Technological advancements in valorisation of industrial effluents employing hydrothermal liquefaction of biomass: Strategic innovations, barriers and perspectives.

Hydrothermal liquefaction (HTL) is identified as a promising thermochemical technique to recover biofuels and bioenergy from waste biomass containing low energy and high moisture content. The wastewater generated during the HTL process (HTWW) are rich in nutrients and organics. The release of the nutrients and organics enriched HTWW would not only contaminate the water bodies but also lead to the loss of valued bioenergy sources, especially in the present time of the energy crisis. Thus, biotechnological as well as physicochemical treatment of HTWW for simultaneous extraction of valuable resources along with reduction in polluting substances has gained significant attention in recent times. Therefore, the treatment of wastewater generated during the HTL of biomass for reduced environmental emission and possible bioenergy recovery is highlighted in this paper. Various technologies for treatment and valorisation of HTWW are reviewed, including anaerobic digestion, microbial fuel cells (MFC), microbial electrolysis cell (MEC), and supercritical water gasification (SCWG). This review paper illustrates that the characteristics of biomass play a pivotal role in the selection process of appropriate technology for the treatment of HTWW. Several HTWW treatment technologies are weighed in terms of their benefits and drawbacks and are thoroughly examined. The integration of these technologies is also discussed. Overall, this study suggests that integrating different methods, techno-economic analysis, and nutrient recovery approaches would be advantageous to researchers in finding way for maximising HTWW valorisation along with reduced environmental pollution.

BODIPY-Based Multichromophoric Tripodal System as a Multifunctional Material.

The strategic design, synthesis, and thorough characterizations of a redox-active BODIPY-based tripodal system (tri-BDP) displaying efficient aggregation-induced emission (AIE), great sensitivity toward the viscosity of a medium, ability for triplet photosensitization, singlet oxygen generation, and photooxidation have been described. The photophysical properties of tri-BDP in various solvents and in the solid state have been extensively investigated. It displayed efficient AIE and green (∼520) emission in acetonitrile/ether mixture and red (∼621 nm) emission in the solid state. Detailed viscosity-dependent studies suggested that it can act as a fluorescent molecular rotor. Triplet photosensitization, singlet oxygen generation, and photooxidation studies in the presence of 1,3-diphenylisobenzofuran and 1,5-dihydroxyl naphthalene suggested its high efficiency toward intersystem crossing and singlet oxygen generation. Detailed electrochemical investigations suggested the redox activity of the system. Hence, this system represents multifunctional features and can be applied as a functional material for various applications.

Zinc(ii), copper(ii) and cadmium(ii) complexes as fluorescent chemosensors for cations.

The fluorescence chemosensing behavior of Zn(ii), Cu(ii), and Cd(ii) based complexes toward cations has been described. Cation detection via conventional mechanisms, metal-metal exchange and chemodosimetric approaches along with the importance of metal ions and the scope, significance, and challenges with regard to the detection of cations by metal complex based probes will be discussed in detail. The fundamentals of photophysical behavior and mechanisms involved in the fluorescence detection of analytes will also be described. This article provides a detailed overview of Zn(ii), Cu(ii), and Cd(ii) based complexes as fluorescent probes for cations, together with essential discussions pertaining to detection mechanisms.

Photophysical properties of some novel tetraphenylimidazole derived BODIPY based fluorescent molecular rotors.

The strategic design, synthesis and thorough characterization of four novel hydroxyl-substituted tetraphenylimidazole (HPI) based boron dipyrromethene (BODIPY) fluorophores (HPIB1-HPIB4) have been reported. Single crystal X-ray structure determination unveiled non-planar twisted orientations for these molecules. The non-planar orientations entirely restrict detrimental π-π interactions and avoid the non-radiative relaxation pathway for excited states in the solid/aggregated state and make them AIE active. The AIE characteristics of these compounds have been related to fine J-aggregation (evident from their crystal structures) along with restricted intra-molecular rotations (RIRs). These compounds display significant sensitivity toward viscosity and can serve as fluorescent molecular rotors due to multiple phenyl groups around the imidazole ring, which has been confirmed by measuring fluorescence quantum yields and lifetimes.

