Voltage- and Power-Conversion Performance of Bi-functional ZrO2 : Er3+ / Yb3+ Assisted and Co-sensitized Dye Sensitized Solar Cells for Internet of Things Applications.

Giant power conversion efficiency is achieved by using bifunction ZrO2 : Er3+ /Yb3+ assisted co-sensitised dye-sensitized solar cells. The evolution of the crystalline structure and its microstructure are examined by X-ray diffraction, scanning electron microscopy studies. The bi-functional behaviour of ZrO2 : Er3+ /Yb3+ as upconversion, light scattering is confirmed by emission and diffused reflectance studies. The bi-function ZrO2 : Er3+ /Yb3+ (pH=3) assisted photoanode is co-sensitized by use of N719 dye, squaraine SPSQ2 dye and is sandwiched with Platinum based counter electrode. The fabricated DSSC exhibited a giant power conversion efficiency of 12.35 % with VOC of 0.71 V, JSC of 27.06 mA/cm2 , FF of 0.63. The results, which motivated the development of a small DSSC module, gave 6.21 % and is used to drive a tiny electronic motor in indoor and outdoor lighting conditions. Small-area DSSCs connected in series have found that a VOC of 4.52 V is sufficient to power up Internet of Things (IoT) devices.

Differential expression of aquaporin genes and the influence of environmental hypertonicity on their expression in juveniles of air-breathing stinging catfish (Heteropneustes fossilis).

Aquaporins (AQPs) are a superfamily of transmembrane channel proteins that are responsible for the transport of water and some other molecules to and from the cell, mainly for osmoregulation under anisotonicity. We investigated here the expression patterns of different AQP isoforms and also during exposure to hypertonicity (300 mOsmol/L) for 48 h in juvenile stages of air-breathing stinging catfish (Heteropneustes fossilis). A total of 8 mRNA transcripts for different isoforms of AQPs and their translated proteins could be detected in the anterior and posterior regions of S1, S2, and S3 stages of juveniles of stinging catfish at variable levels. In general, more expression of mRNAs for different aqp genes was seen in the S2 and S3 juveniles than in the S1 juveniles. Most interestingly, exposure to hypertonicity of S2 juveniles for a period of 48 h led to increased expression of most of the aqp genes both at transcriptional and translational levels, except for aqp3 in the anterior and posterior regions and aqp1 in the anterior region, showing maximum expression at later stages of hypertonic exposure. Thus, it is evident that AQPs play crucial roles in maintaining the water and ionic balances under anisotonic conditions even at the early developmental stages of stinging catfish as a biochemical adaptational strategy to survive and grow in anisotonic environment.

A Trimodal Closomer Drug-Delivery System Tailored with Tracing and Targeting Capabilities.

The construction and application of a unique monodisperse closomer drug-delivery system (CDDS) integrating three different functionalities onto an icosahedral closo-dodecaborane [B12 ](2-) scaffold is described. Eleven B-OH vertices of [closo-B12 (OH)12 ](2-) were used to attach eleven copies of the anticancer drug chlorambucil and the targeting vector glucosamine through a bifurcating lysine linker. The remaining twelfth vertex was used to attach a fluorescent imaging probe. The presence of multiple glucosamine units offered a monodisperse and highly water-soluble CDDS with a high payload of therapeutic cargo. This array enhanced the penetration of the drug into cancer cells by exploiting the overexpression of GLUT-1 receptors present on cancer cells. About 15-fold enhancement in cytotoxicity was observed for CDDS-1 against Jurkat cells, compared to CDDS-2, which lacks the GLUT-1 targeting glucosamine. A cytotoxicity comparison of CDDS-1 against colorectal RKO cells and its GLUT-1 knock-out version confirmed that GLUT-1 mediates endocytosis. Using fluorescent markers both CDDS-1 and -2 were traced to the mitochondria, a novel target for alkylating agents.

Synthesis, relaxation properties and in vivo assessment of a carborane-GdDOTA-monoamide conjugate as an MRI blood pool contrast agent.

