Fabrication of Unique Mixed-Valent CoICoII and CuICuII Metal-Organic Frameworks (MOFs) for Desulfurization of Fuels: A Combined Experimental and Theoretical Approach toward Green Fuel.

Herein, metal-organic framework (MOF)-based adsorbents are designed with distinct hard and soft metal building units, namely, [Co2ICoII(PD)2(BP)] (Co_PD-BP) and [Cu2ICuII(PD)2(BP)] (Cu_PD-BP), where H2PD = pyrazine-1,4-diide-2,3-dicarboxylic acid and BP = 4,4'-bipyridine. The designed MOFs were characterized via spectral and SCXRD techniques, which confirm the mixed-valent states (+1 and +2) of the metal ions. Topological analysis revealed the rare ths and gwg topologies for Co MOF, while Cu-MOF exhibits a unique 8T21 topology in the 8-c net (point symbol for net: {424·64}). Moreover, severe environmental issues can be resolved by effectively removing heterocyclic organosulfur compounds from fuels via adsorptive desulfurization. Further, the developed MOFs were investigated for sulfur removal via adsorptive desulfurization from a model fuel consisting of dibenzothiophene (DBT), benzothiophene (BT), and thiophene (T) in the liquid phase using n-octane as a solvent. The findings revealed that Cu_PD-BP effectively removes the DBT with a removal efficiency of 86% at 300 ppm and an operating temperature of 25 °C, with a recyclability of up to four cycles. The adsorption kinetic analysis showed that the pseudo-first-order model could fit better with the experimental data indicating the physisorption process. Further, the studies revealed that adsorption capacity increased with the increasing initial DBT concentration with a remarkable capacity of 70.5 mg/g, and the adsorption process was well described by the Langmuir isotherm. The plausible reason behind the enhanced removal efficiency shown by Cu_PD-BP as compared to Co_PD-BP could be the soft-soft interactions between soft sulfur and soft Cu metal centers. Interestingly, density functional theory (DFT) studies were done in order to predict the mechanism of binding of thiophenic compounds with Cu_PD-BP, which further ascertained that along with other interactions, the S···π and S···Cu interactions predominate, resulting in a high uptake of DBT as compared to others. In essence, Cu_PD-BP turns out to be a promising adsorbent in the field of fuel desulfurization for the benefit of mankind.

Carbon Nanotubes Decorated with Coordination Polymers for Fluorescence Detection of Heavy-Metal Ions and Nitroaromatic Chemicals.

Herein, [Nd(NO3)3(H2pzdca)] n (MA-1) was synthesized from a reaction of 2,3-pyrazinedicarboxylic acid [H2Pzdca] as an organic linker with salt of Nd(III) under solvothermal conditions. The detailed structural analysis for crystals was performed utilizing single-crystal X-ray diffraction (SCXRD). After that, the neodymium-based coordination polymer (MA-1) crystal was directly generated upon the surface of functionalized carbon nanotubes (F-CNTs) through bonds or affinity between F-CNTs and MA-1 via the solvothermal approach. Meanwhile, the existence of F-CNTs does not affect the production of MA-1 crystals. FT-IR, PXRD, SEM, TEM, and SCXRD studies were used to characterize the crystalline material, MA-1 and MA-1@CNT. To investigate the MA-1@CNT sensing properties, Pb(II), As(III), Cr(VI), and nitrobenzene (NB) were utilized as analytes. It is worth mentioning that MA-1@CNT developed as a susceptible sensor exhibits a fluorescence "turn-on" response for Pb(II) and As(III) ions, while a fluorescence "turn-off" response in the case of Cr(VI) and NB with significantly low limit of detection (LOD) values of 15.9 for Pb(II), 16.0 for As(III), 76.9 for Cr(VI), and 21.1 nM for NB, which are comparable with the lowest LOD available in the literature. Furthermore, MA-1@CNT could be conveniently regenerated and reused for at least three cycles by simply filtering and washing with water several times. The sensing mechanism is ascribed to the inner filter effect owing to the overlap between the emission and/or excitation bands of MA-1@CNT with the absorption bands of Cr(VI) and NB. In contrast, the fluorescence enhancement in the case of Pb(II) and As(III) could be correlated to the chelation-enhanced fluorescence phenomenon. These results indicate that MA-1@CNT is an ideal sensor for Pb(II), As(III), Cr(VI), and NB recognition.