Gasification of poultry litter in a lab-scale bubbling fluidised bed reactor: Impact of process parameters on gasifier performance and special focus on tar evolution.

Poultry litter (PL) gasification was experimentally investigated using a lab-scale bubbling fluidised bed reactor. Characterisation of the gasification process was performed in terms of yields and compositions of both gas and tar, lower calorific value (LCV) of the product gas, cold gas efficiency (CGE) and carbon conversion efficiency (CCE). Experiments were carried out at different temperatures (700-750 °C) and equivalence ratios (ERs). The effect of gasifier temperature at a constant ER of 0.21 shows that an increase in temperature improved the gasification process performance whilst the total tar content decreased, implying that higher temperature enhances the conversion of biomass to product gas. The total gas yield increased from 0.93 to 1.24 N2-free m3/kgfeedstock-daf, LCV increased from 3.38 MJ/m3 to 4.2 MJ/m3, while the tar content was reduced by 24% (5.6-4.25 gtar/kgfeedstock-daf). The detailed analyses of tar compositions reveal that styrene and xylenes were the most abundant compounds in the secondary tar group. Moreover, naphthalene and 1, 2-methyl naphthalene were the dominant compounds found in tertiary polycyclic aromatic hydrocarbons (PAH) and alkyl tertiary groups, respectively. Furthermore, at the highest tested temperature of 750 °C and ER of 0.25, bed agglomeration took place causing the shutdown of the gasifier. The defluidisation of the bed occurred due to the high ash content of PL comprising of low melting temperature alkali compounds. The results obtained from this study showed the performance and potential challenges associated with gasifying PL in a fluidised bed reactor for the combined heat and power production at farm level.

Tar yield and composition from poultry litter gasification in a fluidised bed reactor: effects of equivalence ratio, temperature and limestone addition.

Air gasification of poultry litter was experimentally investigated in a laboratory scale bubbling fluidised bed gasifier. Gasification tests were conducted at atmospheric pressure using silica sand as the bed material. This paper examines the effect of the equivalence ratio (ER) in the range of 0.18-0.41, temperature between 700 and 800 °C, and the addition of limestone blended with the poultry litter on the yield and composition of tar. An off-line solid phase adsorption method was employed in order to quantify tar compounds heavier than styrene, whereas lighter species such as benzene and toluene were measured by means of on-line micro gas chromatography. Total tar yields were in the range from 15.7 to 30.7 gtotal tar kgpoultry litter (dry and ash free basis) -1. These values are considered low with respect to the feedstocks with a higher organic fraction. It also needs to be noted that the yields of benzene and toluene were measured by on-line micro gas chromatography, a technique which inherently delivers higher tar values compared to commonly employed off-line techniques. By varying the ER, poultry litter blended with limestone showed a reduction in total tar yield whereas poultry litter on its own showed an increasing tar yield over the ER range tested. In the presence of limestone, polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, toluene and benzene showed a tendency to reduce over the ER range tested. Since the ER also plays a crucial role in tar reduction, the reduction in tar cannot be unambiguously attributed to calcined limestone/lime (CaCO3/CaO). Increasing the temperature was shown to be effective for reducing the total tar yield but the amounts of polycyclic aromatic hydrocarbons increased. However, no definitive correlation could be established between limestone/lime catalytic activity for tar reduction and elevated gasification temperature, because there was no possibility to study their effects separately. The chemical composition of the tar arising from poultry litter is distinctive compared with conventional lignocellulosic fuels linked to the fact that poultry litter has a higher nitrogen content (≈6.5% w/w (dry and ash free basis)). Nitrogen-containing hydrocarbons such as pyridine, 2-methylpyridine, 2-methyl-1H-pyrrole and benzonitrile were identified in significant amounts. This study has demonstrated that poultry litter gasified in a bubbling fluidised bed yielded a product gas with relatively low tar content while its composition reflects the chemical nature of the feedstock.

Pyrazole appended quinoline-BODIPY based arene ruthenium complexes: their anticancer activity and potential applications in cellular imaging.