The synthesis, relaxivity measurements and in vivo assessment of a carborane-GdDOTA-monoamide (CB-GdDOTA-MA) amphiphilic conjugate as a blood pool contrast agent (BPCA) is reported. This BPCA exhibited excellent binding (87.4%) with human serum albumin (HSA) and showed a higher relaxivity value (r1 = 6.8 mM(-1) s(-1), 7 T) as compared to the clinically used BPCA, MS-325 (r1 = 5.1 mM(-1) s(-1), 9.4 T) in PBS. The blood pool contrast enhancement (CE) capability of CB-GdDOTA-MA was evaluated by performing MR angiography (MRA) in CF1 mice (n = 4) at a Gd dose of 0.1 mmol per kg body weight. The significant CE of blood vessels persisted for about 3-4 min post-injection (p.i.) and quickly diminishes over time. The significant CE of the bladder for up to 3 h p.i. indicated that the renal system is the primary clearance pathway for CB-GdDOTA-MA. However, the CE of liver tissues and intestine (up to 24 h p.i.) is suggestive of a significant hepatic uptake of the CB-GdDOTA-MA.

Constructed wetlands for the removal of organic micropollutants from wastewater: Current status, progress, and challenges.

In this work, the practical utility of constructed wetlands (CWs) is described as a promising treatment option for micropollutants (MPs) in wastewater with the aid of their eco-friendly, low-energy, economically feasible, and ecologically sustainable nature. This paper offers a comprehensive review on CW technology with respect to the key strategies for MP removal such as phytoremediation, substrate adsorption, and microbial degradation. It explores the important factors controlling the performance of CWs (e.g., in terms of configurations, substrates, plant-microbe interactions, temperature, pH, oxygen levels, hydraulic loading rate, and retention time) along with the discussions on the pivotal role of microbial populations in CWs and plant-microbe cooperative remediation dynamics, particularly in relation to diverse organic MP patterns in CWs. As such, this review aims to provide valuable insights into the key strategies for optimizing MP treatment and for enhancing the efficacy of CW systems. In addition, the process-based models of constructed wetlands along with the numerical simulations based on the artificial neural network (ANN) method are also described in association with the data exploratory techniques. This work is thus expected to help open up new possibilities for the application of plant-microbe cooperative remediation approaches against diverse patterns of organic MPs present in CWs.

Experimental and Theoretical Investigations of MAPbX3 -Based Perovskites (X=Cl, Br, I) for Photovoltaic Applications.

This work mainly focuses on synthesizing and evaluating the efficiency of methylammonium lead halide-based perovskite (MAPbX3 ; X=Cl, Br, I) solar cells. We used the colloidal Hot-injection method (HIM) to synthesize MAPbX3 (X=Cl, Br, I) perovskites using the specific precursors and organic solvents under ambient conditions. We studied the structural, morphological and optical properties of MAPbX3 perovskites using XRD, FESEM, TEM, UV-Vis, PL and TRPL (time-resolved photoluminescence) characterization techniques. The particle size and morphology of these perovskites vary with respect to the halide variation. The MAPbI3 perovskite possesses a low band gap and low carrier lifetime but delivers the highest PCE among other halide perovskite samples, making it a promising candidate for solar cell technology. To further enrich the investigations, the conversion efficiency of the MAPbX3 perovskites has been evaluated through extensive device simulations. Here, the optical constants, band gap energy and carrier lifetime of MAPbX3 were used for simulating three different perovskite solar cells, namely I, Cl or Br halide-based perovskite solar cells. MAPbI3 , MAPbBr3 and MAPbCl3 absorber layer-based devices showed ~13.7 %, 6.9 % and 5.0 % conversion efficiency. The correlation between the experimental and SCAPS simulation data for HIM-synthesized MAPBX3 -based perovskites has been reported for the first time.

Regioselective synthesis and photophysical and electrochemical studies of 20-substituted cyanine dye-purpurinimide conjugates: incorporation of Ni(II) into the conjugate enhances its tumor-uptake and fluorescence-imaging ability.

