemical stability and conductivity of these novel ILs were analyzed by electrochemical studies, such as cyclic voltammetry, linear sweep voltammetry and impedance measurements. The applicability of these ILs as electrolytes in Li-ion batteries was studied in the presence of a high concentration of LiTFSI (1 mol kg(-1) electrolyte) and the ether-ether IL was shown to possess a high electrochemical stability window (ESW) of 5.9 V and good conductivity of 2.2 mS cm(-1). The electrochemical stability and conductivity were further complimented by self-diffusion of different ions using pulsed gradient spin-echo (PGSE) NMR, viscosity and thermal properties like TGA and DSC analysis. More importantly, we explored the effect of temperature on the electrochemical stability and conductivity of these ILs by electrochemical impedance spectroscopy.

Fluorous membrane ion-selective electrodes for perfluorinated surfactants: trace-level detection and in situ monitoring of adsorption.

Ion-selective electrodes (ISEs) with fluorous anion-exchanger membranes for the potentiometric detection of perfluorooctanoate (PFO(-)) and perfluorooctanesulfonate (PFOS(-)) were developed. Use of an anion-exchanger membrane doped with the tetraalkylphosphonium derivative (Rf8(CH2)2)(Rf6(CH2)2)3P(+) and an optimized measurement protocol resulted in detection limits of 2.3 × 10(-9) M (1.0 ppb) for PFO(-) and 8.6 × 10(-10) M (0.43 ppb) for PFOS(-). With their higher selectivity for PFO(-) over OH(-), membranes containing the alternative anion exchanger (Rf6(CH2)3)3PN(+)P((CH2)3Rf6)3 with a bis(phosphoranylidene)ammonium group further improved the detection limit for PFO(-) to 1.7 × 10(-10) M (0.070 ppb). These values are comparable with results obtained using well-established techniques such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and liquid chromatography-tandem mass spectrometry (LC-MS-MS), but the measurement with ISEs avoids lengthy sample preconcentration, can be performed in situ, and is less costly. Even when eventual spectrometric confirmation of analyte identity is required, prescreening of large numbers of samples or in situ monitoring with ISEs may be of substantial benefit. To demonstrate a real-life application of these electrodes, in situ measurements were performed of the adsorption of PFOS(-) onto Ottawa sand, which is a standard sample often used in environmental sciences. The results obtained are consistent with those from an earlier LC-MS study, validating the usefulness of these sensors for environmental studies. Moreover, PFOS(-) was successfully measured in a background of water from Carnegie Lake.

Potentiometric sensors based on fluorous membranes doped with highly selective ionophores for carbonate.

Manganese(III) complexes of three fluorophilic salen derivatives were used to prepare ion-selective electrodes (ISEs) with ionophore-doped fluorous sensing membranes. Because of their extremely low polarity and polarizability, fluorous media are not only chemically very inert but also solvate potentially interfering ions poorly, resulting in a much improved discrimination of such ions. Indeed, the new ISEs exhibited selectivities for CO(3)(2-) that exceed those of previously reported ISEs based on nonfluorous membranes by several orders of magnitude. In particular, the interference from chloride and salicylate was reduced by 2 and 6 orders of magnitude, respectively. To achieve this, the selectivities of these ISEs were fine-tuned by addition of noncoordinating hydrophobic ions (i.e., ionic sites) into the sensing membranes. Stability constants of the anion-ionophore complexes were determined from the dependence of the potentiometric selectivities on the charge sign of the ionic sites and the molar ratio of ionic sites and the ionophore. For this purpose, a previously introduced fluorophilic tetraphenylborate and a novel fluorophilic cation with a bis(triphenylphosphoranylidene)ammonium group, (R(f6)(CH(2))(3))(3)PN(+)P(R(f6)(CH(2))(3))(3), were utilized (where R(f6) is C(6)F(13)). The optimum CO(3)(2-) selectivities were found for sensing membranes composed of anionic sites and ionophore in a 1:4 molar ratio, which results in the formation of 2:1 complexes with CO(3)(2-) with stability constants up to 4.1 × 10(15). As predicted by established theory, the site-to-ionophore ratios that provide optimum potentiometric selectivity depend on the stoichiometries of the complexes of both the primary and the interfering ions. However, the ionophores used in this study give examples of charges and stoichiometries previously neither explicitly predicted by theory nor shown by experiment. The exceptional selectivity of fluorous membranes doped with these carbonate ionophores suggests their use not only for potentiometric sensing but also for other types of sensors, such as the selective separation of carbonate from other anions and the sequestration of carbon dioxide.

Curcumin enhances the efficacy of chemotherapy by tailoring p65NFκB-p300 cross-talk in favor of p53-p300 in breast cancer.