Synthesis of an entirely new series of arene ruthenium complexes [Ru(η6-C6H6)(L1)Cl]PF6, (1), [Ru(η6-C10H14)(L1)Cl]PF6 (2), [Ru(η6-C6H6)(L2)Cl]PF6 (3) and [Ru(η6-C10H14)(L2)Cl]PF6 (4) involving 5-[2-(1H-pyrazol-1-yl)quinoline]-BODIPY (L1) and 5-[6-methoxy-2-(1H-pyrazol-1-yl)quinoline]-BODIPY (L2) was described. The ligands and complexes were thoroughly characterized by various physicochemical techniques and the structures of L1, 1 and 4 were determined by X-ray single crystal analyses. Photo-/ and electrochemical property, DNA binding, cytotoxicity, cellular uptake and apoptotic studies on 1-4 were performed by various methods, while singlet oxygen-mediated cytotoxicity via photo-irradiation by visible light was supported by 1,3-diphenylisobenzofuran titration studies. Binding of the complexes in the minor groove of CT-DNA via van der Waals forces and electrostatic interactions was affirmed by molecular docking studies. In vitro antiproliferative activity and photocytotoxicity of 1-4 were examined against the human cervical cancer cell line (HeLa) which clearly showed that these are extremely photocytotoxic under visible light (400-700 nm, 10 J cm-2; IC50 49.15, 1; 25.18, 2; 15.85, 3; 12.87, 4), less toxic in the dark (IC50 > 100 µM) and preferentially accumulate in the lysosome of the HeLa cells. Further, these complexes behave as a potential theranostic agent and their ability to kill cancer cells under visible light lies in the order 4 > 3 > 2 > 1.

AIE active piperazine appended naphthalimide-BODIPYs: photophysical properties and applications in live cell lysosomal tracking.

Piperazine appended naphthalimide-BODIPYs (NPB1-NPB4) exhibiting solvatochromism and aggregation-induced emission with a large Stokes shift (up to 146 nm) have been described. Separation of naphthalimide and BODIPY fluorophores by piperazine in these conjugates creates a donor-acceptor system and induces twisted intramolecular charge transfer, in addition to photoinduced electron transfer. The crucial role of naphthalimide, the alkyl chain length, the piperazine ring, and the solid-state packing on AIE has been extensively investigated by various studies. Superior cell permeability coupled with bio-compatibility of these conjugates offers a unique opportunity for their potential applications in live cell lysosomal tracking.

Substituent-directed ESIPT-coupled Aggregation-induced Emission in Near-infrared-emitting Quinazoline Derivatives.

A series of ESIPT (excited state intramolecular proton transfer) active systems (HQz1-HQz6) derived from quinazoline have been reported. The ESIPT emission for these derivatives gets completely quenched in solvents with diverse polarities which have been restored via aggregation-induced emission (AIE) with large Stokes shift (up to 314 nm). It varied from 450 to 701 nm just by altering substituents at the para position of hydroxy group in the central phenyl ring. As well, HQz1-HQz6 displayed solid state emission [∼455 (blue) to ∼704 nm (red)]. The formyl group on the central hydroxy-phenyl ring of these derivatives induces ESIPT by increasing acidity of the hydroxy proton which has been followed by 1 H NMR studies. Further, it has been clearly shown that emission colour and aggregate morphology can be fine tuned by incorporating apt substituents. The present study offers a simple route to obtain colour tunable ESIPT emission via AIE which is very important for biological imaging and fabrication of optoelectronic devices.

Manipulating Metallogel Properties by Luminogens and Their Applications in Cell Imaging.

Manipulating gelation properties of the isomeric zinc-terpyridine complexes C-1 (nongelator) and C-2 (gelator) using three different luminescent dyes, viz., acridine yellow (AY), ethidium bromide (EB), and azido-boron dipyrromethene, have been described. Hybrid gels created by the combination of C-1, C-2, and above-mentioned dyes have been termed complex-luminogen mixed gels (CLMGs). Ensuing CLMGs have been thoroughly characterized by spectral, morphological, and rheological studies. Cytotoxicity measurements and imaging against breast cancer cell line MDA-MB-231 unveiled that three out of the five CLMGs can be effectively used for cell imaging. Interestingly, direct use of the metal-containing hybrid gels for live cell imaging which is a distinctive approach, has been successfully achieved with significantly encouraging results.

