Hydrogen is the solution to all the problems associated with the energy crisis. Generating hydrogen from water splitting is one of the greener approaches, but it requires an efficient catalyst that is economical for the bulk production of hydrogen. The transition metal-aqua coordination complexes, which are otherwise inactive/unstable for electrochemical hydrogen evolution reaction (HER) activity, can efficiently be utilized for the same by attaching these metal-aqua species on a stable support. With a similar approach, we have synthesized and structurally characterized a two-dimensional polyoxometalate (POM)-copper complex hybrid that supports a copper(II)-aqua-bypyridine complex with a molecular formula of the overall system, [{Cu II . The bis(aqua)-mono(bipyridine) Cu(II)-complex fragment {Cu II (2,2′bpy)(H 2 O) 2 } 2+ , attached to the two-dimensional POM-Cu-complex support, acts as an active catalytic center that catalyzes the electrochemical HER. The electrochemical studies done for this work enabled us to understand the role of compound 1 as an electrocatalyst for the HER in near-neutral medium (pH 4.8), under buffered conditions (acetate buffer). Through detailed electrochemical experiments including controlled ones, we understand that compound 1 follows a proton-coupled electron transfer (PCET) pathway with one proton and one electron involvement in the HER. The overpotential required to achieve a current density of 1 mA/cm 2 is found to be 520 mV with a Faradaic efficiency of 81%.
Myeloid-derived dendritic cells (DCs) generated from monocytes obtained from stage IIIB cervical cancer (CaCx IIIB) patients show dysfunctional maturation; thus, antitumor T cell functions are dysregulated. In an objective to optimize these dysregulated immune functions, the present study is focused on the ability of neem leaf glycoprotein (NLGP), a nontoxic preparation of the neem leaf, to induce optimum maturation of dendritic cells from CaCx IIIB patients. In vitro NLGP treatment of immature DCs (iDCs) obtained from CaCx IIIB patients results in upregulated expression of various cell surface markers (CD40, CD83, CD80, CD86, and HLA-ABC), which indicates DC maturation. Consequently, NLGP-matured DCs displayed balanced cytokine secretions, with type 1 bias and noteworthy functional properties. These DCs displayed substantial T cell allostimulatory capacity and promoted the generation of cytotoxic T lymphocytes (CTLs). Although NLGPmatured DCs derived from CaCx monocytes are generally subdued compared to those with a healthy monocyte origin, considerable revival of the suppressed DC-based immune functions is noted in vitro at a fairly advanced stage of CaCx, and thus, further exploration of ex vivo and in vivo DC-based vaccines is proposed. Moreover, the DC maturating efficacy of NLGP might be much more effective in the earlier stages of CaCx, where the extent of immune dysregulation is less and, thus, the scope of further investigation may be explored.Cervical cancer (CaCx) is the second most common type of tumor worldwide, and its incidence is disproportionately high (Ͼ80%) in the developing world (35). It remains an important health problem for women, especially in underserved and socioeconomically backward classes (29). Immunotherapy with mature monocyte-derived dendritic cells (DCs) pulsed with human papillomavirus type 16 or 18 (HPV16/18) E7 oncoprotein antigens is a promising approach in treating this disease (32). These alternate therapeutic approaches are aimed toward controlling late-stage detection and preventing recurrence (31), an arena where application of traditional therapeutic approaches like radical surgery or radiotherapy is difficult. DCs are extremely potent antigen-presenting cells (APC) that function in vitro and in vivo to initiate T lymphocyte responses to antigens (14). The ability of DCs to stimulate T cells is attributed to their dichotomous nature as immature DCs (iDCs) and mature DCs (mDCs) (30). Immature DCs effectively capture antigens but lack full T cell stimulatory activity and are sensitive to the immunosuppressive effects of an immunoregulatory cytokine, interleukin-10 (IL-10). In contrast, mature DCs exhibit an enhanced level of antigen presentation, full T cell stimulatory activity, production of a type 1 cytokine, IL-12, and low production of a type 2 cytokine, IL-10 (36).In the last few years, a multitude of diagnostic studies have shown a strong immunosuppressive state of the cervical epithelium, which is one major reason for the fragile health of cervical cancer patient...
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