A Peripheral-Free True Random Number Generator Based on Integrated Circuits Enabled by Atomically Thin Two-Dimensional Materials.

A true random number generator (TRNG) is essential to ensure information security for Internet of Things (IoT) edge devices. While pseudorandom number generators (PRNGs) have been instrumental, their deterministic nature limits their application in security-sensitive scenarios. In contrast, hardware-based TRNGs derived from physically unpredictable processes offer greater reliability. This study demonstrates a peripheral-free TRNG utilizing two cascaded three-stage inverters (TSIs) in conjunction with an XOR gate composed of monolayer molybdenum disulfide (MoS2) field-effect transistors (FETs) by exploiting the stochastic charge trapping and detrapping phenomena at and/or near the MoS2/dielectric interface. The entropy source passes the NIST SP800-90B tests with a minimum normalized entropy of 0.8780, while the generated bits pass the NIST SP800-22 randomness tests without any postprocessing. Moreover, the keys generated using these random bits are uncorrelated with near-ideal entropy, bit uniformity, and Hamming distances, exhibiting resilience against machine learning (ML) attacks, temperature variations, and supply bias fluctuations with a frugal energy expenditure of 30 pJ/bit. This approach offers an advantageous alternative to conventional silicon, memristive, and nanomaterial-based TRNGs as it obviates the need for extensive peripherals while harnessing the potential of atomically thin 2D materials in developing low-power TRNGs.

Biocompatible thermoresponsive N-isopropyl-N-(3-(isopropylamino)-3-oxopropyl)acrylamide-based random copolymer: synthesis and studies of its composition dependent properties and anticancer drug delivery efficiency.

A new acrylamide monomer, N-isopropyl-N-(3-(isopropylamino)-3-oxopropyl)acrylamide (M3i), consisting of both isopropyl and isopropylamidopropyl moieties, has been synthesized from isopropylamine and N-isopropylacrylamide via an aza-Michael addition reaction followed by amidation with acryloyl chloride. The homopolymer of M3i (polyM3i) and a series of random copolymers of M3i and poly(ethylene glycol)methyl ether acrylate (PEGA: CH2CHCO2(CH2CH2O)nMe, Mn = 480, n = 9 on average) with varying compositions have been synthesized via reversible addition-fragmentation chain transfer polymerization using 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) as well as 1-phenylethyl phenyl dithioacetate (PEPD) as a RAFT agent. These polymers have been characterized by 1H NMR, FTIR, GPC, UV-Vis, fluorescence, TGDTA, DSC, DLS, and TEM techniques. A lower critical solution temperature (LCST) and glass transition temperature (Tg) for polyM3i prepared using DDMAT were observed at 17 and 133 °C, respectively, while for a polymer formed using PEPD, no LCST was observed until 0 °C and its observed Tg was found at 127.3 °C. The polymers are thermally stable up to 300 °C. Upon an increase in the M3i content in the copolymers, LCST decreases, Tg increases, and the apparent hydrodynamic diameter decreases. Moreover, the effects of concentration and the addition of urea and sodium chloride on the LCST of the copolymer with an LCST close to body temperature were studied. Owing to the incorporation of PEGA, a higher critical micellar concentration and larger TEM particle size of this copolymer were observed with respect to those of polyM3i. The usefulness of the micelles of the copolymers as nano-carriers for the drug doxorubicin was explored. The in vitro tumoricidal activity of the micelles of the doxorubicin-loaded copolymers was also assessed against Dalton's lymphoma cells.

Functionalized polyurethane composite gel electrolyte with cosensitized photoanode for higher solar cell efficiency using a passivation layer.