Synthesis of 2D Metal-Organic Nanosheets (MONs) by Liquid Phase Exfoliation: Applications in Effective Delivery of Antiulcer Drugs and Selective Adsorption and Removal of Cationic Dyes.

Nowadays, the fabrication of 2D metal-organic nanosheets (2D MONs) has entered the research arena fascinating researchers worldwide. However, a lack of efficient and facile methods has remained a bottleneck for the manufacturing of these 2D MONs. Herein, a 2D metal-organic framework (MOF), i.e., 2D Cu-MOF, was synthesized using a facile and convenient stirring method by using 4,4'-trimethylenedipyridine (TMDP) as an organic linker. The as-prepared MOF was characterized in detail and based on single crystal X-ray diffraction analysis, it was established that tangled layers in the 2D Cu-MOF are interconnected to produce thick strands. These tangled layers could be easily separated via ultrasonication-induced liquid phase exfoliation (UILPE) to give the 2D Cu-MON as illustrated through Tyndall light scattering and exhaustive microscopic exploration such as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The application of this 2D Cu-MON was assessed in the field of drug delivery revealing exceptional drug loading for the drug lansoprazole (LPZ) by 2D Cu-MONs as well as drug release in the acidic and neutral medium demonstrating that the 2D Cu-MON is an excellent carrier for antiulcer drug delivery. For environmental protection, the application of 2D Cu-MON was also examined toward the removal of various cationic and anionic dyes with excellent selectivity toward cationic dye removal. The plausible mechanism for dye removal indicated the involvement of cation-π and π-π interactions, for the effective adsorption of cationic dyes as well as a increase in the surface area of 2D Cu-MON by UILPE. Remarkably, the high drug loading and dye removal are imputed to the increase in surface area by UILPE. In a nutshell, the developed 2D Cu-MON will prove to be beneficial for application in the field of drug delivery as well as for wastewater treatment.

How to identify a smoker: a salient crystallographic approach to detect thiocyanate content.

There is an increasing demand for monitoring environmental pollutants and the control requires new sensing materials with better sensitivity, selectivity and reliability. In this study, a series of Co7 clusters incorporating various flexible polyhydroxyamine ligands are explored, with the first report of thiocyanate recognition triggered by crystal formation using a Co7 crystal (1). For this, we have fortunately synthesized three new mixed metal Co7 clusters with fascinating structural features. The clusters were characterized by spectroscopic and single crystal X-ray diffraction methods and later by DFT calculations. Due to its better emission spectrum, 1 was further utilized for evaluating its sensing ability towards various anions in water. Surprisingly, 1 shows better quenching ability towards the recognition of SCN- with a better binding constant. The luminescence quenching towards SCN- detection was further verified by the single crystal method, HSAB principle (symbiosis) and theoretical calculations such as DFT studies. The SCXRD data clearly suggest that the Co7 (1) can be converted into Co14 (1a) by direct reaction with NaSCN under ambient conditions. Besides the soft/hard acid-base concept (symbiosis), the energies of formation, and Co-NCS and Co-OH2 bond energies (as unravelled by DFT) are responsible for this transformation. Therefore, 1 can be used as a selective and sensitive sensor for the detection of thiocyanate anions based on the fluorescence amplification and quenching method. Further, the designed cluster has also been utilized to detect anions in human blood samples to differentiate a smoker and a non-smoker. It has been concluded that the samples of smokers have a high degree of thiocyanate (∼12 or 9.5 mg L-1) in comparison to those of non-smokers (2-3 mg L-1). Thus, this kind of cluster material has high potentiality in the field of bio-medical science in future endeavours for identification of the extent of thiocyanate content in smokers.

Factors associated with Achilles tendon pain in cyclists in eastern province of Saudi Arabia.