We report herein a simple and efficient approach to the synthesis of a variety of meso-substituted purpurinimides. The reaction of meso-substituted purpurinimide with N-bromosuccinimide regioselectively introduced a bromo functionality at the 20-position, which on further reaction with a variety of boronic acids under Suzuki reaction conditions yielded the corresponding meso-substituted analogues. Interestingly, the free base and the metalated analogues showed remarkable differences in photosensitizing efficacy (PDT) and tumor-imaging ability. For example, the free-base conjugate showed significant in vitro PDT efficacy, but limited tumor avidity in mice bearing tumors, whereas the corresponding Ni(II) derivative did not produce any cell kill, but showed excellent tumor-imaging ability at a dose of 0.3 µmol kg(-1) at 24, 48, and 72 h post-injection. The limited PDT efficacy of the Ni(II) analogue could be due to its inability to produce singlet oxygen, a key cytotoxic agent required for cell kill in PDT. Based on electrochemical and spectroelectrochemical data in DMSO, the first one-electron oxidation (0.52 V vs. SCE) and the first one-electron reduction (-0.57-0.67 V vs. SCE) of both the free base and the corresponding Ni(II) conjugates are centered on the cyanine dye, whereas the second one-electron reduction (-0.81 V vs. SCE) of the two conjugates is assigned to the purpurinimide part of the molecule. Reduction of the cyanine dye unit is facile and occurs prior to reduction of the purpurinimide group, which suggests that the cyanine dye unit as an oxidant could be the driving force for quenching of the excited triplet state of the molecules. An interaction between the cyanine dye and the purpurinimide group is clearly observed in the free-base conjugate, which compares with a negligible interaction between the two functional groups in the Ni(II) conjugate. As a result, the larger HOMO-LUMO gap of the free-base conjugate and the corresponding smaller quenching constant is a reason to decrease the intramolecular quenching process and increase the production of singlet oxygen to some degree.

cRGD peptide-conjugated icosahedral closo-B12(2-) core carrying multiple Gd3+-DOTA chelates for α(v)ß3 integrin-targeted tumor imaging (MRI).

A vertex-differentiated icosahedral closo-B(12)(2-) core was utilized to construct a α(v)ß(3) integrin receptor-targeted (via cRGD peptide) high payload MRI contrast agent (CA-12) carrying 11 copies of Gd(3+)-DOTA chelates attached to the closo-B(12)(2-) surface via suitable linkers. The resulting polyfunctional MRI contrast agent possessed a higher relaxivity value per-Gd compared to Omniscan, a small molecular contrast agent commonly used in clinical settings. The α(v)ß(3) integrin receptor specificity of CA-12 was confirmed via in vitro cellular binding experiments and in vivo MRI of mice bearing human PC-3 prostate cancer xenografts. Integrin α(v)ß(3)-positive MDA-MB-231 cells exhibited 300% higher uptake of CA-12 than α(v)ß(3)-negative T47D cells. Serial T1-weighted MRI showed superior contrast enhancement of tumors by CA-12 compared to both a nontargeted 12-fold Gd(3+)-DOTA closomer control (CA-7) and Omniscan. Contrast enhancement by CA-12 persisted for 4 h postinjection, and subsequent enhancement of kidney tissue indicated a renal elimination route similar to Omniscan. No toxic effects of CA-12 were apparent in any mice for up to 24 h postinjection. Post-mortem ICP-OES analysis at 24 h detected no residual Gd in any of the tissue samples analyzed.

Discrete nanomolecular polyhedral borane scaffold supporting multiple gadolinium(III) complexes as a high performance MRI contrast agent.

An icosahedral closo-B(12)(2-) scaffold supports 12 copies of Gd(3+)-chelate held in close proximity with each other by suitable linkers which employ azide-alkyne click chemistry. This design is the first member of a new class of polyfunctional MRI contrast agents carrying a high payload of Gd(3+)-chelate in a sterically constrained configuration. The resulting contrast agent shows higher relaxivity values at high magnetic fields. MRI contrast agents currently in use are not as effective in this regard, presumably due to a lack of steric constraint of gadolinium centers and lower water exchange rates. In vivo MRI studies in mice show excellent contrast enhancement even at one-seventh of the safe clinical dose (0.04 mmol Gd/kg) for up to a 1 h exposure.

Efficient synthesis of diverse heterobifunctionalized clickable oligo(ethylene glycol) linkers: potential applications in bioconjugation and targeted drug delivery.