Graphene oxide was chemically tagged with thermoplastic polyurethane, chain extended using butanediol to obtain the varying molecular weight of the polymer. Graphene-tagged polyurethane was functionalized using propane sultone to introduce the polar sulphonate groups in the main chain. The chain extension, tagging of GO and functionalization have been verified through spectroscopic techniques such as NMR, FTIR, UV and gel permeation chromatography. Thermal stability and the nature of the interaction were explored through thermal measurements to understand the effect of GO and functionalization. Electrical conduction was improved by the chemical attachment of graphene with the polymer (5.08 × 10-7 S cm-1), which further increases through functionalization and subsequent use of the additive (1.07 × 10-3 S cm-1) and make them suitable for gel electrolyte, being in the range of semiconductors. Quantum dots of CdS and CdSe were prepared using a capping agent and their characteristic properties and dimensions were worked out for their suitability as active materials in a solar cell. The optical band gap of quantum dots and HOMO/LUMO band structure of functionalized polyurethanes were measured using UV-vis and cyclic voltammetry, and thereby, constructing the overall energy diagrams for a possible combination of materials. Conducting carbon has been incorporated in the gel electrolyte to modulate the conductivity, while the ZnSe layer has been inserted as a passivation layer between the active material and the gel electrolyte. Solar cell devices were fabricated using the suitable materials, through the suitable energy diagram, and found a significantly high power conversion efficiency of 1.71%. The reason behind the improved efficiency is understood from the greater light harvesting behaviour, higher level of conductivity and blocking capacity of the various layered structures to reduce the electron-hole pair recombination.

Correction: Nanochannel conduction in piezoelectric polymeric membrane using swift heavy ions and nanoclay.

[This corrects the article DOI: 10.1039/C3RA23176C.].

Colorimetric detection of hydrogen peroxide and cholesterol using Fe3O4-brominated graphene nanocomposite.

Fe3O4-brominated graphene (Fe3O4-GBR) nanocomposites were synthesized via an in situ method using the precursors FeSO4.7H2O and GBR in different (1:1, 1:2, 2:1, 1:5, 1:10, 1:20, and 5:1) weight ratios at pH 11.5. The Fe3O4-GBR (1:5) nanocomposite in combination with H2O2 and 3,3',5,5'-tetramethylbenzidine (TMB) showed swift and superior intrinsic peroxidase mimetic enzyme activity compared with the other Fe3O4-GBR composites, GBR and Fe3O4, as observed by colorimetry. It was characterized using high-resolution scanning electron microscopy (HRSEM), energy dispersive X-ray spectroscopy (EDX), Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). Its catalytic activity was optimized by varying different parameters, and the optimum conditions for peroxidase mimetic activity were observed using 100 µL Fe3O4-GBR (1 mg/mL), 50 µL TMB (1 mg/mL), and 200 µL H2O2(1 mM) in 400 µL of acetate buffer of pH 2.3 at 30 °C temperature. Kinetic analysis has revealed the Michaelis-Menten kinetic behavior of peroxidase activity with Michaelis-Menten constants (Km) and maximum initial velocities (Vmax) of 0.082 mM and 14.1 nMs-1 respectively, for H2O2 and 0.086 mM and 5.1 nMs-1, respectively for TMB. The limit of detection and linear range were found to be 49.6 µM and 100-880 µM, respectively, for H2O2 and 41.9 µM and 47.6-952.3 µM, respectively, for cholesterol. On this basis, a simple, swift, sensitive, selective, and reproducible colorimetric assay to detect cholesterol levels in blood serum samples using Fe3O4-GBR nanocomposite has been developed. Thus, Fe3O4-GBR composite as compared to Fe3O4 and GBR has shown better peroxidase mimicking activity for biosensing.

Gelatin grafted poly(D,L-lactide) as an inhibitor of protein aggregation: An in vitro case study.