BACKGROUND: Cyclists are predisposed to different types of injuries whose patterns and distribution change over time. During bicycling, the high demand on lower extremities to produce speed places high load on the legs resulting in overuse injuries of which pain in the Achilles tendon is one. This study assessed Achilles tendon pain in cyclists in the eastern province of Saudi Arabia. MATERIALS AND METHODS: This was a cross-sectional study of active cyclists in the eastern province of Saudi Arabia. Data were collected using validated and pretested web-based self-administered questionnaire. Of the 511 cyclists invited, 311 completed the questionnaire yielding 60.62% response rate. SPSS was used for data entry and analysis. Descriptive statistics included calculation of frequencies and percentages for categorical variables, and median, mean and standard deviation for continuous variables. Chi-square test measured the associations between Achilles pain and various risk factors. Student's t-test, or Mann-Whitney test as appropriate, was used to compare continuous variables. RESULTS: Ten percent of mature and 9.1% professional cyclists reported that they had Achilles tendon pain. The pain was reported by significantly higher proportion of cyclists who raced (25%) and cyclists who rode mountain bicycles off-road (60.0%); average duration of the Achilles tendon pain was 7 days. Of the cyclists who had Achilles tendon pain, 32.1% reported that the pain increased when they were in running load and 28.6% reported increased pain in cycling load. Most cyclists described the pain as mild (67.9%) and moderate (32.1%). Overweight and underweight cyclists reported significantly higher rates of Achilles tendon pain (60% and 12.5%) compared to other body mass index classes. CONCLUSION: Achilles tendon pain commonly affects both amateur and professional cyclists. The study underpins the importance of a gradual increase in the training load, proper conditioning, bike fitting, and the maintenance of ideal body weight of cyclists to prevent Achilles tendon pain.

A-ring-substituted estrogen-3-O-sulfamates: potent multitargeted anticancer agents.

Efficient and flexible syntheses of 2-substituted estrone, estradiol and their 3-O-sulfamate (EMATE) derivatives have been developed using directed ortho-lithiation methodology. 2-Substituted EMATEs display a similar antiproliferative activity profile to the corresponding estradiols against a range of human cancer cell lines. 2-Methoxy (3, 4), 2-methylsulfanyl (20, 21) and 2-ethyl EMATEs (32, 33) proved the most active compounds with 2-ethylestradiol-3-O-sulfamate (33), displaying a mean activity over the NCI 55 cell line panel 80-fold greater than the established anticancer agent 2-methoxyestradiol (2). 2-Ethylestradiol-3-O-sulfamate (33) was also an effective inhibitor of angiogenesis using three in vitro markers, and various 2-substituted EMATEs also proved to be inhibitors of steroid sulfatase (STS), a therapeutic target for the treatment of hormone-dependent breast cancer. The potential of this novel class of multimechanism anticancer agents was confirmed in vivo with good activity observed in the NCI hollow fiber assay and in a MDA-MB-435 xenograft mouse model.

A clinical pharmacological study of the potential beneficial effects of a propolis food product as an adjuvant in asthmatic patients.

The aqueous extract of propolis has been formulated as a nutritional food product and administered, as an adjuvant to therapy, to patients with mild to moderate asthma daily for 2 months in the framework of a comparative clinical study in parallel with a placebo preparation. The diagnosis of asthma was made according to the criteria of patient classification of the National Institutes of Health and Global Initiative for Asthma Management. At inclusion, the pulmonary forced expiratory volume in the first second (FEV1) as a percentage of the forced vital capacity (FVC) was more than 80% in mild persistent cases, and between 60 and 80% in moderate persistent cases, showing an increase in the degree of reversibility of > 15% in FEV1. All patients were on oral theophylline as controller therapy, none was receiving oral or inhaled corticosteroids, none had other comorbidities necessitating medical treatment, and all were from a middle-class community and had suffered from asthma for the last 2-5 years. Twenty-four patients received the placebo, with one drop-out during the study, while 22 received the propolis extract, with no drop-outs. The age range of the patients was 19-52 years; 36 were male and 10 female. The number of nocturnal attacks was recorded on a weekly basis, while pulmonary function tests were performed on all patients at the beginning of the trial, 1 month later and at the termination of the trial. Immunological parameters, including various cytokines and eicosanoids known to play a role in asthma, were measured in all patients at the beginning of the trial and 2 months later. Analysis of the results at the end of the clinical study revealed that patients receiving propolis showed a marked reduction in the incidence and severity of nocturnal attacks and improvement of ventilatory functions. The number of nocturnal attacks dropped from an average of 2.5 attacks per week to only 1. The improvement in pulmonary functions was manifested as a nearly 19% increase in FVC, a 29.5% increase in FEV1, a 30% increase in peak expiratory flow rate (PEFR), and a 41% increase in the forced expiratory flow rate between 25 and 75% of the vital capacity (FEF25-75). The clinical improvement was associated with decreases by 52, 65, 44 and 30%, respectively, of initial values for the pro-inflammatory cytokines tumor necrosis factor (TNF)-alpha, ICAM-1, interleukin (IL)-6 and IL-8, and a 3-fold increase in the 'protective' cytokine IL-10. The levels of prostaglandins E2 and F2alpha and leukotriene D4 were decreased significantly to 36, 39, and 28%, respectively, of initial values. Patients on the placebo preparation showed no significant improvement in ventilatory functions or in the levels of mediators. The findings suggest that the aqueous propolis extract tested is potentially effective as an adjuvant to therapy in asthmatic patients. The benefits may be related to the presence in the extract of caffeic acid derivatives and other active constituents.