Herein we describe the sequential synthesis of a variety of azide-alkyne click chemistry-compatible heterobifunctional oligo(ethylene glycol) (OEG) linkers for bioconjugation chemistry applications. Synthesis of these bioorthogonal linkers was accomplished through desymmetrization of OEGs by conversion of one of the hydroxyl groups to either an alkyne or azido functionality. The remaining distal hydroxyl group on the OEGs was activated by either a 4-nitrophenyl carbonate or a mesylate (-OMs) group. The -OMs functional group served as a useful precursor to form a variety of heterobifunctionalized OEG linkers containing different highly reactive end groups, e.g., iodo, -NH(2), -SH and maleimido, that were orthogonal to the alkyne or azido functional group. Also, the alkyne- and azide-terminated OEGs are useful for generating larger discrete poly(ethylene glycol) (PEG) linkers (e.g., PEG(16) and PEG(24)) by employing a Cu(I)-catalyzed 1,3-dipolar cycloaddition click reaction. The utility of these clickable heterobifunctional OEGs in bioconjugation chemistry was demonstrated by attachment of the integrin (α(v)ß(3)) receptor targeting peptide, cyclo-(Arg-Gly-Asp-D-Phe-Lys) (cRGfKD) and to the fluorescent probe sulfo-rhodamine B. The synthetic methodology presented herein is suitable for the large scale production of several novel heterobifunctionalized OEGs from readily available and inexpensive starting materials.

Synthesis and relaxivity studies of a DOTA-based nanomolecular chelator assembly supported by an icosahedral closo-B12²â» core for MRI: a click chemistry approach.

An icosahedral closo-B12²â» scaffold based nano-sized assembly capable of carrying a high payload of Gd³âº-chelates in a sterically crowded configuration is developed by employing the azide-alkyne click reaction. The twelve copies of DO3A-t-Bu-ester ligands were covalently attached to an icosahedral closo-B12²â» core via suitable linkers through click reaction. This nanomolecular structure supporting a high payload of Gd³âº-chelate is a new member of the closomer MRI contrast agents that we are currently developing in our laboratory. The per Gd ion relaxivity (r1) of the newly synthesized MRI contrast agent was obtained in PBS, 2% tween/PBS and bovine calf serum using a 7 Tesla micro MRI instrument and was found to be slightly higher (r1 = 4.7 in PBS at 25 °C) compared to the clinically used MRI contrast agents Omniscan (r1 = 4.2 in PBS at 25 °C) and ProHance (r1 = 3.1 in PBS at 25 °C).

Valorization of organic wastes using bioreactors for polyhydroxyalkanoate production: Recent advancement, sustainable approaches, challenges, and future perspectives.

Microbial polyhydroxyalkanoates (PHA) are encouraging biodegradable polymers, which may ease the environmental problems caused by petroleum-derived plastics. However, there is a growing waste removal problem and the high price of pure feedstocks for PHA biosynthesis. This has directed to the forthcoming requirement to upgrade waste streams from various industries as feedstocks for PHA production. This review covers the state-of-the-art progress in utilizing low-cost carbon substrates, effective upstream and downstream processes, and waste stream recycling to sustain entire process circularity. This review also enlightens the use of various batch, fed-batch, continuous, and semi-continuous bioreactor systems with flexible results to enhance the productivity and simultaneously cost reduction. The life-cycle and techno-economic analyses, advanced tools and strategies for microbial PHA biosynthesis, and numerous factors affecting PHA commercialization were also covered. The review includes the ongoing and upcoming strategies viz. metabolic engineering, synthetic biology, morphology engineering, and automation to expand PHA diversity, diminish production costs, and improve PHA production with an objective of "zero-waste" and "circular bioeconomy" for a sustainable future.

A holistic approach for process intensification of nicotinamide mononucleotide production via high cell density cultivation under exponential feeding strategy.

Nicotinamide mononucleotide (NMN) subsists in all living organisms and has drawn tremendous attention as a nutraceutical and pharmaceutical product for several diseases such as Alzheimer's, cancer, aging, and vascular dysfunction. Here, NMN was produced intracellularly in a high cell density bioreactor using an engineered Escherichiacoli strain via exponential feeding of co-substrates. Fed-batch culture via exponential feeding of co-substrate (glucose) and continuous feeding of substrate (nicotinamide) were performed using different cumulative nicotinamide concentrations. The highest concentration of 19.3 g/L NMN with a dry cell weight of 117 g/L was acquired from a cumulative nicotinamide concentration of 7.2 g/L with a conversion of 98 % from nicotinamide in 28 h. Further, liquid chromatography-mass spectrometry analysis validated the NMN production. This approach will be beneficial in achieving simultaneously low cost and ensuring high quality and quantity of NMN production.