Time dependent aggregation induced emission enhancement and the study of molecular packing in closely related azo-phenol BODIPY species.

Fluorescent azo-phenol BODIPYs (1-3) have been obtained by the substituent (-OCH3/-CH3) directed synthesis of ortho (L1) and para (L2-L3) azo-phenol aldehydes. These display aggregation caused quenching (ACQ, 1) and aggregation induced emission enhancement (AIEE, 2 and 3) depending on the position of azo relative to the phenolic hydroxyl group. An intriguing time dependent morphological transition from nanospheres to ordered nanorods and subsequent emission changes in AIEE active azo-phenol BODIPYs have been successfully realized by time dependent fluorescence, scanning electron (SEM), transmission electron (TEM) and fluorescence optical microscopy (FOM) studies. The existence of one-dimensional (1D) nanorods as ultimate species in these compounds (2-3) has been supported by crystal packing patterns. Diverse aggregated forms and hierarchical nanostructures have been related to variable extents of fluorescence enhancement. The plausible charge transfer process and its role in AIEE have been supported by DFT studies.

Anticancer Activity of Iridium(III) Complexes Based on a Pyrazole-Appended Quinoline-Based BODIPY.

A pyrazole-appended quinoline-based 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (L1, BODIPY) has been synthesized and used as a ligand for the preparation of iridium(III) complexes [Ir(phpy)2(L1)]PF6 (1; phpy = 2-phenylpyridine) and [(η5-C5Me5)Ir(L1)Cl]PF6 (2). The ligand L1 and complexes 1 and 2 have been meticulously characterized by elemental analyses and spectral studies (IR, electrospray ionization mass spectrometry, 1H and 13C NMR, UV/vis, fluorescence) and their structures explicitly authenticated by single-crystal X-ray analyses. UV/vis, fluorescence, and circular dichroism studies showed that complexes strongly bind with calf-thymus DNA and bovine serum albumin. Molecular docking studies clearly illustrated binding through DNA minor grooves via van der Waals forces and their electrostatic interaction and occurrence in the hydrophobic cavity of protein (subdomain IIA). Cytotoxicity, morphological changes, and apoptosis have been explored by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and Hoechst 33342 staining. IC50 values for complexes (1, 30 µM; 2, 50 µM) at 24 h toward the human cervical cancer cell line (HeLa) are as good as that of cisplatin (21.6 µM) under analogous conditions, and their ability to kill cancer cells lies in the order 1 > 2. Because of the inherent emissive nature of the BODIPY moiety, these are apt for intracellular visualization at low concentration and may find potential applications in cellular imaging and behave as a theranostic agent.

Influence of substituents on DNA and protein binding of cyclometalated Ir(iii) complexes and anticancer activity.

Synthesis of terpyridyl based ligands 3-([2,2':6',2''-terpyridin]-4'-yl)-7-methoxy-2-(methylthio)-quinolone, (L1); 3-([2,2':6',2''-terpyridin]-4'-yl)-6-methoxyquinolin-2(1H)-one, (L2); 3-([2,2'-:6',2''-terpyridin]-4'-yl)-6-methylquinolin-2(1H)-one (L3) and cyclometalated iridium(iii) complexes [[Ir(ppy)2L1]+PF6- (1), [Ir(ppy)2L2]+PF6- (2), [Ir(ppy)2L3]+PF6- (3) (2-phenylpyridine = Hppy)] involving these ligands has been described. The ligands L1-L3 and complexes 1-3 have been thoroughly characterized by elemental analyses, spectral studies (IR, 1H, 13C NMR, UV/vis and fluorescence) ESI-MS, and the structure of 3 has been unambiguously authenticated by single crystal X-ray analyses. UV/vis, fluorescence and circular dichroism spectroscopic studies showed rather efficient binding of 1 with CT-DNA (calf thymus DNA) and BSA (bovine serum albumin) relative to 2 and 3. Molecular docking studies unveiled binding of 1-3 with minor groove of CT-DNA via van der Waal's forces and electrostatically with the hydrophobic moiety of HSA (human serum albumin). The ligands and complexes exhibited moderate cytotoxicity towards MDA-MB-231 (breast cancer cell line) and significant influence on HeLa (cervical cancer cell line) cells. Cytotoxicity, morphological changes, and apoptosis have been followed by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide) assay, Hoechst 33342/PI (PI = propidium iodide) staining, cell cycle analysis by FACS (fluorescence activated cell sorting), and ROS (reactive oxygen species) generation by DCFH-DA (dichlorodihydrofluorescein diacetate) dye. Confocal microscopy images revealed that the drug efficiently initiates apoptosis in the cell cytosol. The IC50 values showed superior cytotoxicity of 1-3 against the HeLa cell line relative to cisplatin, and their ability to induce apoptosis is in the order 1 > 2 > 3.