Amyloids are a group of proteins that are capable of forming aggregated amyloid fibrils, which is responsible for many neurodegenerative diseases including Alzheimer's disease (AD). In our previous study, synthesis and characterization of star-shaped poly(D,L-lactide)-b-gelatin (ss-pLG) have been reported. In the present work, we have extended our work to study ss-pLG against protein aggregation. To the best of our knowledge, this is the first report on the inhibition of amyloid fibrillation by protein grafted poly(D,L-lactide). Bovine serum albumin (BSA) was chosen as the model protein, which readily forms fibril under high temperature. We found that ss-pLG efficiently suppressed the fibril formation of BSA compared with gelatin (Gel), which was supported by Thioflavin T assay, circular dichroism (CD) spectroscopy and atomic force microscopy (AFM). In addition, ss-pLG significantly curtailed amyloid-induced hemolysis. We also found that incubation of ss-pLG with neuroblastoma cells (MC65) protected the cells from fibril-induced toxicity. The rescuing efficiency of ss-pLG was better than Gel, which could be attributed to the reduced lamella thickness in branched ss-pLG. These results suggest the significance of gelatin grafting, which probably allows gelatin to interact with the key residues of the amyloidogenic core of BSA effectively.

Doxorubicin loaded pH responsive biodegradable ABA-type Amphiphilic PEG-b-aliphatic Polyketal-b-PEG block copolymer for therapy against aggressive murine lymphoma.

A novel ABA-type polyethylene glycol (PEG)-b-polyketal (PK)-b-PEG block copolymer was synthesized via click reactions between the monoazido-monomethoxy-PEG and dialkyne terminated aliphatic polyketal with no carboxylic/amide linkages. Formation of the novel block copolymer was confirmed by 1H NMR, GPC, TGA, and DSC studies. The formed copolymer has shown faster degradation at acidic pH. Self-assembly of this block copolymer (average size 6.2 nm) was assessed by fluorescence study using pyrene as a probe. Doxorubicin loaded block copolymeric micelles (69.9 nm) have shown pH dependent elevated drug release at pH 6.4, indicating its potential as a pH responsive nano-carrier for anticancer therapy. The nano-sized copolymer demonstrated tumoricidal activities against the lymphoma of murine and human origin with significant levels of growth inhibition and apoptosis. Therapy with doxorubicin loaded copolymer reduced the tumor size and augmented the life span of the tumor bearing animals with improved histopathological parameters, compared with the untreated control.

Highly selective fluorescence 'turn off' sensing of picric acid and efficient cell labelling by water-soluble luminescent anthracene-bridged poly(N-vinyl pyrrolidone).

A novel, water-soluble, luminescent anthracene-bridged AA-type bi-arm poly(N-vinylpyrrolidone) (ATC-PNVP) was synthesized using a click reaction between alkyne-terminated PNVP and 9,10-bis(azidomethyl)anthracene. The resultant anthracene-bridged PNVP (ATC-PNVP) was characterized using 1H NMR, FTIR, UV-Vis, and fluorescence spectroscopic methods and GPC analysis. ATC-PNVP showed effective fluorescence properties in an aqueous medium. It showed highly selective "turn off" sensing behaviour towards picric acid, a common nitro-aromatic explosive, with a wide linear range of detection of 0.01-0.3 mM and LOD value of 0.006 mM in water. ATC-PNVP-based paper sensors also showed very effective detection of picric acid in the concentration range 0.001-1.0 mM. Its binding with bovine serum albumin (BSA) was studied using steady-state, synchronous and 3D fluorescence spectroscopy and this study showed effective quenching of the intrinsic fluorescence of BSA and occurrence of a FRET-type interaction. Furthermore, this luminescent ATC-PNVP was efficiently used as a fluorescence microscopy labelling agent in NIH-3T3 and HeLa cells, and showed greater uptake and hence better fluorescent labelling in the cytosols of the tested cells than free 9,10-bis(azidomethyl) anthracene. The cell viability study also showed a very good biocompatible and non-toxic nature of ATC-PNVP at lower working concentrations towards each of the types of cells tested.

Fluorescent-functionalized graphene oxide for selective labeling of tumor cells.