Synthesis of vertex-differentiated icosahedral closo-boranes: polyfunctional scaffolds for targeted drug delivery.

We report methods for the synthesis of vertex-differentiated icosahedral closo-boranes. A single B-OH vertex of the icosahedral borane [closo-B(12)(OH)(12)](2-) was derivatized to prepare [closo-B(12)(OR)(OH)(11)](2-) using optimized alkylation conditions and purification procedures. Several representative vertex-differentiated icosahedral closo-boranes were prepared utilizing carbonate ester and azide-alkyne click chemistries on the surface of the closo-B(12)(2-) core.

Nanomaterial-Based Therapy for Wound Healing.

Poor wound healing affects millions of people globally, resulting in increased mortality rates and associated expenses. The three major complications associated with wounds are: (i) the lack of an appropriate environment to enable the cell migration, proliferation, and angiogenesis; (ii) the microbial infection; (iii) unstable and protracted inflammation. Unfortunately, existing therapeutic methods have not solved these primary problems completely, and, thus, they have an inadequate medical accomplishment. Over the years, the integration of the remarkable properties of nanomaterials into wound healing has produced significant results. Nanomaterials can stimulate numerous cellular and molecular processes that aid in the wound microenvironment via antimicrobial, anti-inflammatory, and angiogenic effects, possibly changing the milieu from nonhealing to healing. The present article highlights the mechanism and pathophysiology of wound healing. Further, it discusses the current findings concerning the prospects and challenges of nanomaterial usage in the management of chronic wounds.

Green Production of Functionalized Few-Layer Graphene-Silver Nanocomposites Using Gallnut Extract for Antibacterial Application.

Recently, there has been much attention paid to functionalized few-layer graphene (FFG) owing to its many biomedical applications, such as in bioimaging, biosensors, drug delivery, tissue scaffolds, nanocarriers, etc. Hence, the preparation of FFG has now become of great interest to researchers. The present study systematically investigates the utilization of gallnut extract (GNE) during the process of high-shear exfoliation for the efficient conversion of expanded graphite to FFG. Various parameters, such as GNE concentration, graphite concentration, exfoliation time, and the rotation speed of the high-shear mixer, were initially optimized for FFG production. The prepared FFG was characterized in terms of surface functionality and morphology using Raman spectra, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, and scanning electron microscopy analyses. Further, the conjugation of FFG with Ag was confirmed by XRD, XPS, and energy-dispersive X-ray spectra. The Ag-FFG composite exhibited antibacterial activity against both Gram-positive and Gram-negative bacteria through the agar well diffusion method. This study provides an efficient, economical, and eco-friendly FFG and Ag-FFG production method for biomedical applications.

Electrohydrodynamics Analysis of Dielectric 2D Nanofluids.

The purpose of this present study is to prepare a stable mineral-oil (MO)-based nanofluid (NF) for usage as a coolant in a transformer. Nanoparticles (NPs) such as hexagonal boron nitride (h-BN) and titanium oxide (TiO2) have superior thermal and electrical characteristics. Their dispersion into MO is likely to elevate the electrothermal properties of NFs. Therefore, different batches of NFs are prepared by uniformly dispersing the insulating h-BN and semiconducting TiO2 NP of different concentrations in MO. Bulk h-BN NP of size 1µm is exfoliated into 2D nanosheets of size 150-200 nm, subsequently enhancing the surface area of exfoliated h-BN (Eh-BN). However, from the zeta-potential analysis, NP concentration of 0.01 and 0.1 wt.% are chosen for further study. The thermal conductivity and ACBDV studies of the prepared NF are performed to investigate the cooling and insulation characteristics. The charging-dynamics study verifies the enhancement in ACBDV of the Eh-BN NF. Weibull statistical analysis is carried out to obtain the maximum probability of ACBDV failure, and it is observed that 0.01 wt.% based NF has superior cooling and insulation properties than MO and remaining batches of NFs.

Synthesis, spectroscopic, and in vitro photosensitizing efficacy of ketobacteriochlorins derived from ring-B and ring-D reduced chlorins via pinacol-pinacolone rearrangement.