Spacer length dependent architectural diversity in bis-dipyrrin copper(ii) complexes.

A series of copper(ii) complexes (1-9 and 3') derived from bis-dipyrrin ligands (L1-L9 and L3') with diverse spacer lengths [-(CH2)n-] have been described. Structural diversities in these complexes have been explicitly established by spectral and structural studies on these and a closely related nickel(ii) complex (3''). All the ligands and complexes have been thoroughly characterized by spectroscopic studies (ESI-MS, IR, 1H, 13C NMR, UV/vis) and structures of 2, 3', 3'', 6, 8 and 9 were determined by X-ray single crystal analyses. It has been unambiguously established that ligands with n ≤ 6 gave heteroleptic binuclear (1-5), while those with n ≥ 7 yielded homoleptic mononuclear (6-9) bis-dipyrrinato complexes. Spectral and structural studies revealed distorted square planar (1-5) and distorted tetrahedral geometries (6-9) about the copper(ii) centre in these complexes which has further been evidenced by EPR and electrochemical studies. Structural differences based on the odd and even number of methylene spacers in these complexes have been supported by DFT studies. A line between the syn- and anti-conformations of the complexes has been drawn on the basis of a limiting spacer length.

p53 dependent apoptosis and cell cycle delay induced by heteroleptic complexes in human cervical cancer cells.

We previously reported synthesis of novel arene ruthenium (Ru) complexes and evaluated their antitumor activity in murine lymphoma (DL) cells. In this present study we further investigated the mechanism of action of two ruthenium complexes [complex 1 (η6-arene)RuCl(2-pcdpm)] and complex 2 (η6-arene)RuCl(4-mtdpm)] in cervical cancer cell line (HeLa). Our studies demonstrate that anticancer property of these two complexes was due to induction of apoptosis through p53 mediated pathway as well as arrest of cells in G2/M phase of cell cycle. It is worth to note that the complexes did not cause any substantial cytotoxic effect on normal cells. Further in comprehensive studies, apoptosis inducing property of both complexes were established in accordance with array of morphological changes ranging from membrane blebbing to formation of apoptotic bodies and followed by DNA fragmentation assay. Furthermore, Flow cytometry by Annexin V/PI staining delineate that complex 1 and 2 have strident impact to induce apoptosis in HeLa cells. The complex 1 and 2 treated cells show increased level of intracellular ROS generation which was preceded by p53 activation. Apoptosis induced by 1 and 2 was preceded by mitochondrial aggregations which were monitored by mitotracker. In addition flow cytometry analysis showed that both complexes also effectively arrest cells at G2/M phase of cell cycle. Western blot, RT-PCR as well as Real Time analysis were used to further confirm that the complexes induced apoptosis in p53 dependent pathway. Thus, our promising results can contribute to the rational design of novel potential anticancer agents.

Artificial neural network based modelling approach for municipal solid waste gasification in a fluidized bed reactor.

In this paper, multi-layer feed forward neural networks are used to predict the lower heating value of gas (LHV), lower heating value of gasification products including tars and entrained char (LHVp) and syngas yield during gasification of municipal solid waste (MSW) during gasification in a fluidized bed reactor. These artificial neural networks (ANNs) with different architectures are trained using the Levenberg-Marquardt (LM) back-propagation algorithm and a cross validation is also performed to ensure that the results generalise to other unseen datasets. A rigorous study is carried out on optimally choosing the number of hidden layers, number of neurons in the hidden layer and activation function in a network using multiple Monte Carlo runs. Nine input and three output parameters are used to train and test various neural network architectures in both multiple output and single output prediction paradigms using the available experimental datasets. The model selection procedure is carried out to ascertain the best network architecture in terms of predictive accuracy. The simulation results show that the ANN based methodology is a viable alternative which can be used to predict the performance of a fluidized bed gasifier.