Fluorescence probe has attracted significant attention for biomedical imaging in recent years due to their high resolution at the cellular level. Organic-based fluorescent probes with high quantum yield are widely applied in bioimaging, but most of them suffer from a serious obstacle called aggregation-caused quenching in cellular systems. New fluorophore has been designed through functionalization of graphene oxide which emphatically exhibits aggregation-induced emission along with pH-responsive nanoprobe. Significantly higher emission of this material in slightly acidic media helps to detect tumor cell by creating a sharp contrast with the image of normal cells. The reason for pH-induced enhanced emission phenomenon is revealed through aggregation of sulfonated species in acidic media. Furthermore, the biocompatible nature of the newly developed material is found to be suitable for its application in biomedical imaging for cancer detection with better accuracy at lower cost. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 107A: 1917-1924, 2019.

Efficacy of polyurethane graft on cyclodextrin to control drug release for tumor treatment.

Hydrophilicity of cyclodextrin is controlled through grafting of polyurethane of varying graft density, thereby maintain the hydrophilic-hydrophobic balance, to sustain the drug delivery rate for better tumor treatment. Grafting is verified through nuclear magnetic resonance (1H NMR) and other spectroscopic techniques along with the hydrodynamic volume measurement of grafted species and the degree of substitution has been calculated from the integrated peak areas. Thermal and mechanical stability of the graft copolymers have improved significantly with respect to cyclodextrin and the formation of smaller blobs having larger in number has been obtained from small angle neutron scattering, atomic force microscopy and optical images. Sustained drug delivery has been achieved using graft copolymer as opposed to burst release in pure cyclodextrin and polyurethane and the phenomenon is understood from the specific interactions, as observed though spectroscopic and thermal measurement, between graft copolymer and drug followed by this novel architecture of the graft copolymers. Biocompatibility of graft copolymers has been checked using cellular studies through 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and cell adhesion. Importantly, the cell killing efficiency has been demonstrated by embedding anti-cancer drug in polymer matrices causing mortality rate of 80% using graft copolymer against meagre 20% using pure drug or drug embedded in cyclodextrin and the result is realised from the sustained release of drug from the graft copolymer vis-à-vis burst release in other systems. Cellular studies have been translated into an animal model showing the efficacy of newly developed patch, made of drug embedded in copolymer, towards the significant suppression of tumors in mice as compared to control. Histopathological images and biochemical parameters indicate the normal body organ/blood in copolymer treated mice against severely damaged organ especially liver/blood in the mice treated with pure drug or drug embedded in cyclodextrin arising from burst release. Thus, graft copolymer with unique architecture is found to be an effective drug delivery vehicle for melanoma cancer treatment without side effect.

Grafted cyclodextrin as carrier for control drug delivery and efficient cell killing.

The presence of hydroxyl groups in cyclodextrin (CD) makes it highly hydrophilic and simultaneously allows its chemical modification to graft polyurethane to control the drug release for longer period of time by maintaining the hydrophobic-hydrophilic balance through varying extent of grafting. Grafting of polyurethane on CD is confirmed through 1 H NMR and molecular weight measurement while FTIR and UV visible studies further support grafting and emphasize the interaction among polymer chains as a whole. Degree of grafting is evaluated from the integrated peak area in NMR spectra. Thermal and mechanical measurements show improved stability and strength of the graft polymers with respect to pure CD. The conversion of particle nature of CD to strip-like morphology in graft copolymers is evident from atomic force microscopy. Sustained drug release has been achieved using graft copolymer against burst release from pure CD and specific interactions, as observed through spectroscopy and thermal measurements, are responsible for sustained release of drug. Biocompatibility of graft copolymers has been checked using cellular studies through MTT assay and cell adhesion. Importantly, the cell killing efficiency has been demonstrated by embedding anticancer drug in polymer matrices causing mortality rate of 75% using graft copolymer against scanty 25% using pure drug or drug embedded in CD and the result is understood from the sustained release of drug from the graft copolymer vis-à-vis burst release in other systems. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 107A: 434-444, 2019.

Cell proliferation influenced by matrix compliance of gelatin grafted poly(d,l-Lactide) three dimensional scaffolds.