In this report, we present a regioselective oxidation of a series bacteriochlorins, which on reacting with either ferric chloride (FeCl(3)) or 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) yielded the corresponding ring-B or ring-D reduced chlorins. The effect of the number of electron-withdrawing groups present at the peripheral position, with or without a fused isocyclic ring (ring-E), did not make any significant difference in regioselective oxidation of the pyrrole rings. However, depending on the nature of substituents, the intermediate bis-dihydroxy bacteriochlorins on subjecting to pinacol-pinacolone reaction conditions gave various ketochlorins. The introduction of the keto-group at a particular position in the molecule possibly depends on the stability of the intermediate carbocation species. The newly synthesized bacteriochlorins show strong long-wavelength absorption and produced significant in vitro (Colon26 cells) photosensitizing ability. Among the compounds tested, the bacteriochlorins containing a keto-group at position 7 of ring-B with cleaved five-member isocyclic ring showed the best efficacy.

Novel methods to incorporate photosensitizers into nanocarriers for cancer treatment by photodynamic therapy.

OBJECTIVE: A hydrophobic photosensitizer, 2-[1-hexyloxyethyl]-2-devinyl pyropheophorbide-a (HPPH), was loaded into nontoxic biodegradable amine functionalized polyacrylamide (AFPAA) nanoparticles using three different methods (encapsulation, conjugation, and post-loading), forming a stable aqueous dispersion. Each formulation was characterized for physicochemical properties as well as for photodynamic performance so as to determine the most effective nanocarrier formulation containing HPPH for photodynamic therapy (PDT). MATERIALS AND METHODS: HPPH or HPPH-linked acrylamide was added into monomer mixture and polymerized in a microemulsion for encapsulation and conjugation, respectively. For post-loading, HPPH was added to an aqueous suspension of pre-formed nanoparticles. Those nanoparticles were tested for optical characteristics, dye loading, dye leaching, particle size, singlet oxygen production, dark toxicity, in vitro photodynamic cell killing, whole body fluorescence imaging and in vivo PDT. RESULTS: HPPH was successfully encapsulated, conjugated or post-loaded into the AFPAA nanoparticles. The resultant nanoparticles were spherical with a mean diameter of 29 ± 3 nm. The HPPH remained intact after entrapment and the HPPH leaching out of nanoparticles was negligible for all three formulations. The highest singlet oxygen production was achieved by the post-loaded formulation, which caused the highest phototoxicity in in vitro assays. No dark toxicity was observed. Post-loaded HPPH AFPAA nanoparticles were localized to tumors in a mouse colon carcinoma model, enabling fluorescence imaging, and producing a similar photodynamic tumor response to that of free HPPH in equivalent dose. CONCLUSIONS: Post-loading is the promising method for loading nanoparticles with hydrophobic photosensitizers to achieve effective in vitro and in vivo PDT.

Selenite bioreduction and biosynthesis of selenium nanoparticles by Bacillus paramycoides SP3 isolated from coal mine overburden leachate.

A native strain of Bacillus paramycoides isolated from the leachate of coal mine overburden rocks was investigated for its potential to produce selenium nanoparticles (SeNPs) by biogenic reduction of selenite, one of the most toxic forms of selenium. 16S rDNA sequencing was used to identify the bacterial strain (SP3). The SeNPs were characterized using spectroscopic (UV-Vis absorbance, dynamic light scattering, X-ray diffraction, and Raman), surface charge measurement (zeta potential), and ultramicroscopic (FESEM, EDX, FETEM) analyses. SP3 exhibited extremely high selenite tolerance (1000 mM) and reduced 10 mM selenite under 72 h to produce spherical monodisperse SeNPs with an average size of 149.1 ± 29 nm. FTIR analyses indicated exopolysaccharides coating the surface of SeNPs, which imparted a charge of -29.9 mV (zeta potential). The XRD and Raman spectra revealed the SeNPs to be amorphous. Furthermore, biochemical assays and microscopic studies suggest that selenite was reduced by membrane reductases. This study reports, for the first time, the reduction of selenite and biosynthesis of SeNPs by B. paramycoides, a recently discovered bacterium. The results suggest that B. paramycoides SP3 could be exploited for eco-friendly removal of selenite from contaminated sites with the concomitant biosynthesis of SeNPs.