Novel therapeutic and prevention approaches for schistosomiasis: review.

Schistosomiasis is a debilitating disease affecting approximately 600 million people in 74 developing countries, with 800 million, mostly children at risk. To circumvent the threat of having praziquantel (PZQ) as the only drug used for treatment, several PZQ derivatives were synthesized, and drugs destined for other parasites were used with success. A plethora of plant-derived oils and extracts were found to effectively kill juvenile and adult schistosomes, yet none was progressed to pre- and clinical studies except an oleo-gum resin extracted from the stem of Commiphora molmol, myrrh, which action was challenged in several trials. We have proposed an essential fatty acid, a component of our diet and cells, the polyunsaturated fatty acid arachidonic acid (ARA) as a remedy for schistosomiasis, due to its ability to activate the parasite tegument-bound neutral sphingomyelinase, with subsequent hydrolysis of the apical lipid bilayer sphingomyelin molecules, allowing access of specific antibody molecules, and eventual worm attrition. This concept was convincingly supported using larval and adult Schistosoma mansoni and Schistosoma haematobium worms in in vitro experiments, and in vivo studies in inbred mice and outbred hamsters. Even if ARA proves to be an entirely effective and safe therapy for schistosomiasis, it will not prevent reinfection, and accordingly, the need for developing an effective vaccine remains an urgent priority. Our studies have supported the status of S. mansoni calpain, glutathione-S-transferase, aldolase, triose phosphate isomerase, glyceraldehyde 3-phosphate dehydrogenase, enolase, and 2-cys peroxiredoxin as vaccine candidates, as they are larval excreted-secreted products and, contrary to the surface membrane molecules, are entirely accessible to the host immune system effector elements. We have proposed that the use of these molecules, in conjunction with Th2 cytokines-inducing adjuvants for recruiting and activating eosinophils and basophils, will likely lead to development and implementation of a sterilizing vaccine in a near future.

Synthesis, in vitro and in vivo activity of benzophenone-based inhibitors of steroid sulfatase.

Steroid sulfatase (STS) is an important new therapeutic target in oncology. Attempts to design nonsteroidal STS inhibitors, because of the oestrogenicity of the original lead oestrone 3-O-sulfamate in rodents, have led to the discovery of benzophenone-4,4'-O,O-bis-sulfamate (BENZOMATE, 3). The nonfused bicyclic BENZOMATE is a highly potent STS inhibitor in vitro, inhibiting STS activity in intact MCF-7 breast cancer cells by > 70% at 0.1 microM and in placental microsomes by > 98% at 10 microM. When MCF-7 cells were pre-treated with 3 at 1 microM and then washed to remove unbound inhibitor, the initial 94% inhibition was reduced to 89% suggesting that 3, like other sulfamate-based STS inhibitors, inhibits the enzyme irreversibly. This agent also inhibits rat liver STS activity by 84% and 93% respectively 24 h after a single dose of 1 or 10 mg/kg, demonstrating that BENZOMATE possesses similar in vivo potency to the established potent nonsteroidal inhibitor 667COUMATE. Several modifications were made to BENZOMATE structurally and effects on in vitro activity were examined. These structure-activity relationship studies show that its carbonyl and bis-sulfamate groups are pivotal for activity, although conformational flexibility is not required. Two rigid anthraquinone-based sulfamate derivatives however showed inhibitory activity significantly better than BENZOMATE in the MCF-7 cell assay. BENZOMATE and related analogues therefore represent an important class of non-steroidal STS inhibitor and lead compounds for future drug design.