Breast cancer cells often develop multiple mechanisms of drug resistance during tumor progression, which is the major reason for the failure of breast cancer therapy. High constitutive activation of NFκB has been found in different cancers, creating an environment conducive for chemotherapeutic resistance. Here we report that doxorubicin-induced SMAR1-dependent transcriptional repression and SMAR1-independent degradation of IkBα resulted in nuclear translocation of p65NFκB and its association with p300 histone acetylase and subsequent transcription of Bcl-2 to impart protective response in drug-resistant cells. Consistently SMAR1-silenced drug-resistant cells exhibited IkBα-mediated inhibition of p65NFκB and induction of p53-dependent apoptosis. Interestingly, curcumin pretreatment of drug-resistant cells alleviated SMAR1-mediated p65NFκB activation and hence restored doxorubicin sensitivity. Under such anti-survival condition, induction of p53-p300 cross-talk enhanced the transcriptional activity of p53 and intrinsic death cascade. Importantly, promyelocyte leukemia-mediated SMAR1 sequestration that relieved the repression of apoptosis-inducing genes was indispensable for such chemo-sensitizing ability of curcumin. A simultaneous decrease in drug-induced systemic toxicity by curcumin might also have enhanced the efficacy of doxorubicin by improving the intrinsic defense machineries of the tumor-bearer. Overall, the findings of this preclinical study clearly demonstrate the effectiveness of curcumin to combat doxorubicin-resistance. We, therefore, suggest curcumin as a potent chemo-sensitizer to improve the therapeutic index of this widely used anti-cancer drug. Taken together, these results suggest that curcumin can be developed into an adjuvant chemotherapeutic drug.

Ionic transformations in extremely nonpolar fluorous media: easily recoverable phase-transfer catalysts for halide-substitution reactions.

Solutions of the fluorous alkyl halides R(f8)(CH(2))(m)X (R(fn)=(CF(2))(n-1)CF(3); m=2, 3; X=Cl, Br, I) in perfluoromethylcyclohexane or perfluoromethyldecalin are inert towards solid or aqueous NaCl, NaBr, KI, KCN, and NaOAc. However, halide substitution occurs in the presence of fluorous phosphonium salts (R(f8)(CH(2))(2))(R(f6)(CH(2))(2))(3)P(+)X(-) (X=I (1), Br (3)) and (R(f8)(CH(2))(2))(4)P(+)I(-) (10 mol %), which are soluble in the fluorous solvents under the reaction conditions (76-100 degrees C). Stoichiometric reactions of a) 1 with R(f8)(CH(2))(2)Br and b) 3 with R(f8)(CH(2))(2)I were conducted under homogenous conditions in perfluoromethyldecalin at 100 degrees C and yielded the same R(f8)(CH(2))(2)I/R(f8)(CH(2))(2)Br equilibrium ratio ( approximately 60:40). This shows that ionic displacements can take place in extremely nonpolar fluorous phases and suggests a classical phase-transfer mechanism for the catalyzed reactions. Interestingly, the nonfluorous salt (CH(3)(CH(2))(11))(CH(3)(CH(2))(7))(3)P(+)I(-) (4) also catalyzes halide substitutions, but under triphasic conditions with 4 suspended between the lower fluorous and upper aqueous layers. NMR experiments established very low solubilities in both phases, which suggests interfacial catalysis. Catalyst 1 is easily recycled, optimally by simple precipitation onto teflon tape.

Contribution of p53-mediated Bax transactivation in theaflavin-induced mammary epithelial carcinoma cell apoptosis.

Theaflavins, the bioactive flavonoids of black tea, have been demonstrated to inhibit proliferation and induce apoptosis in a variety of cancer cells. However, the contribution of p53 in mammary epithelial carcinoma cell apoptosis by theaflavins remains unclear. It has been reported that p53 triggers apoptosis by inducing mitochondrial outer membrane permeabilization through transcription-dependent and -independent mechanisms. Using wild-type and mutant p53-expressing as well as p53-null cells we found a strong correlation between p53 status and theaflavin-induced breast cancer cell apoptosis. Apoptogenic effect was more pronounced in functional p53-expressing cells in which theaflavins raised p53 protein levels that harmonized with Bax up-regulation and migration to mitochondria. However, in the same cells, when p53-mediated transactivation was inhibited by pifithrin-alpha, theaflavins not only failed to increase transcription but also to induce apoptosis although p53 up-regulation was not altered. In contrast, Bax over-expression restored back theaflavin-induced apoptosis in pifithrin-alpha-inhibited/dominant-negative p53-expressing cells. Inhibition of Bax by RNA-interference also reduced theaflavin-induced apoptosis. These results not only indicated the requirement of p53-mediated transcriptional activation of Bax but also its role as down-stream effecter in theaflavin-induced apoptosis. Bax up-regulation resulted in mitochondrial transmembrane potential loss and cytochrome c release followed by activation of caspase cascade. In contrast, mitochondrial translocation of p53 and its interaction with Bcl-2 family proteins or activation of caspase-8 could not be traced thereby excluding the involvement of p53-mediated transcription-independent pathways. Together these findings suggest that in breast cancer cells, p53 promotes theaflavin-induced apoptosis in a transcription-dependent manner through mitochondrial death cascade.

Black tea-induced decrease in IL-10 and TGF-beta of tumor cells promotes Th1/Tc1 response in tumor bearer.

Several lines of evidence support that impairment of host immune function by tumor may be related to several strategies of tumor escape from immunosurveillance. We found that in Ehrlich's ascites carcinoma (EAC)-bearing mice, the tumor cells secrete immunosuppressive cytokines, transforming growth factor beta (TGF-beta) and interleukin-10 (IL-10) that induce a general T helper cells type 2 (Th2) dominance dampening the T cytotoxic cells type 1 (Tc1) population. Interestingly, black tea at the antitumor dose of 2.5% significantly reduced TGF-beta and IL-10 in tumor cells in vivo, thereby preventing Th2 dominance in the tumor bearers and initiating a Th1/Tc1 response. Thus, apart from its anticancer activity, this popular beverage also rejuvenates cancer immunosurveillance by modulating cytokine profiles and establishing Th1/Tc1 dominance in the tumor-bearing host.