Surface and mechanical properties of the biomaterials are determinants of cellular responses. In our previous study, star-shaped poly(d,l-Lactide)-b-gelatin (ss-pLG) was reported for possessing improved cellular adhesion and proliferation. Here, we extended our investigation to establish the cellular compatibility of gelatin-grafted PDLLA with respect to mechanical properties of biological tissues. In this view, linear PDLLA-b-gelatin (l-pLG) was synthesized and tissue-level compatibility of 1-pLG and ss-pLG against fibroblasts (L929), myoblasts (C2C12) and preosteoblasts (MG-63) was examined. The cell proliferation of C2C12 was significantly higher within l-pLG scaffolds, whereas L929 showed intensified growth within ss-pLG scaffolds. The difference in cell proliferation may be attributed to the varying mechanical properties of scaffolds; where the stiffness of l-pLG scaffolds was notably higher than ss-pLG scaffolds, most likely due to the variable levels of gelatin grafting on the backbone of PDLLA. Therefore, gelatin grafting can be used to modulate mechanical property of the scaffolds and this study reveals the significance of the matrix stiffness to produce the successful 3D scaffolds for tissue engineering applications.

Osteoconductive Amine-Functionalized Graphene-Poly(methyl methacrylate) Bone Cement Composite with Controlled Exothermic Polymerization.

Bone cement has found extensive usage in joint arthroplasty over the last 50 years; still, the development of bone cement with essential properties such as high fatigue resistance, lower exothermic temperature, and bioactivity has been an unsolved problem. In our present work, we have addressed all of the mentioned shortcomings of bone cement by reinforcing it with graphene (GR), graphene oxide (GO), and surface-modified amino graphene (AG) fillers. These nanocomposites have shown hypsochromic shifts, suggesting strong interactions between the filler material and the polymer matrix. AG-based nanohybrids have shown greater osteointegration and lower cytotoxicity compared to other nanohybrids as well as pristine bone cement. They have also reduced oxidative stress on cells, resulting in calcification within 20 days of the implantation of nanohybrids into the rabbits. They have significantly reduced the exothermic curing temperature to body temperature and increased the setting time to facilitate practitioners, suggesting that reaction temperature and settling time can be dynamically controlled by varying the concentration of the filler. Thermal stability and enhanced mechanical properties have been achieved in nanohybrids vis-à-vis pure bone cement. Thus, this newly developed nanocomposite can create natural bonding with bone tissues for improved bioactivity, longer sustainability, and better strength in the prosthesis.

Controlled drug release through regulated biodegradation of poly(lactic acid) using inorganic salts.

Biodegradation rate of poly(lactic acid) (PLA) has been regulated, both increase and decrease with respect to the biodegradation of pure PLA, by embedding meager amount of inorganic salts in polymer matrix. Biodegradation is performed in enzyme medium on suspension and film and the extent of biodegradation is measured through spectroscopic technique which is also verified by weight loss measurement. Media pH has been controlled using trace amount of inorganic salt which eventually control the biodegradation of PLA. High performance liquid chromatography confirms the hydrolytic degradation of PLA to its monomer/oligomer. Induced pH by metal salts show maximum degradation at alkaline range (with calcium salt) while inhibition is observed in acidic medium (with iron salt). The pH of media changes the conformation of enzyme which in turn regulate the rate of biodegradation. Thermal degradation and increment of modulus indicate improvement in thermo-mechanical properties of PLA in presence of inorganic salts. Functional stability of enzyme with metal salts corresponding to acidic and alkaline pH has been established through a model to explain the conformational changes of the active sites of enzyme at varying pH influencing the rate of hydrolysis leading to regulated biodegradation of PLA. The tuned biodegradation has been applied for the controlled release of drug from the polymer matrix (both sustained and enhanced cumulative release as compared to pure polymer). The cell proliferation and adhesion are influenced by the acidic and basic nature of polymeric material tuned by two different inorganic salts showing better adhesion and proliferation in calcium based composite and, therefore, suggest biological use of these composites in biomedical applications.