Fine-Tuning of Saponification-Triggered Gelation by Strategic Modification of Peripheral Substituents: Gelation Regulators.

A pioneering approach towards controlling the efficiency of saponification assisted gelation in ethyl ester based ZnII -complexes have been described. Using four new ester containing bis-salen ZnII complexes (C1-C4) involving different para-azo phenyl substituted ligands it has been clearly shown that gelation efficiency is greatly influenced by the electronic effects of the substituents (-H (C1), -CH3 (C2), -NO2 (C3), and -OCH3 (C4)). Morphological, photophysical, and rheological investigations corroborated the experimental observations well and established that gelation efficiency was enhanced with electron-withdrawing characteristics of substituents (C4

Hydrothermal carbonisation of poultry litter: Effects of treatment temperature and residence time on yields and chemical properties of hydrochars.

In this study, hydrochars were prepared by hydrothermal carbonisation (HTC) of poultry litter (PL) at temperatures between 150-300°C with residence times of 30, 120 and 480min. The effects of treatment temperature and residence time on the yield and composition of hydrochar were investigated. Both treatment temperature and residence time effects were observed however, the effect of residence time was lower. The results indicated that the HHV was improved by up to 25.17% and the overall ash in hydrochar was significantly lower compared to PL, however this coincided with a lower hydrochar yield.

N,N-Diethylamine appended binuclear Zn(ii) complexes: highly selective and sensitive fluorescent chemosensors for picric acid.

Novel binuclear Zn(ii) complexes (1-2) derived from bis-chelating salen type ligands (H2L(1) and H2L(2)) possessing N,N-diethylamine moieties on the periphery of the molecules have been synthesized and thoroughly characterized by satisfactory elemental analyses and spectral (FT-IR, (1)H, (13)C NMR, UV-vis, fluorescence and ESI-MS) studies. The structures of H2L(1) and 1 have been authenticated by single crystal X-ray diffraction analyses. Complexes 1 and 2 strongly fluoresce and act as highly selective and sensitive chemosensors for picric acid in different organic as well as aqueous media. Both 1 and 2 showed strong potential to detect traces of PA in vapour/solid phase through contact mode analysis. Spectral and theoretical (DFT) studies suggested that the observed fluorescence quenching may be associated with ground state (GS) charge transfer as well as electrostatic interactions between 1/2 and PA. The fluorescence lifetime for the representative complex 1 displayed a double exponential curve and unaltered lifetime (τav, 0.63 nm) in the absence and presence of PA and strongly suggested that quenching follows a static mechanism. Further, DFT calculations on 1 and 2 strongly supported the static mechanism through GS charge transfer between complexes and PA. In addition, (1)H NMR spectral studies on 1-2 in the presence of PA firmly advocated strong hydrogen bonding and π-π stacking between the phenolic rings of 1-2 and the aromatic ring of PA. These complexes are capable of detecting PA either individually or in a competitive environment of other nitro- explosives. Florescence spectral studies on the model complex M lacking N,N-diethylamine groups revealed moderate selectivity and sensitivity towards PA and supported the key role of N,N-diethylamine moieties in the selectivity and sensitivity of complexes.

Anion triggered metallogels: demetalation and crystal growth inside the gel matrix and improvement in viscoelastic properties using Au-NPs.

Progelator complex Zn-TRPA-2 undergoes Cl(-) triggered gelation to afford ZTP2G, while Zn-TRPA-2 capped Au-NPs under similar conditions gave another gel GNZTP2G which also represents a rare nano-composite metallogel. When Zn-TRPA-2 was triggered by Cl(-) and NO3(-) simultaneously, crystals of demetalated species NA-TRPA-2 grew inside the ZTP2G matrix. Interestingly, GNZTP2G exhibits superior viscoelastic properties over ZTP2G.