Tailored Chemical Properties of 4-Arm Star Shaped Poly(d,l-lactide) as Cell Adhesive Three-Dimensional Scaffolds.

Biodegradable poly(lactic acid) (PLA) is widely used to fabricate 3D scaffolds for tissue regeneration. However, PLA lacks cell adhering functional moieties, which limit its successful application in tissue engineering. Herein, we have tailored the cell adhesive properties of star shaped poly(d,l-lactide) (ss-PDLLA) by grafting gelatin to their 4 arms. Grafting of gelatin on PDLLA backbone was confirmed by 1H NMR and FTIR. The synthesized star shaped poly(d,l-lactide)-b-gelatin (ss-pLG) exhibited enhanced wettability and protein adsorption. The modification also facilitated better cell adhesion and proliferation on their respective polymer coated 2D substrates, compared to their respective unmodified ss-PDLLA. Further, 3D scaffolds were fabricated from gelatin grafted and unmodified polymers. The fabricated scaffolds were shown to be cytocompatible to 3T3-L1 cells and hemocompatible to red blood cells (RBCs). Cell proliferation was increased up to 2.5-fold in ss-pLG scaffolds compared to ss-PDLLA scaffolds. Furthermore, a significant increase in cell number reveals a high degree of infiltration of cells into the scaffolds, forming a viable and healthy 3D interconnected cell community. In addition to that, burst release of docetaxal (DTX) was observed from ss-pLG scaffolds. Hence, this new system of grafting polymers followed by fabricating 3D scaffolds could be utilized as a successful approach in a variety of applications where cell-containing depots are used.

Functionalized Graphene Tagged Polyurethanes for Corrosion Inhibitor and Sustained Drug Delivery.

Surface functionalization of graphene oxide with sulfonate group and subsequent grafting with polyurethane chains leads to the significant improvement in the properties of polymer and modified graphene as a filler. Modification of graphene oxide is revealed through spectroscopy while grafting of polymer chain over sulfonated graphene is confirmed through 1H NMR and other techniques. Higher order of self-assembly phenomena is observed in nanohybrids as compared to pure polymer through greater interaction between polymer chain and sulfonated graphene. Significant improvement in corrosion inhibition phenomena is observed using nanohybrids at low concentration as compared to pure polymer indicating its superior efficiency as a corrosion inhibitor. Nanohybrids also exhibit better biocompatible nature in lower concentration of filler with considerable sustained release of drug vis-à-vis pure polymer suggest its potential to use as a biomaterial for tissue engineering applications.

Brominated Graphene as Mimetic Peroxidase for Sulfide Ion Recognition.

Brominated graphene (GBR) with ∼3% bromine content has shown novel peroxidase mimetic activity toward 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Optimum activity has been observed at pH 4.48 and after a minimum ∼30 min of equilibration time. Among the different analytes studied using the sensor combining TMB, H2O2, and GBR in phosphate buffer of pH 4.48, the S2- ion has effectively shown a short duration of sensing (∼2 min) within the detection range of 0.04-1 mM. A calibration curve for S2- ion estimation has been constructed with the experimental linearity in 0.04-0.4 mM range and having the limit of detection (LOD) value of 25.3 µM. A standard addition experiment has validated the method. A paper strip sensor has been fabricated for successful detection of S2- ion.

Study of the Fluorescence Based Applications of Pyrene-Tagged Poly(N-vinyl-2-pyrrolidone).

In this study we have explored the fluorescence based applications of luminescent pyrene-tagged PNVP (PyPNVP) reported in our previous work (Int. J. Polym. Mater. Polym. Biomater. 2016, 65, 269-276). PyPNVP has successfully acted as "turn off" chemosensor for metal ions Cu2+, Hg2+, and Pb2+. It has also successfully acted as a fluorescent probe for critical micellar concentration (CMC) determination of amphiphilic block copolymer of poly(d,l-lactide) and poly(N-vinylpyrrolidone) (PDLLA42-b-PNVP120) (Mn = 19 400 g/mol and PD = 1.52). It has also successfully shown an interaction with both plasmid and calf thymus (CT) deoxyribonucleic acids (DNAs) as evidenced by its fluorescence quenching. A different magnitude and type of quenching has been observed for both the cases which may be useful in distinguishing different kinds of DNAs. In order to further understand the potential of PyPNVP in various biotechnological processes, its binding property with bovine serum albumin (BSA) has also been studied. The efficient quenching of intrinsic fluorescence of BSA by PyPNVP through binding and the occurrence of the fluorescence resonance energy transfer (FRET) type of interaction have been studied using steady state, synchronous, and 3D fluorescence spectroscopies. Moreover, a fluorescence microscopic cell imaging study has revealed the significant uptake of PyPNVP in the nucleus of HEPG2 and U87 cells compared to free Py. In addition, the cytotoxicity study showed the tolerance of PyPNVP in all the cell lines tested with no significant cytotoxicity at lower concentrations.

Methotrexate-Loaded Four-Arm Star Amphiphilic Block Copolymer Elicits CD8+ T Cell Response against a Highly Aggressive and Metastatic Experimental Lymphoma.

We have synthesized a well-defined four-arm star amphiphilic block copolymer [poly(DLLA)-b-poly(NVP)]4 [star-(PDLLA-b-PNVP)4] that consists of D,L-lactide (DLLA) and N-vinylpyrrolidone (NVP) via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesis of the polymer was verified by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic four-arm star block copolymer forms spherical micelles in water as demonstrated by transmission electron microscopy (TEM) and 1H NMR spectroscopy. Pyrene acts as a probe to ascertain the critical micellar concentration (cmc) by using fluorescence spectroscopy. Methotrexate (MTX)-loaded polymeric micelles of star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer were prepared and characterized by fluorescence and TEM studies. Star-(PDLLA15-b-PNVP10)4 copolymer was found to be significantly effective with respect to inhibition of proliferation and lysis of human and murine lymphoma cells. The amphiphilic block copolymer causes cell death in parental and MTX-resistant Dalton lymphoma (DL) and Raji cells. The formulation does not cause hemolysis in red blood cells and is tolerant to lymphocytes compared to free MTX. Therapy with MTX-loaded star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer micelles prolongs the life span of animals with neoplasia by reducing the tumor load, preventing metastasis and augmenting CD8+ T cell-mediated adaptive immune responses.

Collection-limited theory interprets the extraordinary response of single semiconductor organic solar cells.

The bulk heterojunction (BHJ) organic photovoltaic (OPV) architecture has dominated the literature due to its ability to be implemented in devices with relatively high efficiency values. However, a simpler device architecture based on a single organic semiconductor (SS-OPV) offers several advantages: it obviates the need to control the highly system-dependent nanoscale BHJ morphology, and therefore, would allow the use of broader range of organic semiconductors. Unfortunately, the photocurrent in standard SS-OPV devices is typically very low, which generally is attributed to inefficient charge separation of the photogenerated excitons. Here we show that the short-circuit current density from SS-OPV devices can be enhanced significantly (∼100-fold) through the use of inverted device configurations, relative to a standard OPV device architecture. This result suggests that charge generation may not be the performance bottleneck in OPV device operation. Instead, poor charge collection, caused by defect-induced electric field screening, is most likely the primary performance bottleneck in regular-geometry SS-OPV cells. We justify this hypothesis by: (i) detailed numerical simulations, (ii) electrical characterization experiments of functional SS-OPV devices using multiple polymers as active layer materials, and (iii) impedance spectroscopy measurements. Furthermore, we show that the collection-limited photocurrent theory consistently interprets typical characteristics of regular SS-OPV devices. These insights should encourage the design and OPV implementation of high-purity, high-mobility polymers, and other soft materials that have shown promise in organic field-effect transistor applications, but have not performed well in BHJ OPV devices, wherein they adopt less-than-ideal nanostructures when blended with electron-accepting materials.